TRANSACTIONS

CONNECTICUT ACADEMY
OF

ARTS AND SCIENCES.

VOX^XJJVIE III

t7>

NEW

AYEN

PUBLISHED BY THE ACADEMY,

1874
TulUr, Murehouse

to 1878.

Taylor, Printers,

New Ha

CONTENTS.
PAGE

List of Additions to the Library,..,.

Art.

I.

Report

on the dredgings

By

George's Banks, in 1872.

H arger.

Plates

Art. IL Descriptions
DROIDS from the

the region of

S.

Smith and O.

I.

-8,

op

new and rare

NeW EnGLAND

species of Hy-

By

COAST.

S.

F,

58

On the Chondrodite from the

III.

St.

Plates 9-10,

Clark.
Art.

in

By

IRON mine, Brewster, N. Y,

E. S.

Tilly-Foster

Dana,

Plates

11-13,

67

Art. IV.

sin

ic

On the Transcendental curves sin y sin iny=.

By II. A. Newton and A. W.
sin ??a; -|^''-

Philips.

Art.

Plates 14-37,

On the

V.

97

equilibrium of heterogeneous sub-

By J. W. Gibbs. First Part,

The Hydroids of the Pacific coast of the
United States south of Vancouver Island, with a
report upon those in the Museum of Yale Coixege.

108

By

249

stances.

Art. VI.

S.

F. Clark.

By

Y.

Plates 38-41,

On the anatomy and

Art. VII.

M, Turnbull.

Art. VIII.

habits of Nereis virens.

Plates 42-44,

Median and paired

the history of vertebrate

265

fins, a contribution to

limbs.

By

J.

Plates 49-60,

K. Thacher,
281

Early stages op Hippa talpoida, with a note

ON THE structure OF THE MANDIBLES AND MAXILLJE IN
Hipp A and Remipes. By S. I. Smith. Plates 45-48, 311
Art. X.
On the equilibrium op heterogeneous sub-

Art. IX.

stances (concluded).

By

J.

W.

Gibbs,

343

OFFICERS OF THE ACADEMY.

President,

ELIAS LOOMIS.

Vice-President,

HUBERT

NEWTON.

A.

/Secretary,

OSCAR HARGER.

Librarian,

ADDISON VAN NAME.

Treasurer,

HENRY

KINGSLEY.

C.

PtihlisJdng Committee,

HUBERT
GEORGE
CHESTER

A.
J.
S.

NEWTON,

ELIAS LOOMIS,
E. VERRILL,

ADDISON
WILLIAM

BRUSH,

LYMAN,

D.

WHITNEY.

Auditiiig Committee,

HUBERT

A.

NEWTON,

HENRY

T.

DANIEL
BLAKE.

C.

EATON,

V. On the Equilibrium of Heterogeneous Substances.

Bt J. WlLLARD GiBBS.
" Die Energie der Welt ist constant.
Die Entropie der Welt strebt einera

Maximum zu."
CLAfsitrs.*

The comprehension

of the laws which govern any material system

by considering the energy and entropy of the

system in the various states of which it is capable. As the difference
of the values of the energy for any two states represents the combined amount of work and heat received or yielded by the system
when it is brought from one state to the other, and the difference of

is

greatly facilitated

entropy

is

the limit of

[dQ denoting
and

all

the possible values of the integral

/
,

the element of the heat received from external sources,

the temperature of the part of the system receiving

varying values of the energy and entropy characterize

essential the effects producible

by the system

in

it,)

the

that

in all

is

passing from one

For by mechanical and theiTuodynamic conany supply of work and

heat may be transformed into any other which does not differ from
it either in the amount of work and heat taken together or in the
state

to

another.

trivances, supposed

theoretically perfect,

value of the integral /

But

it

external relations of a system that

predominant importance.

As

is

its

not only in respect to the

energy and entropy

in the case of

ai'e

of

simply mechanical sys-

tems, (such as are discussed in theoretical mechanics,) which are capable

of only one kind of action upon external systems,

viz.,

the perform-

ance of mechanical work, the function which expresses the capability

of the system for this kind of action also plays the leading part in

the theory of equilibrium, the condition of equilibrium being that

the variation of this function shall vanish, so in a thermodynamic

system, (such as

two

all

material systems actually are,) which

different kinds of action

is

capable of

upon external systems, the two functions

which express the twofold capabilities of the system afford an almost

equally simple criterion of equilibrium.
*Pogg. Ann. Bd. cxxv (1865),

S.

400; or Mechanische Warmetheorie, Abhand.

ix., S.

44.

W. Gihhs

J.

Equilibrium of Hetexogeneous Substances.

109

CRITERIA OF EQUILIBRIUM AND STABILITY.

The
from

system which

criterion of equilibi-ium for a material

all

external influences

may

is

isohited

be expressed in either of the follow-

ing entirely equivalent forms

I.

For

of any isolated system

the equilibrium

it

and

necessary

is

sufficient that in all possible variations

of the state of the system

which do not alter its energy, the va.riatio7i of its entropy shall either
vanish or be negative. If a denote the energy, and // the entropy of
the system, and we use a subscript letter after, a variation to indicate
a quantity of which the value is not to be varied, the condition of
equilibrium

may be

written
{^V)e ^0.

II.

For

the equilibrium

of any isolated system

sufficient that in all possible

which do not

(1)

variations in

alter its entropy, the variation

vanish or be positive.

This condition

m,=

may

it

is

of

its

the system

energy shall either

be written
(2)

appear from the conalways possible to increase both the energy and
will

the entropy of the system, or to decrease both together,

imparting heat to any part of the system or by taking

if

condition (1)

state of the

is

system in

viz.,

away.

it

by

For,

not satisfied, there must be some variation in the

system for which

S}j

therefore,

and

necessary

of

0.

That these two theorems are equivalent

sideration that

it is

the state

>

and 6e

=0;

by diminishing both the energy and the entropy of the

its varied state, we shall obtain a state for which (considered

as a variation

from the original

state)

dTf=iO and d"<0;

therefore condition (2)
is

is

not satisfied.

Conversely,

if

condition (2)

not satisfied, there must be a variation in the state of the system

for

which

d<

and St/z^ 0;

hence there must also be one for which

de=iO and
therefore condition (1)

is

not

(J//

>

satisfied.

The equations which express the condition

its

statement in words, are to be interpreted

of equilibrium, as also
in

accordance with the

general usage in respect to difterential equations, that

is,

infinitesimals

110

tf.

W. Gibbs Equilibrium of Heterogeneous

of higher orders than the

fii-st

relatively to tliose

amount of change of the system

Substances.

which express the

But to distin-

are to be neglected.

guish the different kinds of equilibrium in respect to stability,

must have regard to the absolute values of the

use

We

variations.

we
will

as the sign of variation in those equations which are to be con-

strued strictly,

i.

e.,

which infinitesimals of the higher orders are

in

With

this understanding, we may express the

necessary and sufficient conditions of the different kinds of equilibrium as follows; for stable equilil)rium

not to be neglected.

(^;/),<0,
for neutral equilibrium there

i.

e.,

(A6),^>0:

(3)

must be some variations

in

the state of

the system for which

(A//)^

0,

i.

e., {Af),^

0,

(4)

while in general
{^V)e ^0,

and

i.e.,

for unstable equilibrium there

(Af),^^0;

(5)

must be some variations

for

which

(A;/),>0,
i.

e.,

there must be

some

for

(6)

which

(^f),<0,

(V)

while in general

(d7),^0,i.e., (c^f),^0.

(8)

In these criteria of equilibrium and stability, account

oi })ossible variations.
to be understood.

It is

In the

is

taken only

necessary to explain in what sense

first place, all

tliis is

variations in the state of

the system which involve the transportation of any matter through

any

finite

distance are of course to be excluded from consideration,

although they

may

tions of quantities

For example,

if

be capable of expression by infinitesimal varia-

which perfectly determine the state of the system.

the system contains

stance, not in contact, nor connected

or containing the same substance or

two masses of the same subby other masses consisting of

its

components, an infinitesimal

increase of the one mass with an equal decrease of the other

be considered as a possible variation

is

not to

in the state of the system.

addition to such cases of essential impossibility,

if

In

heat can pass by

conduction or radiation from every part of the system to every other,

only those variations are to be rejected as impossible, which involve

changes which are prevented by passive forces or analogous

ances to change.
there

is

But,

if

resist-

the system consist of parts between which

supposed to be no thermal communication,

it

will

be neces-

sary to regard as impossible any diminution of the entropy of any of

J.

W. Gihhs

Equilihrium of Heterogeneous Substances.

Ill

these parts, as sueli a change can not take place without the passage

This limitation may most conveniently l>e aiplied to the

second of the above forms of the condition of equilibrium, which will
of heat.

then become

ri\ ?/', etc.,

there

is

denoting the entropies of the various parts between which

no communication of heat.

When

the condition of equi-

librium is thus expressed, the limitation in respect to the

of heat will need

conduction

no farther consideration.

In order to apply to any system the criteria of equilibrium which

have been given, a knowledge

is

requisite of its passive forces or

resistances to change, in so far, at least, as they are capable of pre-

(Those passive forces which only retard change,

Such properties of a system
like viscosity, need not be considered.)

venting change.

ai-e in

general easily recognized upon the most superficial knowledge

of

nature.

its

friction

As examples, we may instance the passive force of

which prevents sliding when two surfaces of solids are

pressed together,

that which

prevents the different components of

from having different motions one

which sometimes prevents
either of two forms of the same substance (simple or compound),
which are capable of existing, from passing into the other, that
which prevents the changes in solids which imply plasticity, (in other
words, changes of the form to which the solid tends to return,) when
a solid, and sometimes of a

from another,

that

fluid,

resistance to change

the deformation does not exceed certain limits.

It is a characteristic of all these passive resistances

vent a certain kind of motion or change, however the

that they preinitial state

of

may be modified, and to whatever external agencies of force

it may be subjected, within limits, it may be, but yet within

the system

and heat
which allow finite variations in the values of all the quantities which express the initial state of the system or the mechanical
or thermal influences acting on it, without producing the change in
The equilibi-ium which is due to such passive properties
question.
limits

is

thus widely distinguished from that caused

by the balance

of the

where an external influence, or a

change in the initial state, infinitesimal in amount, is sufficient to produce change either in the positive or negative direction. Hence the
Only in
ease with which these passive resistances are recognized.
the case that the state of the system lies so near the limit at which

active tendencies of the system,

the resistances cease to be operative to ])revent change, as to create a

112

J.

W. Gihhs

EqniUbrlum of Heterhgeneotis Substances.

doubt whether the case

within or without the limit, will a more

falls

accurate knowledge of these resistances be necessary.

To

establish the validity of the criterion of equilibrium,

consider

first

dition as expressed in either of the

In the

first

we

place,

if

the system

two equivalent

is in

forms.

a state in which

greater than in any other state of the same energy,

equilibrium, as any change of state

must involve

its

it is

entropy

We may add that

lated system.

either a decrease of

change of

any external bodies) can produce a

state, as this Avould

iso-

this is a case of stable equilibrium, as

(whether relating to a variation of the

infinitely small cause

state or to the action of

is

evidently in

entropy or an increase of energy, which are alike impossible for an

no

will

the sufficiency, and afterwards the necessity, of the con-

initial
finite

involve a finite decrease of entropy or

increase of energy.

We

will next suppose that the

consistent with

with

its

its

system has the greatest entropy

energy, and therefore the least energy consistent

entropy, but that there are other states of the same energy

and entropy as its actual state. In this case, it is impossible that

any motion of masses should take place for if any of the energy
of the system should come to consist of vis viva (of sensible motions),
a state of the system identical in other respects but without the
motion would have less energy and not less entropy, which would be
;

(But we cannot apply this reasoning to

contrary to the supposition,

the motion within any mass of

directions, as

in

balance one another.)

its

Avhen

difiiision,

Nor,

difierent

the

components

momenta

in the case supposed,

in diiferent

of the components

can any conduction

of heat take place, for this involves an increase of entropy, as heat

is

only conducted from bodies of higher to those of lower temperatiire.

It is

l)e produced by the

The condition which we have sup-

equally impossible that any changes should

transfer of heat

posed

is

by

radiation.

therefore sufficient for equilibrium, so far as the motion of

masses and the transfer of heat are concerned, but to show that the
same is true in regard to the motions of difiiision and chemical or
molecular changes, when these can occur without being accompanied
or followed

by the motions

of masses or the transfer of heat,

we must

have recourse to considerations of a more general nature. The following considerations seem to justify the belief that the condition is
sufficient for equilibrium in

every respect.

Let us suppose, in order to test the tenability of such a hypothesis,

that a system may have the greatest entropy consistent with its
energy without being

in equilibrium.

In sucli a case, changes in the

J.

W. Gibhs

Equilibrinm of Heterogeneous Substances.

113

system must take place, but these will necessarily be

such that the energy and the entropy will remain unchanged and
the system will continue to satisfy the same condition, as initially, of
having the greatest entropy consistent with its energy. Let us constate of the

change which takes place

change may be regarded as uniform
sider the

in

any time so short that the

throughout that time.

in nature

This time must be so chosen that the change does not take place in
infinitely slowly,

which

is

it

always easy, as the change which we sup-

pose to take place cannot be infinitely slow except at particular

moments. Now no change whatever in the state of the system,

and which commences

which the system was supposed at the com-

w^hich does not alter the value of the energy,

with the same state

in

short time considered, will cause an increase of

Hence, it will generally be possible by some slight varia-

mencement of the
entropy.

tion in the circumstances of the case to

make

of the system like or nearly like that which

all

is

changes

in the state

supposed actually to

occur, and not involving a change of energy, to involve a necessary

decrease of entropy, which would render any such change impossible.

be in the values of the variables which determine

the state of the system, or in the values of the constants which determine the nature of the system, or in the form of the functions which
express its laws, only there must be nothing in tbe system as modiThis variation

may

fied

which

is

For example, we might

thermodynamically impossible.

suppose temperature or pressure to be varied, or the composition of

the difierent bodies in the system, or,

no small variations which

if

could be actually realized would produce the required result,

we

might suppose the properties themselves of the substances to undergo

variation, subject to the general laws of matter.

any tendency toward change in the system as

tendency which can be entirely checked by an
in

As

the circumstances of the case.

first

has the greatest entropy consistent with

when

it

is

in

its

will evidently

its

not the least of which the system

is

entropy.

apply to any case in which

such a state that -^//^O for any possible

imal variation of the state for which A

be

energy, or, in

has the least energy consistent with

The same considerations

a system

is

always in equilibrium

when

believe that a system

is

it is

this supposition cannot

we must

it

then, there

supposed,

infinitesimal variation

allowed,

other words,

If,

0,

even

if

infinites-

the entropy

is

capable with the same energy.

(The term possible has here the meaning pi-eviously defined, and the
character A is used, as before, to denote that the equations are to be
Trans. Conn. Acad., Vol.

III.

15

October, 1875.

114

ff.

W. Gibbs

construed

Equilibrium of Heterogeneous Substances.

sti'ictly,

i.

e.,

without neglect of the infinitesimals of the

higher orders.)

The only

case in which the sufficiency of the condition of equi-

librium which has been given remains to be proved

in

our notation

6ij

is

that in which

for all possible variations not affecting the

energy, but for some of these variations A;;>.0, that

when

is,

the

some respects the characteristics of a minimum. In

this case the considerations adduced in the last paragraph will not
apply without modification, as the change of state may be infinitely
slow at first, and it is only in the initial state that the condition
But the differential coefficients of all orders of
(Jz/p^O holds true.
the quantities which determine the state of the system, taken with
respect of the time, must be functions of these same quantities.
None of these differential coefficients can have any value other than
For otherwise, as
0, for the state of the system for which dr]^ ^ 0.
be
possible,
before,
infinitely small
would
generally
as
some
it
by
modification of the case, to render impossible any change like or nearly
like that which might be supposed to occur, this infinitely small
modification of the case would make a finite difference in the value
of the differential coefficients which had before the finite values, or
in some of lower orders, Avhich is contrary to that continuity which
we have reason to expect. Such considerations seem to justify us
entropy has

in

in

regarding such a state as

equilibrium

we

are discussing as one of theoretical

although as the equilibrium

is

evidently unstable,

it

cannot be realized.

We

have

still

to prove that the condition enunciated

case necessary for equilibrium.

It

is

evidently so in

is

in

every

cases in

all

which the active tendencies of the system are so balanced that

changes of every kind, except those excluded

in the

the condition of equilibrium, can take place reversibly,

statement of
(i.

e.,

both

in

the positive and the negative direction,) in states of the system differing infinitely little from the state in question.

may omit

In this case,

we

the sign of inequality and write as the condition of such a

state of equilibrium
((J;/),

But

0,

i.e.,

to prove that the condition

(rJ6),

previously enunciated

(10)
is

in every

must be shown that whenever an isolated system

remains without change, if there is any infinitesimal variation in its
state, not involving a finite change of position of any (even an infinitesimal part) of its matter, which would diminish its energy by a
case necessary,

it

Gihhs

J. TF,

quantity which

EqtiiUhrinm

of Heterogeneons Svhstwtces.

115

not infinitely small relatively to the variations

is

of the quantities which determine the state of the system, without

altering

its

without

or,

entropy,

altering

the

if

the system has thermally isolated parts,

entroi)y

of

any such part,

this

involves changes in the system which are pi*evented by

forces or analogous resistances

to

Now,

change.

variation in the state of the system diminishes

variation
its

passive

as the described

its

energy without

must be regarded as theoretically possible to

produce that variation by some process, perhaps a very indirect one,
so as to gain a certain amount of work (above all expended on the
Hence we may conclude that the active forces or tendensystem).
cies of the system favor the variation in question, and that equilibrium cannot subsist unless the variation is prevented by passive
altering its entropy,

it

forces.

The preceding considerations

will suffice,

it is

believed, to establish

the validity of the criterion of equilibrium which has been given.

The

criteria of stability

We

librium.

will

may

readily be deduced from that of equi-

now proceed

to apply these principles to

systems

consisting of heterogeneous substances and deduce the special laws

which

a|)])ly to different classes

shall use the

it

of phenomena.

For

this

purpose we

second form of the criterion of equilibrium, both because

admits more readily the introduction of the condition that there

shall be

no tliermal communication between the different parts of the

it is more convenient, as respects the form of

system, and because

the general equations relating to equilibrium, to

make the entropy

one of the independent variables which determine the state

system, than to

make

of the

the energy one of these variables.

THE CONDITIONS OF EQUILIBRIUM FOR HETEROGENEOUS MASSES IN

CONTACT WHEN UNINFLUENCED BY GRAVITY, ELECTRICITY, DISTORTION
OF THE SOLID MASSES, OR CAPILLARY TENSIONS.
In order to arrive as directly as possible at the most characteristic

and

essential laws of chemical equilibrium,

attention to a case of the simplest kind.

we

will first give

We will

our

examine the con-

mass of matter of various kinds enclosed

and fixed envelop, which is impermeable to and unalterable by any of the substances enclosed," and perfectly non-conducting
ditions of equilibrium of a

in a rigid

to heat.

We

will

suppose that the case

action of gravity, or
solid portions of the

by any

is

not complicated by the

electrical influences,

mass the pressure

is

and that

in

the

the same in every direction.

116

W. Gihhs Equilibrium of Heterogeneous

J.

We

Substances.

problem by supposing that the variaand entropy which depend upon the
surfaces separating heterogeneous masses are so small in comparison
with the variations of the parts of the energy and entropy which
will farther simplify the

tions of the parts of the energy

depend upon the quantities of these masses, that the former may be
neglected by the side of the latter; in other words, we will exclude
the considerations which belong to the theory of capillarity.
It will be observed that the supposition of a rigid and nonconducting envelop enclosing the mass under discussion involves no

any mass of matter is in equilibrium, it

the whole or any part of it were enclosed in an

real loss of generality, for if

would

be

also

so, if

envelop as supposed

therefore the conditions of equilibrium for a

mass thus enclosed are the general conditions which must always
be satisfied

As

case of equilibrium.

in

which have been made,

which are here excluded

other suppositions

for the

and considerations

the circumstances

all

afterward be

will

made

of

subject

the

sj^ecial discussion.

Conditions relating

Let us

first'

between the initially existing

to the Equilihr'nim

Homogeneous Parts of

the given

Mass.

consider the energy of any homogeneous part of the

given mass, and

any possible variation in the com(By homogeneous is meant that the

uniform throughput, not only in chemical comphysical state.) If we consider the amount and
variation for

its

position and state of this part.

part in question

is

position, but also in

kind of matter in this homogeneous mass as fixed,

function of

its

entropy

and

7/,

its

volume

energy

its

and the

y,

f is

differentials

of these quantities are subject to the relation

de
t

dt]

J) dv,

(1 1)

denoting the (absolute) temperature of the mass, and

its

pressure.

the heat received, and p dv the work done, by the mass

change of state. But if we consider the matter in the
m for the quantities of the
mass as variable, and write mj, mg,
S^ of which the mass is composed, e
various substances aS,, S2,
will evidently be a function of ?;, w, my, ni^,
?, and we shall

For
*

dn

during

is

its

have for the complete value of the

de^itdi]
y^ J,

7^2 5

/'n

pdv -\- iJy dm

differential of e
-\- yw^ ^^'"2

+/^"

denoting the differential coefficients of

respect to m,, mg,

The substances

aS^,,

^^'"n?

(1-)

taken with

?w.

S21

^m of which we consider the mass

composed, must of course be such that the values of the

differen-

J.

W. Gihbs

tials d'm^,

dm2,

Equilibrium of Heterogeneous Substances.

.

dm

shall

llV

be independent, and shall express

every possible vaination in the composition of the homogeneous mass

considered, including those produced
different

from any

initially present.

to have terms in the equation

which do not

initially

by the absorption of substances

It

may

relating

to

therefore be necessary

component substances

occur in the homogeneous mass considered,

provided, of course, that these substances, or their components, are

some part of the whole given mass.

mentioned are satisfied, the choice of the substances which we are to regard as the components of the mass considered, may be determined entirely by convenience, and independently
of any theory in regard to the internal constitution of the mass.
The
number of components will sometimes be greater, and sometimes
less, than the number of chemical elements present.
For example,
in considering the equilibrium in a vessel containing water and fi'ee
hydrogen and oxygen, we should be obliged to recognize three components in the gaseous part. But in considering the equilibrium of
dilute sulphuric acid with the vapor which it yields, we should have
only two components to consider in the liquid mass, sulphuric acid
(anhydrous, or of any particular degree of concentration) and (addito be found in

If the conditions

tional) water.

state of

If,

maximum

might possibly

however, we are considering sulphuric acid in a

concentration in connection with substances which

affoi'd

water to the

acid, it

must be noticed that the

condition of the independence of the differentials will require that

consider the acid in the state of

maximum

The quantity of

the components.

ble of variation both

this

in the positive

component

and

in

we

concentration as one of
will then be capa-

the negative sense, while

the quantity of the other component can increase but cannot decrease

below the value

0.

For brevity's sake, we may call a substance S,, an actucd component

of any homogeneous mass, to denote that the quantity m of that
substance in the given mass may be either increased or diminished
(although we may have so chosen the other component substances
that rn^
and we may call a substance S,, a jiossible component
0)
to denote that it may be combined with, but cannot be substracted
from the homogeneous mass in question. In this case, as we have
seen in the above example, we must so choose the component substances that W4 =z 0.
The units by which we measure the substances of which we regard
the given mass as composed may each be chosen independently.
To
fix our ideas for the purpose of a general discussion, we may suppose

118
all

W. Gihhs

J.

Equilibrium of Heterogeneous Substances.

Yet

substances measured by weight or mass.

may be more

in special cases, it

convenient to adopt chemical equivalents as the units

of the component substances.

may be

It

observed that

not necessary for the validity of

is

it

equation (12) that the variations of nature and state of the mass to
which the equation refers should be such as do not disturb its homogeneity, provided that in all parts of the mass the variations of
For,

nature and state are infinitely small.

not violated, an equation like (12)

if this last

homogeneous mass
the energy, entropy, etc., of any

itesimal parts of the (initially)

Z>f, Dt], etc., for

cWn

clD)}

- p dlJv

-\- /<

dDm^-\-

whence we may derive equation

initially homogeneous mass.

We

now suppose

will

all

the infin-

e., if

we write

certainly valid for

is

fx,

(12)

cWni^

i.

infinitesimal part,
-f- //

by integrating

that the whole mass

is

condition be

clDm^,

for the

(13)

whole

divided into parts so

that each part is homogeneous, and consider such variations in the

energy of the system as are due to variations in the composition and
state of the several parts remaining (at least approximately) homoge-

neous, and together occupying the whole space within the envelop.
will at first suppose the case to be such that the component sub-

We

stances are the same for each of the parts, each of the substances
If we
aS being an actual component of each part.
S'2,
/S
.

distinguish the letters referring to the different parts

by

accents,

the variation in the energy of the system may be expressed by

^f _|_ (Jf" _j- etc., and the general condition of equilibrium requires
'

that
Se' _|-

for all variations

ds"

etc.

(14)

conflict with the equations

which do not

of condi-

These equations must express that the entropy of the whole

tion.
given mass does not vary, nor its volume, nor the total quantities of
will suppose that there
aS.
any of the substances >S\, /6'g,
.

We

are no other equations of condition.

It will

then be necessary for

equilibrium that
t'

_|_ t"

-f-

for

-2^'^v' +///(ym,'

Sr,'

S7/"

etc.

-\-

-p" Sv" -\- pi^" dm^" +

juj 6rn,J
/A2"

6m,"

.+//'
.

//,."

(Jm'

6m ^'
(15)

any values of the variations

cJ//'

+ (J7" 4-

for

(5/7'"

which

^'j^Svnj^Sv"'-\-

etc.

etc.

0,

=0,

(16)
(17)

W. Gibbs

J.

and

For

this

it is

Equilibrium of Heterogeneous Substances.

-f

Sm^"

dm.^'

dni.^"

+ dm^'" +
+ Sni^'" +

(^m/

dm^'

Si/i"

-\-

-j-

(ym"'

etc.
etc.

-\- etc.

=
=

=r

119

0,
0,

0.

/jg\

evidently necessary and sufficient that

t'

= = t"'=

jj

=ip" =p"'

t"

yu

'

A<2'

//,/

etc.

(19)

etc.

(20)

= =
=
= A'2" = /<2"'= etc.
= //" =
=
yu

"

'"

yU

etc.

etc.

/u"'

"]

^21)
J

Equations (19) and (20) express the conditions of thermal and

mechanical equilibrium, viz., that the temperature and the pressure

must be constant throughout the whole mass. In equations

have the conditions characteristic of chemical equilibrium.
call

a quantity

may be

If

by such an equation as (12), the potential

homogeneous mass considered, these con-

as defined

//,,

for the substance S^ in the

ditions

we
we

(21)

expressed as follows

TTie potential

for each component substance must

be

constant

throughout the lohole mass.

be remembered that we have supposed that there

is no
upon the freedom of motion or combination of the component substances, and that each is an actual component of all parts

It will

restriction

of the given mass.

The

state of the

whole mass will be completely determined

(if

we

regard as immaterial the position and form of the various homoge-

neous parts of which

it is

composed), when the values are determined

of the quantities of which the variations occur in (15).

of these quantities, which

we may

call the

evidently (/i-j-2)r, v denoting the

into which the whole mass

is

The number

independent variables,

number of homogeneous

divided.

All

the quantities which

occur in (19), (20), (21), are functions of these variables, and

regarded as known functions,

a function of

ponents.

its

if

the energy of each part

is

entropy, volume, and the quantities of

(See eq. (12).)

is

parts

may be

known
its

Therefore, equations (19), (20), (21),

as

com-

may

be I'egarded as {y \) [n { 2) independent equations between the

independent variables. The volume of the whole mass and the total
quantities of the various substances being
tional equations.

mass, or

its total

If

we

entropy,

are independent variables.

also

we

know
will

known

aiford n-\-

addi-

the total energy of the given

have as many equations as there

120

tT

W. Gibbs

Equilibrium of Heteroyeneous Substances.

S^ are only possible comany of the substances ^S'j, -8^

ponents of some parts of the given mass, the variation 6m of the
quantity of such a substance in such a part cannot have a negative

But

if

of equilibrium (15) does not

value, so that the general condition

require that the potential for that substance in that part should be

equal to the potential for the same substance in the parts of which it
In this
is an actual component, but only that it shall not be less.
case instead of (21)

we may

for all parts of

which

for all parts of

which S^

S^i

is

is

write

an actual component, and

a possible (but not actual) com-

ponent,

/'2

for all parts of

which S^

is

for all parts of

which S2

is

^-^2

(22)

an actual component, and

a possible (but not actual) com-

Donent,
etc.,

J/j, J/2? ^^^-5 clenoting constants of which the value

is

only deter-

mined by these equations.

If

we now suppose

that the components (actual or possible) of the

various homogeneous parts of the given mass are not the same, the

be of the same character as before, provided that all the

components are independent., (i. e., that no one can be made
out of the others,) so that the total quantity of each component is
The general condition of equilibrium (15) and the equations
fixed.

result will
different

of condition (16), (17), (18)

any of the substances

possible) of

any

/S'j,

part, the

will require no change, except that, if

S^

term

//

is

not a component (actual or

dru for that substance and part will

and the Sin in the latter. This will require

form
of
the particular conditions of equilibrium as
no change
expressed by (19), (20), (22); but the number of single conditions
contained in (22) is of course less than if all the component subWhenever, therefore, each
stances were components of all the parts

be wanting

in the former,

in the

of the different homogeneous parts of the given mass

as

composed of some or of

all

of the same

may

is

no one
which (with

set of substances,

of Avhich can be formed out of the others, the condition

equality of temperature and pressure)

be regarded

necessary and sufficient for

equilibrium between the different parts of the given mass

expressed as follows:

may be

J.

W. Gibhs

Equilibrium of Heterogeneous Substances.

121

The potential for each of the component substances must have a

j)'irts of the gioen mass of which that substance
is an actual component, and have a, value not less than this in all
parts of ^ohich it is a jtossible comjjonent.
The number of equations aiForcled by these conditioiiH, after elimination of iJfj, J/2,
J/, will be less than {n + 2) (k - 1) by the number of terms in (15) in which the variation of the form 6rn is either
The number of
necessarily nothinij or incapable of a negative value.
variables to be determined is diminished by the same number, or, if
constant value in all

we

choose,

we may

these terms.

m=

write an equation of the form

part concerned, there will also

l)e

is

a possible

show whether the supposition that the substance

component is consistent with equilibrium.

We will
all

now suppose

that the substances

independent of each other,

We

out of others.

i.

for each of

component of the
a condition (expressed by ^ ) to

when the substance

]>ut

e.,

*S\, aSj,

that some of

not an actual

is

will first consider a very simple case.

composed of S^ and

Sr,

combined

in

6'

are not

them can be formed

the ratio of a to

b,

Let

Sr^

be

S^ and S^

occurring as actual components in some parts of the given mass, and

/iS'g
in other parts, which do not contain S^ and 82 as separately
variable
still
IX

6m

components.

The general

condition

of equilibrium

will

have the form of (15) with certain of the terms of the form
omitted.

:^'{t6if)

It

may

be written more briefly

-:^{pSv)-\-:^{/J,dm^)-\-^{;i2d^m.,).

[(23)
,

.-^2:{/./drn)^0,

the sign i' denoting summation in regard to the diiferent parts of

the given mass.

But instead of the three equations

2 dm = 0, 2 6m = 0,
1

we

shall

have the two.

:2 6m ^

of condition,
0,

(24)

122

W.

J.

(jrlbbs

For, although
yet

may

it

be that

for example, is greater than J/^,

/z^',

6m

can only be so when the following

it

Hence,

tive value.
(23)

EquUihrium of Heterageneou's Substances.

is satisfied,

if (27)

must

(27)

is satisfied,

(2;3)

^'

is

incapable of a nega-

must

Again,

also be.

if

also be satisfied, so long as the variation

in all the parts of

of the quantity of every substance has the value
But as this limitation does not
it is not an actual component.

which

it

may

drn^, and '2 6m^,

6m^,
range of the possible values of
be disregarded. Therefore the conditions (23) and (27) are

afiect the

when (19), (20), (22) are satisfied. Now, by

means of the equations of condition (25), we may eliminate :^ dm^
and 2 6ni2 from (27), which becomes
entirely equivalent,

- a3I,2 6m ^-bM^^ 6rn^ +

i.

e.,

as the value of

which

is

6m^ may

+b) M^:S 6m^^

{a

(28)

0,

be either positive or negative,

{a + b) M^,

M^ -^-bM^

(29)

the additional condition of equilibrium which

is

necessary

in this case.

The

between the component substances

relations

may

be

less

simple than in this case, but in any case they will only affect the
equations of condition, and these may always be found without difiiculty, i^nd will enable us to eliminate from the general condition of

equilibrium as
after

many

which the

variations as there are equations of condition,

coefficients of the

remaining variations

may be

set

equal to zero, except the eoefiicients of variations which are incapable

of negative values, which coefficients must be equal to or greater
It will

than zero.

ticular case, but

it

be easy to perform these operations in each parbe intei-esting to see the form of the resultant

may

equations in general.

We will suppose that the various

as having in all n components,

homogeneous parts

*S'i,

S^,

/S,

are considered

and that there

is

no

freedom of motion and combination. But we

generality of the problem as to suppose that
the
limit
far
so
will
is an actual component of some part of
components
these
of
each
of
these components can be formed out of
some
If
mass.*
the given

restriction

upon

their

others, all such relations can be expressed

a(Ba+P ;, +
where a,
*

(Sj, i-, etc.

When we come

7c

3,

+ A @, +

as

etc.

(30)
S^,, Sf,,

etc.,

to seek the conditions of equilibrium relating to the formation of

of the equilibrium of
it

=:

denote the units of the substances S,

masses unUke any previously

and give

<^tc.

by equations such

existing,

we

shall take

up de novo the whole problem

heterogeneous masses enclosed in a non-conducting envelop,

a more general treatment, vs^hich will be free from this hmitation.

(that
etc.

J.

W. Gibbs EquiUhrium of Heterogeneous

is,

of certain of the substances

S ^,

These are not,

denote nnmhers.

So,

between abstract quantities, but the sign

We

well as quantitative equivalence.

relating to the

It is

f^,)

it

and

<-(-,

fi,

;(-,

denotes qualitative as

The equations

component substances may

from these equations, but

particularly.

will suppose that there are

r independent equations of this character.

dition

be observed, equations

will

it

123

Sitbstances.

of con-

easily be derived

be necessary to consider them

will not

evident that they will be satisfied by any values

of the variations which satisfy equations (18); hence, the particular

conditions of equilibrium (19), (20), (22) must be necessary in this
case, and, if these are satisfied, the general equation of equilibrium
(15) or

reduce to

will

(2.3)

^ 6m + 3I2 2 Sin,^

J/j

-\-

2 (hn^

JI

0.

(31)

This will appear from the same considerations which were used in

regard to equations (23) and

2 Srn^, 2

give to
etc,

in equation (30),

making

2 Sm =^
a 31^

or,

It will

Now

(27).

2 dm^.,

Snii,^

etc.

evidently possible to

n,

therefore

- k 31, - X etc. =^
+ etc.
a 31, + p 31, + etc. = h 31, + A 31, + etc.
-f /i 31,,

be observed that

cients as equation (30),

/J,

and also the same values taken negatively,

each of the other terms

in

is

it

values proportional to a,

31,,

(33)

has the same form and

this equation

31 taking the

(32)

0,

place of .

coeffi-

It is evident that

there must be a similar condition of equilibrium for every one of the

which (30) is an example, which may be obtained simWhen these condiply by changing in these equations into 3f.
any
possible values of
tions are satisfied, (31) will be satisfied with
2 6111^. For no values of these quantities are
Sdm^, 2 Sm^,
r equations of

possible, except siich that the equation

{2 6m ,)(^,

+ {2 6m.,) ^

+ (^' 6m,) =

after the substitution of these values, can be derived

tions like (30),

by the ordinary

from the

(34)
r

equa-

processes of the reduction of linear

Therefore, on account of the correspondence between (31)

and between the r equations like (33) and the r equations
like (30), tiie conditions obtained by giving any possible values to
the variations in (31) may also be derived from the r equations like
equations.

and

(33)
(33)
(19),

(34),

that

is,

the condition (31)

is

satisfied, if the

equations like

Therefore the r equations like (33) are with

(20), and (22) the equivalent of the general condition (15)

are

or (23).

satisfied.

124

W. Gibbs EquUlbrhun of J{eterof/e)ieo%is

J.

For

fleterminiiig the state of a given

and having

^Substances.

mass when

equilibrium

in

given volume and given energy or entropy, the condi-

tion of equilibrium affords an additional equation corresponding to

each of the r independent relations between the

stances.

matter

in

r in

ti component subBut the equations which express our knowledge of the

the given mass will be correspondingly diminished, being

number,

quantities of the

the former

by

the equations of condition relating to the

like

component substances, which may be derived from

differentiation.

Conditions relating

to tlie possible Jb^ormation

of Masses Unlike any

Previoush/ Existing.

The

we have

variations which

hitherto considered do not embi'ace

every possible infinitesimal variation in the state of the given mass,

already formed, although always

so that the particular conditions

necessary for equilibrium (when there are no other equations of con-

than such as we have supposed), are not always

dition

sufficient.

For, besides the infinitesimal vai'iations in the state and composition

may be

of different parts of the given mass, infinitesimal masses

and composition from any initially

Such parts of the whole mass in its varied state as
existing.
cannot be regarded as parts of the initially existing mass which
have been infinitesimally varied in state and composition, we will
These will necessarily be infinitely small. As it is
call nev) parts.

formed entirely

different in state

more convenient to

I'egard a

vacuum

as a limiting case of exti'eme

rarefaction than to give a special consideration to the possible for-

mation of empty spaces within the given mass, the term new parts

empty spaces which may be formed,

We will use De, Dr], Dv, Dm^,
D}n to denote the infinitesimal energy, entropy, and volDm^,
ume of any one of these new parts, and the infinitesimal quantities
The component substances /S\, Sg,
S must
of its components.

will

be used to include

when such have not

.

anj^

existed initially.

now be taken

to include

ponents (actual or possible) of

existing, but also the

formation of which

not only the independently variable comall

parts of the given mass as initially

components of

we have

all

new parts, the possible

The character (i will be

the

to consider.

used as before to express the infinitesimal variations of the quantities

which are only infinitesimally varied in state

I'elating to those parts

and composition, and which

for distinction

we

will call original parts,

including under this term the empty spaces,

within the envelop bounding the system.

given mass into as

many

parts as

we

if

such exist

As we may

initially,

divide the

choose, and as not only the

W. Gibhs

J.

initial

Eqailihriuni of Heterogeneous Substances.

125

boundaries, but also the movements of these boundaries during

any variation

system are

in the state of the

we may

arl)iti'ary,

so

we have called original, that we may consider

homogeneous and remaining so, and as initially con-

define the parts wliieh

them

as initially

stituting the whole system.

The most general value

of

energy of the whole system

the

is

evidently

:^6-\-:^D,
the

first

summation

to all the

new

6 or

letter

parts.

relating to

(35)

the original parts, and the second

all

(Throughout the discussion of this pi'oblem, the

surticiently indicate whether the sum-

D following ^ will

mation relates to the original or to the new

general condition of equilibrium

parts.)

Therefore the

is

:^6e^0,

:2de->[-

(36)

[(^V)
we substitute the value of 6e taken from equation (12),
2De+^{txhj) - 2{pr3v) + 2U.i,6, ,)+^{i,^6w.,) +2{i<^hn:)^ 0.

or, if

If

any of the substances

we

S ^,

S^^

will suppose, as before (see

can be formed out of others,

*S'

page

122), that

such relations are

expressed by equations between the units of the different substances.

Let these be

^1

^2

^>n

I r equations.

etc.

(38)

The equations of condition will be (if there is no restriction upon the

freedom of motion and composition of the components)

2 di] -f 2 By = 0,
2 Sv + ^ Dv 0,

(39)

z=z

and n

r equations of
h^

{^dm^ + ^Dm^)

-j-h^

+
tj

(40)

the form

{2Sm, +2Dm.^)

+i.^

{^(hn^ +
{2 Sm

^ Dm^

{^dm +

2 JDm^J
+ 2 1)m) =

-f /

{2 Sm

JS"

-1

I)m)
.

(41)^

etc.

* In regard to the relation between the

coefficients in

(41)

and those in

(38),

the

the coefficients of any one of equations (41)

are such as would satisfy aU the equations (38) if substituted for S,, S.^,
S- and

reader will easily convince liimself

tliat

that this

is

sets of coefficients shall

pendent equations
equations

is

the only condition which these coefficients must satisfy, except that the

and that

a reciprocal one.

be independent,

this relation

i.

e.,

shall

between the

be such as to form inde-

coefficients of the

two

sets of

126

J.

Now,

tract

W. Gibhs

Equilibrium of Heterogeneous Substances.

"method

using Lagrange's
{^^ di]

-[

21)!/)

of multipliers,"*

P{2 6v + 2 D)j)

from the

yand

of the general condition of equilibrium (37),

we

will sub-

member

iirst

P being constants

is as yet arbitrary.
We might proceed in the
same way with the remaining equations of condition, but we may
obtain the same result more simply in another way.
We will first

of which the value

observe that

{2 6m^

-f

2Dm^) , + {2 6m + 2D)n^)
+ {2 6m + 2 Dm,,) = 0,

which equation would hold identically

(42)

any possible values of the

for

of the letters i, 'B-^,

were
substituted their values in terms of the others as derived from equa-

quantities in the parentheses,

tions (38).
ties,

(Although

(5

J,

if for r

2,

do not represent abstract quanti-

yet the operations necessary for the reduction of linear equations

Therefore, equation (42)

are evidently ap])licable to equations (38).)

"Sn we substitute n numbers which

j, 2?
M be such numbers, i. e.,
Let il/j, J/o,
equations (38).

will hold true if for

satisfy

let

a^M^ + a^Jf.^
b^M^ + b^M^

3f

-f *

0,

M =

0, 1 r

etc.

equations, (43)

then

This

{^dm^^^Bm^)
+ J/ {2 Sm + 2 Dm,,) = 0. (44)
r of the constants M^, M2,
expression, in which the values of

J/,

{2 6m^-r2I)m^) + M2

11

are

still

arbitrary,

we

from the

will also subtract

first

mem-

ber of the general condition of equilibrium (37), which will then

become

- 2 Sv) -f 2 {^ (hn,)
2 De + 2
T2 67] + F2 8v - M^2dm^
- T2Dr]-^P2Dv -M^ 2Dm^
{t (J;/)

That

is,

{]>

having assigned to

sistent with (43),

we may

T,

it is

..

+ 2 (yM (hn)
+ M 2 6m
^3I2Dm>.0.

(45)

-^n any values connecessary and sufficient for

P, 31^, J/2,

assert that

equilibrium that (45) shall hold true for any variations in the state
of the system consistent with the equations of condition (39), (40),
(41).

But

it

will

always be possible,

such values to T, P, 31^,

*

On

account of the sign

iHfg,

in (3T),

3f,

in case of equilibrium, to assign

without violating equations

and because some

(43),

of the variations are incapable

of negative values, the successive steps in the reasoning will be developed at greater

length than would be otherwise necessary.

W. Gihhs

J.

Equilibrium of Heterogeneous Substances.

that (45) shall hold tnie for

all

127

variations in the state of the system

and in the quantities of the various substances composing it, even

though these variations are not consistent with the equations of conFor, when it is not possible to do this, it
dition (39), (40), (41).
must be possible by applying (45) to variations in the system not
necessarily restricted by the equations of condition (39), (40), (41) to
M, some of
obtain conditions in regard to 1\ P, Jf,, M2,
which will be inconsistent with others or with equations (43). These
.

we

conditions

will represent

by

.4^0,

^^0,

etc.,

(46)

Then it
A, B^ etc. being linear functions of T, P, 31 1, J/g,
31,.
will be possible to deduce from these conditions a single condition of
the form
.

aA+/3B+

a,

/3,

etc,

(47)

0,

being positive constants, which cannot hold true consistBut it is evident from the form of (47)

etc.

ently with equations (43).

any of the conditions

that, like

from

directly

by applying

(45)

the system (perhaps not restricted

Now

(40), (41)).
it is

formula to a ceitain change

by

in

the equations of condition (39),

as (47) cannot hold true consistently with eqs. (43),

evident, in the

fore in the

could have been obtained

(46), it

this

change

first

place, that

cannot contain

it

system just mentioned

in the

T or

P, therewhich (45)

(for

reduces to (47))

2 d?f + :^ 1)1} = 0,

and

:^

60

+ :2 Bv = 0,

so that the equations of condition (39) and (40) are satisfied.

Again,

same reason, the homogeneous function of the first degree of

iHfj, Jfg,
3f in (47) must be one of Avhich the value is fixed by
eqs. (43).
But the value thus fixed can only be zero, as is evident
from the form of these equations. Therefore

for the

2 dm + 2 Bm ,).,+
1

(>;

dm

, -f- li'

X>>/i,

31^

+ 2 dm 2 Bm) 3/ ~

(48)

-{-

any values of J/,, 3^2 ..

for

which

3f

satisfy

eqs.

(43),

and

therefore

{2^Smj

+ 2 Bm^)

(Bi+ {2dm2 + 2Bm2)(B2

+ {2 6m + 2 Bm) =

any numerical values of

(49)

(S^, ^2,
which satisfy eqs. (38).
This equation (4D) will therefore hold true, if for r of the letters

for

(S

Sg,

Bn we substitute

their values in terms of the others

taken from eqs. (38), and therefore

it

will

hold true when

we

use

128

J,

W. Gibbs

J.

(2 2,

Equilibrium

of Heterogeneous Substances.

, as before, to denote the units of the various com-

Thus understood, the equation expresses that the values

ponents.

of the quantities in the pai'entheses are such as are consistent with

The change in the system, there(41).

which we are considering, is not one which viohites any of the
equations of condition, and as (45) does not hokl true for this change,
and for all values of T, P, M^, M.^,
M^ which are consistent
with eqs, (43), the state of the system cannot be one of equilibrium.
the equations of condition
fore,

Therefore
that

it

necessary, and

it is

shall

evidently sufficient for equilibrium,

it is

be possible to assign to

T^

P, 31^, J/gi

^^n snch values,

consistent with eqs. (43), that the condition (45) shall hold true for

any change

system irrespective of the equations of condition

in the

(39), (40), (41).

For

this

it is

necessary and sufficient that

p = P,

t=l\
fj.^

Sm.^^

M^ dm ^,

/.I2

(^t2=^ ^^2 ^'^^21

'

(50)

Mn^f^n^ MSni

for each of the original parts as previously defined,

Jje
for

TI))j-\-PI>v

J/,

Dm^ - M^Dn,^

...

(51)

and that

- M,,Drn^^

(52)

0,

each of the new parts as previously defined. If to these condiwe add equations (43), we may treat 1\ P, Jf^, J/g?
-^n

tions

simply as unknown quantities to be eliminated.

In regard to conditions (51), it will be observed that
stance,

'S'j,

is

distinguished
negative, and

if

a sub-

an actual component of the part of the given mass

by
we

a single ac<'ent,
shall

have

/<i'

6m ^' may
^f^

but

be either positive or

if

S^

only a possible

is

component of that part, 6in^' will be incapable of a negative value,

and we will have /^/^ J/,.
The formulae (50), (51), and (43) express the same particular conditions of equilibrium which we have before obtained by a less genThis formula must hold
It remains to discuss (52).
eral process.
in its varied state which
in
the
system
mass
infinitesimal
any
of
true
any
of the surrounding
with
homogeneous
approximately
is not
B?n denoting
Bm^,
Bm
Be,
Bv,
expressions
/>//,
^,
the
masses,
mass, and the
infinitesimal
this
volume
of
and
entropy,
the energy,
as comregard
which
we
*S'
substances
A'j,
S^,
the
of
quantities
.

posing

it,

If there

is

(not

indepenAently variable components).

necessarily as

more than one way

in

which

this

mass may be considered

as composed of these substances, we may choose whichever is most

convenient. Indeed it follows directly from the relations existing

between J/j, M^,

and

that the result

would be the same

in

W. Gihhs

J.

any

Now,

case.

Dm.^,

for

JEquilibriwui of Ileterofjeneous Substances.

we assume that the vahies

if

of

Z><^, />//,

7>y,

129

Dm^.,

Dnin are proportional to the A^alues of f, //, t;, mj, y/^^,

any large homogeneous mass of similar composition, and of
.

the same

temperature aud pressure, the condition

equivalent to

is

this, that
f

for

_ T)i^Pv -

J/,

-J/2

///^

J/,

'''n

(53)

any large homogeneous body which can be formed out of the

substances 8^,82
'S'.
But the validity of this last transformation cannot be admitted
.

without considerable limitation.

It

is

assumed that the relation

between the energy, entropy, volume, and the quantities of the

dif-

components of a very small mass surrounded by substances

of different composition and state is the same as if the mass in quesWe started,
tion formed a ])ait of a large homogeneous body.
neglect
the
part of the
that
might
the
assumption
indeed, with
we
ferent

depending upon the surfaces separating heterogeneous

Now, in many cases, and for many purposes, as, in general,
masses.
when the masses are large, such an assumption is quite legitimate,
energy,

but

in

etc.,

the case of these masses which are formed within or

among

substances of different nature or state, and which at their first formation must be infinitely small, the same assumption is evidently
entirely inadmissible, as the surfaces must be regarded as infinitely
We shall see hereafter what
large in proportion to the masses.
modifications are necessary in our formulge in order to include the

which are due to the surfaces, but this will

be on the assumption, which is usual in the theory of capillarity,
parts of the energy,

etc.,

that the radius of curvature of the surfaces

is

the radius of sensible molecular action, and

the lamina of matter at the surface which

neous

in

is

large in proportion to

also to the thickness of

not (sensibly) homoge-

respects with either of the masses which

all

But although the formulae thus modified

will

accuracy to masses (occurring within masses of a

much

smaller than

yet their failure

dimensions

is

if

it

separates.

apply with sensible

diffei'ent

nature)

the terms relating to the surfaces were omitted,

when applied

to masses infinitely small in all their

not less absolute.

Considerations like the foregoing might render doubtful the validity

even of (52) as the necessary and sufiicient condition of equilibrium

regard to the formation of masses not apprpximately homogeneoiis

in

with those previously existing, when the conditions of equilibrium

between the

latter are satisfied, unless

it is

shown that

in establishing

this formula there have been no quantities neglected relating to the

Trans. Conn. Acad., Vol.

III.

17

October, 1ST5.

130

W.

J.

iJribhs

EnuiUbriura of Ileteroyeaeous Substances.

mutual action of the new and the original parts, which can affect the
result.
It will be easy to give such a meaning to the expressions

Dm^,

De, Dtf, Dv,

case.

It will

Dnio^

I>m that

this shall

be evidently the

be observed that the qtiantities represented by these

have not been perfectl^^ defined. In the first place, we

have no right to assume the existence of any surface of absolute discontinuity to divide the new parts from the original, so that the
ex])ressions

position given to the dividing surface

Even

energy

is

to a certain extent arbitrary.

separating the masses wei-e determined, the

surface

the

if

be attributed to the masses separated would be partly

to

arbitrary, since a part of the total energy depends

action of

tlie

two masses.

We

upon the mutual

ought perhaps to consider the case

the same in regard to the entropy, although the entropy of a system

never depends upon the mutual relations of parts at sensible

tances from one another.
the quantities De,

none of

tlie

iJi],

Now

Do, Dra^, ^'"2

assumptions are the following:

new

that

^^^^

if

defined that

parts, shall

not affected by

entropy, volume,

the vicinity of the

etc.,

be violated.

These

the relation between the varia-

tions of the enei'gy, entropy, volume, etc., of

represented

-^"^n

'^^'^

assumptions which have been made, tacitly or otherwise,

relating to the formation of these

is

dis-

the condition (52) will be valid

new

any of the original parts

parts; and that the energy,

of the system in its varied state are correctly

by tbe sums

of the energies, entropies, volumes, etc., of

the vai'ious parts (original and new), so far at least as any of these
quantities are determined or affected
parts.

We

suppose De,

will

TJi],

Dv,

by the formation of the new

Dm Dm^
^,

so defined that these conditions shall not be violated.

done

in various ways.

surfaces separating the

We may

Dm,, to be
This

may

be

suppose that the position of the

new and the

original parts has been fixed in

This will detei-mine the space and the matter

any suitable way.

belonging to the parts separated.

If this does not determine the

we may supi)Ose this determined in any suitThus we may suppose the total enei'gy in and

division of the entropy,

able arbitrary way.

about any new part to be so distributed that equation (12) as applied

by the formation of the

to the original parts shall not be violated

new

parts.

Or,

it

may seem more

simple to suppose that the

imaginary surface which divides any new part fi-om the original is
so placed as to include all the matter which is affected by the
vicinity of the

new

formation, so that the part or parts which

we

regard as original may be left homogeneous in the strictest sense,

including uniform densities of energy and entropy, up to the very

W. Gihhs

J.

JEquiUhriuni of Hetercxje.neoxx

Siihsfaiices.

13]

The lioniogeneity of the new parts is of no conwe have made no assumption in that respect. It may
be doubtful whether we can consider the new parts, as thus bonnded,
bounding

surface.

sequence, as

But

to be infinitely small even in their earliest stages of development.

if

they are not

infinitely small, the

the validity of our formuhe will be

condition,

way

in

which

this can affect

virtue of the equations of

tliat in

in virtue of the evident necessities of the case, finite

e.,

i.

otdy

variations of the energy, entropy, volume, etc., of the original })arts

will be caused, to

But

apply.

which

it

might seem that equation

we

integrate the equation under

the equation will hold true for

first

may

be considered as

Hence,

the above limitation.)

finite

provided that the

differences,

nature and state of the mass be infinitely

ferences

would not

(This appears at once,

tion (12) will hold true of finite differences.

if

(12)

the natui-e and state of the mass be not varied, equa-

if

little

For the

varied.

made up of two

dif-

parts, of whicJi the

are for a constant nature and state of the mass, and the second

We may

are infinitely small.

bounded

therefore regard the

new

parts to be

supposed without prejudice to the validity of any of our

as

results.

The condition

(52)

understood

in

either

ways

of these

(or

in

others which will suggest themselves to the reader) will have a per-

and

suffi-

cient condition of equilibrium in regard to the formation of

new

fectly definite meaning,

when

parts,

and

will be valid as the necessary

the conditions of equilibrium in regard to the original

parts, (50), (51),

and

(43), are satisfied.

In regard to the condition (53),

(51),
it is

fied,

and

(43)

it is

always

it

may

be shown that with

sufficient for equilibrium.

To

only necessary to show that when (50), (51), and (43) are
and (52) is not, (53) will also not be satisfied.

We

will first observe that

T}/

(50),

pi-ove this,
satis-

an expression of the form

- Po -f M^

m^

+ 31^ m^

+ Mm

(54)

denotes the work obtainable by the formation (by a reversible prom are the energy,
cess) of a body of which f, //, v, m^, vy/g,
.

entropy, volume, and the quantities

of the

components, within a

medium having the pressure P, the temperature 7\ and tiie potentials

(The medium is supposed so large that its propM.
ilfj, M2,
erties are not sensibly altered in any part by the formation of the
body.) For e is the energy of the body formed, and the remaining
terms represent (as may be seen by applying equation (12) to the
.

medium) the decrease

of

tlie

energy of the medium,

if,

after the

J.

1:52

W. Gibhs EqiiiUhrmm of Itetero'geneous Substances.

formation of the body, the joint entropy of the

medium and

the

body, their joint volumes and joint quantities of matter, were the

same

medium

as the entropy, etc., of the

body.

may

This consideration

vahies of v and of T, P, M.^

when

f, ;/, //ij,

etc. are

finite

expivssion cannot be infinite

etc. this

before the formation of the

convince us that for any given

determined by any real body, whether homo-

geneous or not, (but of the given volume), even when

T^

P,

Jif^, etc.

do not represent the values of the temperature, pressure, and potenof any real substance.

tials
all

(If

the substances

tS'^,

a>'.,,

S are

of any homogeneous part of the system of

actual components

which the equilibrium is discussed, that part will afibrd an example

body having the temperature, pressure, and potentials of the

of a

medium

supposed.)

Now by

integrating equation (12) on the supposition that the

nature and state of the mass considered remaiii unchanged,

we

obtain

the equation

which
for

t7/

~-pv-\- /i^m^-\- /.(^m^

any one of the original

f-

7'//

pai-ts,

+ Pw- J/,

If the condition (52)

is

/^

by

J/2?2

and

new part occurring

the condition

not satisfied.

It

is

Therefore

(51),

Mn>^=zO.

not satisfied in regard to

parts, let i\^be a

is

(50)

(55)

+//n"?r.

hold true of any homogeneous mass whatever.

will

all

(56)

possible

in an original part 0, for

new

which

evident that the value of the

expression
e

Ti] + Py - M^ m^ J/^ m.2

JV

be negative, and

is

Avill

Mm

(57)

including some very small masses like

applied to a mass like

will

...

decrease

if

the

number of

iV^,

these masses like

increased, until there remains within the whole mass no portion

of any sensible size without these masses like iV, which,

But
cannot become

remembered, have no sensible

limit, as the value of (54)

size.

it

will be

cannot decrease without

it

infinite.

Now we

need not

inquire wliether the least value of (57) (for constant values of T, P,

M) would be obtained by excluding entirely the
J/j, il/2,
.

iV^

and filling the whole space considered with masses

or whether a certain mixture would give a smaller value,

mass

like 0,

like
it

is

certain that the least possible value of (57) per unit of volume, and

that a negative value, will be realized

homogeneity.

If the

new

by

mass having a certain

part iVfor which the condition (52)

is

not

satisfied occurs between two different original jjarts 0' and O", the
may consider the
ai'gument need not be essentially varied.

We

J.

W.

(rihhs

EqitUlhrmm of Heterogeneous Substcmces.

133

value of (57) lor a body consisting of masses like O' and 0" sepaThis value may be decreased by increasing

rated by a lamina N.

the extent of this lamina, which

may be done

by giving

it

a convoluted form

and

it

will

within a given volume

be evident, as before,

that the least possible value of (57) will be lor a

And

be negative.

aiul that the value will

homogeneous mass,

such a mass will be not

merely an ideal combination, but a body capable of existing, for as the

expression (57) has for this mass in the state considered
sible value per unit of

its least

volume, the energy of the mass included

posa

in

volume is the least possible for the same matter with the
same entropy and volume, hence, if confined in a non-conducting
unit of

vessel,

when

it

will

be

(50), (51),

isfied in

in a state

and

regard to

of not unstable equilibrium.

Therefore

(43) are satisfied, if the condition (52)

all

possible

new

parts, there will

not sat-

is

be some homo-

geneous body which can be formed out of the substances

aS'j,

iS^,

S which will not satisfy condition (53).

Therefore,

if

the initially existing

masses satisfy the conditions

(50), (51), and (43), and condition (53) is satisfied by every homogeneous body which can be formed out of the given matter, there will

be equilibrium.

On

the other hand, (53)

is

not a necessary condition of equilibrium.

For we may easily conceive that the condition (52) shall hold true
(for any very small formations within or between any of the given
masses), while the condition (53)

is

not satisfied (for

all

large masses

formed of the given matter), and experience shows that

often the

case.

this is

very

Supersaturated solutions, superheated w%ater,

etc.,

are familiar examples.

cally unstalde.

By

Such an equilibrium

this

is

however, be practimeant that, although, strictly speakino-^

will,

change may not be

sufficient to

destroy the equilibrium, yet a very small change in the

initial state,

an

infinitely small disturbance or

perhaps a circumstance which entirely escapes our powers of percej)The presence of a small portion of
tion, will be sufficient to do so.
the substance for which the condition (53) does not hold true,
cient to produce this result,

when

this substance forms

is suffi-

a variable

component of the original homogeneous masses. In other cases,

when, if the new substances are formed at all, different kinds must be
formed simultaneously, the initial presence of the different kinds,
and that in immediate proximity, may be necessary.
be observed, that from (56) and (53) we can at once obtain
and (51), viz., by applying (53) to bodies diftering infinitely
from the various homogene<ms tarts of the given mass. There-

It will

(50)
little

134

./

TK Gibbs

Equilibrium of Heterogeneous Substances.

homogeneous parts
bodies
which can be
any
of the given mass) and (53)
are
always
sufficient
for equiwith
formed of the given matter)
(43)
shall be
equilibrium
which
for
an
librium, and always necessary
fore, the

condition (56)

(relating to the various

(relating to

practically stable.

And,

in regard to equations

with

(38), it is

if

we

choose,

For,

(43).

easy to see that

it

if

is

we may get rid of limitation

we compare these equations

always immaterial,

the tests (56) and (53) to any body, how we

Hence, in applying these tests, we may consider
posed.

consider

it

applying

in

to be
all

com-

bodies to

be composed of the ultimate components of the given mass. Then

the terms in (56) and (53) which relate to other components than
Such
these will vanish, and we need not regard the equations (43).
of the constants Jij, M.^
ponents,

may

be regarded,

like

ject only to the conditions (56)

as relate to the ultimate

T anc\
and

compo

J\as unknown quantities sub-

(53).

These two conditions, which are

for equilibrium

sufficient

and

necessary for a practically stable equilibrium, may be united in one,

viz., (if we choose the ultimate components of the given mass for

m relate) that it
the component substances to which m^, m^,
shall be possible to give such values to the constants T, F, M^, M^.,
.

M in the expression {b1) that the value of the expression for

each of the homogeneous parts of the mass in question shall be as
small as for any body whatever made of the same components.
Effect

of Solidity of any Part of

the given

Mass.

If any of the homogeneous masses of which the equilibrium is in

question are solid, it will evidently be proper to treat the proportion
of their components as invariable in the application of the criterion

of equilibrium, even in the case of conqiounds of variable proportions,

even when bodies can exist which are compounded in proportions infinitesimally varied from those of the solids considered.

e.

(Those solids which are capable of absorbing fluids form of course an

It is true
exception, so far as their fluid components are concerned.)
that a solid may be increased by the formation of new solid matter

on the surface where it meets a fluid, which is not homogeneous with

the previously existing solid, but such a deposit will properly be
treated as a distinct part of the system, (viz., as one of the parts

which we have called new). Yet it is worthy of notice that if a homogeneous solid which is a compound of variable proportions is in
contact and equilibrium with a fluid, and the actual components of
the solid (considered as of variable composition) are also actual com-

 Equilihrlmn of Heteroye/ieous Substuitees.

W. Gihbs

./

135

fluid, and the condition (53) is satisfied in regard to

bodies which can be formed out of the actual components of the

ponents of the
all

fluid,

(which will always be the case unless the fluid

is

unstable,) all the conditions will hold true of the solid,

be necessary for equilibrium

if it

were

practically-

which would

fluid.

This follows directly from the principles stated on the })recedinoFor in this case the value of (57) will be zero as determined
pages.
either for the solid or for the fluid considered with reference to their

ultimate components, and will not be negative for any body whatever
which can be formed of these components; and these conditions are
sufticient for equilibrium

Yet the point

masses.
a

is

independently of the solidity of one of the

perhaps of sufticient importance to demand

more detailed consideration.

Let

its

*S,

possible

fluid)

S,, be the actual components of the solid, and A',,,

components (w^hich occur as actual components

then, considering

we

solid as variable,

cW =

shall

t ill]'

dv'

But the

difierentials dm,,'

f.1,,'

dm J
dm,,'

//,/

dm^.',

body by equation

this

-\- //'

equation the potentials

this

S^

the proportion of the components of the

have for

+
By

in the

-i- fx^:

dm.,:.

(58)

are perfectly defined.

//^.'

(12)

-f- fuj dmj

considered as independent,

evi-

dently express variations which are not possible in the sense required
in the criterion of equilibrium.
might, however, introduce them

We

into the general condition of equilibrium, if Ave should express the

dependence between them by the proper equations of condition.

But it will be more in accordance with our method hitherto if we
consider the solid to have only a single independently variable component S^, of which the nature is represented by the solid itself.

We

may

then write

=t' dt/

de'

p' dv' -\-

t-ij

d}uj.

(59)

In regai'd to the relation of the potential /// to the potentials occurring in equation (58) it will be observed, that as we have by integration of (58)

and

(59)

^'

and

if

//^'

"'

=
mj =
e'

therefore

Now,

- p'

i' '/'

t'

+ /'/ ni,!
//

fij

- p'

mj

the fluid has besides S

components

S,

iS,

we may

v>

//,'

S^

+
mj
//,/

and

(60)

//,; 1)1,;,

(61)

m,'.
S,,

write for the fluid

(62)
.

S^.

the actual

J W.

136

6e" =z

a8

Equilihriuin of Heieroyeneous Substances.

p"

t" (h/"

din,,"

l-i,,"

-\-

and

Glbbs

Sv"

+,/'" (^nta'

-^

-\-l-'J' ^^",i"

Sm^:'-\-i.i,'' 6)11,"

ji,:'

l^i"

(hv'\

((53)

by supposition

mj 2r =

m,,' '

ill,'

(64)

equations (43), (50), and (51) will give in this case on elimination of
the constants T, P, etc.,

t'

and

m;

i.>;

u,,; }i:'

may

Equations (65) and (66)

=p\

t",

+*;

may

But
of S
6

t"

-\-iii,l

:=zm-^

f.1,1

condition (53) liolds true of

if

)/

S,

-f-

*S',,,

p"

11

S/

aS'x.,

//" nt
.

jS,

and the

The

fluid.

iA"

all

-j-inj

last con-

(67)

p{J'.

bodies which can be formed

we may

write for

m,,

/V'??J^. ///'w?,

...
.

(66)

be expressed by the equation

also, in virtue of (62),

m,///,,'

//".

be regarded as expressing the condi-

tions of equilibi-ium between the solid

dition

(65)

all

such bodies

///'

//,/' rn,j

(In applying this formula to various bodies,

)ij'

m^

(68)

0.

to be observed that

it is

only the values of the unaccented letters are to be deterraiued

the different bodies to which
letters
(65),

being already determined by the given

and

(67), the value of the first

Avhen applied to the solid in

member

given

its

by

applied, the values of the accented

is

it

Now, by

fluid.)

of this condition

As

state.

is

(60),

zero

the condition must

hold true of a body differing infinitesimally from the

solid,

we

shall

0,

(69)

have
(It

t"

di/ -{-})" dv'

f.i,i'

diitj

or,

and

(65),

Mc")

dnij

(/'//-/'/,")

dm,'

by equations

(58)

{l-ij

/<//'

dm,j

f.1,'/

dm,' ...

-{- {i-ij

;j,'')

(/<,'-//,")

///' diiti!

d)iij

dm,'^

0.

(70)

Therefoi'e, as these differentials are all independent,

/jj

/u,;',

/Y,;

=;/,;',

M,.'= Hi!\

(71)
/V;
which we would

Mt,'^

which with (65) are evidently the same conditions

have obtained if we had neglected the fact of the solidity of one of
the masses.

W. Gibbs

J.

Equilibrium

of Heterogeneous Substances.

137

We

have su2)posed the solid to be homogeneous. But it is evident

that in any case the above conditions must hold for every separate
Hence, the temperature and
point where the solid meets the fluid.
pressure and the potentials for all the actual components of the solid
must have a constant value in the solid at the surface where it meets

by the nature and

number the independent variations
Hence, if we reject as
of which its nature and state are capable.
improbable the supposition that the nature or state of a body can
vary without affecting the value of any of these quantities, we may
the

fluid.

Now,

these quantities are determined

state of the solid,

and exceed

in

conclude that a solid which varies (continuously) in nature or state

at its surface
tains, as

cannot be in equilibrium with a stable

fluid

which con-

independently variable components, the variable components

of the solid.

(There

stable fluid, ^finite

may

mth the same

composed of the
nature and state

be, however, in equilibrium

number of different

solid bodies,

variable components of the fluid, and having their

completely determined by the fluid.)*

Effect

As

of Additional Equations of Condition.

the equations of condition, of which

we have made

use, are

such as always apply to matter enclosed in a rigid, impermeable, and

non-conducting envelop, the particular

which we have found will always be

the

number

conditions of

equilibrium

sufficient for equilibrium.

But

of conditions necessary for equilibrium, will be dimin-

the number of equations

Yet
the
problem
of equilibrium which has
of condition is increased.
sufficiently
indicate
method
the
to be pursued in all
been treated will
cases and the general nature of the results.
It will be observed that the position of the various homogeneous
ished, in a case otherwise the same, as

parts of the given mass, which

is

otherwise immaterial,

mine the existence of certain equations of condition.

different parts of the

system

in

which a certain substance

able component are entirely separated from one another

which

this substance is not a

may

deter-

Thus, when

by

component, the quantity of

is

a vari-

parts of
this sub-

stance will be invariable for each of the parts of the system which are

thus separated, which will be easily expressed by equations of condition.

Other equations of condition may

arise

from the passive forces

(or resistances to change) inherent in the given masses.

*

The

solid

has been considered as subject only to isotropic stresses.

In the probThe

effect of

other stresses will be considered hereafter.

Trans. Conn. Acad., Vol.

III.

18

Novejiber, 1875.

138

W. Glbbs Equilibriain of Heterogeneous

tT.

Suhstcmces.

lem which we are next to consider there are equations of condition

due to a cause of a different nature.

of a Diaphragm {Equilibrmm <f Osmotic Forces).

Effect

If the given mass, enclosed as before,

each of which

is

homogeneous and

divided into two parts,

is

fluid,

a diaphragm which

by

and

capable of supporting an excess of pressure on either side,

is

is

per-

meable to some of the components and impermeable to others, we

shall have the equations of condition

6v'=0,
and

for the

6v"=Qi,

(73)

components which cannot pass the diaphragm

67)1^=0,

dmj'=0,

6mi;=0,

6m,''=0,

etc.,

(74)

and for those which can

Sm/ +
With
rium

doi/ -f 6m/'

drn,''=. 0,

0,

etc.

(75)

these equations of condition, the general condition of equilib(see (15)) will give the following particular conditions:
t'

and

for the

t",

(76)

components which can pass the diaphragm,

if

actual com-

ponents of both masses,

1.1,!

biit

///=//;",

=11,!',

p'

not

nor

/.i,!=/.i",

the diaphragm

= p",
=

/,<j'

/-/,,",

etc.,

(77)

etc.

permeable to the components in certain

Again, if
proportions only, or in proportions not entirely determined yet subis

may be expressed by
equations
linear
between diti^\
will
be
which
equations of condition,
deduction
of
the
the
particular conknown
6m.,', etc., and if these be
difficulties.
no
We
will however
ditions of equilibrium will present
(being
etc.
actual
components
observe that if the components S^, /S2,
certain conditions, these conditions

ject to

on each side) can pass the diaphragm simultaneously in the proportions a

25 ^^^- (^vithout other resistances than such as vanish with
,

the velocity of the current), values proportional to j, a^, etc. are

possible for 6i/i^', 6m J, etc. in the general condition of equilibrium,
6m, "

we

etc. having the same values taken negatively, so that

have for one particular condition of equilibrium

6m o",

shall

aj yUj'+ 2

/'2'

There will evidently be

as

tc.

= !

/f

,"

+ a2

many independent

//2"+

etc.

(78)

equations of this form

J.

as

TT".

Gibhs

Equilibrium of Hete^'ogeueoas Substances.

139

are independent combinations of the elements whicli can

t.liere

pass the diaphragm.

These conditions of equilibrium do not of course depend in any

the supposition that the volume of each fluid mass is kept
In
constant, if the diaphragm is in any case supposed immovable.
fact, we may easily obtain the same conditions of equilibrium, if we

way upon

suppose the volumes variable.

In this case, as the equilibrium must

be preserved by forces acting upon the external surfaces of the

fluids,

the variation of the energy of the sources of these forces must appear
in the general condition of equilibrium,
di:'-\-

(U"

I"

(5v'

which will be

P" dv" ^

(79)

0,

P' and P" denoting the external forces per unit of area.

(Compare
From this condition we may evidently derive the same
(14).)
internal conditions of equilibrium as before, and in addition the
external conditions

p'

= r,

In the preceding paragraphs

the diaphragm
ofiers

is

perfect,

and

p"

its

= F".

(80)

assumed that the

is

it

permeabilit}'^ of

impermeability absolute,

no resistance to the passage

of the

that

e.,

i.

components of the

certain proportions, except such as vanishes with the velocity,

that in other proportions the components cannot pass at

far these conditions are satisfied in

any particular case

is

it

fluids in

all.

and

How

of course to

be determined by experiment.
If the

diaphragm

restriction, the

is

permeable to

all

the n components without

temperature and the potentials for

all the components

must be the same on both sides. Now, as one may easily convince
himself, a mass having n components is capable of only?i + l independent variations in nature and state. Hence, if the fluid on one
side of the diaphragm remains without change, that on the other side

cannot

(in

general) vary hi nature or state.

not necessarily be the same on botli sides.

sure

is

a function of the temperature

Yet the pressure

will

For, although the pres-

and the n potentials,

it

may

be

a many-valued function (or any one of several functions) of these

But when the pressures are difierent on the two sides,
variables.

the fluid which has the less pressure wdll be practicalhj unstable., in
the sense in which the term has been used on page 133.
For
f"

_ ^''^i"+yu" yu/'m/' //^''^a"

//"/;/"

0,

(81)

as appears from equation (12) if integrated on the supposition that

the nature and state of the mass remain unchanged.

p'

<p"

while

t^

^^t".,

;(j'=;/i",

etc.,

Therefore,

if

140

W. Gihbs

J.

e"

t'

Equilihrium of Heterogeneous Snhstances.

ij" -\-2)'

v"

).i^'

m^"

j.io' n't'2"

This relation indicates the instability of

tlie fluid

/'n'

(82)

>'n"<0.

to Avhicli the single

(See page 133.)

accents refer.

But independently of any assumption

in

regard to the permeability

any case in
which each of the two fluid masses may be regarded as uniform
throughout in nature and state. Let the character d be used with
the variables which express the nature, state, and quantity of the
of the diaphragm, the following relation will hold true in

denote the increments of the values of these quantities actu-

fluids to

Then, as the

ally occurring in a time either finite or infinitesimal.

heat received

by

the

two masses cannot exceed t'mf +t"

the increase of their energy

d?/',

and

as

equal to the diflTerence of the heat

is

they receive and the work they do,

Dt'
i.e.,

by

Ttt"

^t'Di/

t"r)>/'

2)'vv' p"Tni",

(83)

(12),

//,'

Dm/ -\-

or
(//,"
It is

-(-

Ml" ^h"

+ /^2'

///) i>m,"-|-

evident that the sign

+ /^2" D^'s" +

i^'^'s'

i/io"

- Ms)

i>"'2"+

etc.

etc.

^ 0,

to.

(84)
(85)

holds true only in the limiting case in

which no motion takes place.

DEFINITION AND PROPERTIES OF FUNDAMENTAL EQUATIONS.

which we have been

depend upon the equations which
express the relations between the energy, entropy, volume, and the
quantities of the various components, for homogeneous combinations
Tlie solution of the problems of equilibrium

considering has been

made

to

of the substances which are found in the given mass.

The nature

of

such equations must be determined by experiment. As, however, it

is only differences of energy and of entropy that can be measured, or
indeed, that have a physical meaning, the values of these quantities
are so far arbitrary, that

we may choose independently

simple substance the state in which

its

energy and

its

for

each

entropy are

both zero. The values of the energy and the entropy of any compound bodv in any particular state will then be fixed. Its energy
will be the sum of the work and heat expended in bringing its components from the states in which their energies and their entropies
and its
are zero into combination and to the state in question
;

entropy

is

the value of the integral /

for

any

reversible process

141

W. GihhsEqulUhruim of Heterogeneous Substances.

J.

[dQ denoting an element of the

treated, and t the tempeiature
thus
heat communicated to the matter
both of the energy
determination
In the
of the matter receiving il).
that change

by which

effected

is

and of the entropy, it is understood that at the close of the process,

all bodies which have been used, other than those to which the determinations relate, have been restored to their original state, with the
exception of the sources of the work and heat expended, which must

be used only as such sources.,

We know, however, a priori, that

homoge-

the quantity of any

if

independently variable components varies

neous mass containing n

m will
and not its nature or state, the quantities f, ?/, v, m,, mg,
learn
if
we
sufficient
is
it
therefore
all vary in the same proportion
quanof
these
one
from experiment the relation between all but any
.

Or,

given constant value of that one.

tities for a

we may

we have to learn from experiment the

quantities
between the 7i 4- 2 ratios of the n -{

relation

that

f, ij,

'i

etc.,

To

m^.
that

and

-,

is,

which

ni in m
,

may

take for these ratios

m^,

rn^,

-, -,

^,

-,

is

be called the densities of energy and entropy.

but one component,

w + 1 independent
mined by experiment.
if f is

it

variables, of

known

function of

may

be more convenient to

In any case,

as the three variables.

tion of

Now

we may

v,

the separate densities of the components, and the ratios

But when there

choose

our ideas

fix

consider

subsisting

it is

which the form

//,

w,

/1 2

m^, m^,

is

?,

only a functo be deter-

as

by equa-

tion (12)

dE=Lt

di]

pdv

^^ dni^

dni2

/<dni,

(86)

t, p, pi-i, 1^21
/^'n ^'"^ functions of the same variables, which may
be derived from the original function by differentiation, and may
therefore be considered as known functions.
This will make n -\- 3
independent known relations between the 2n + 5 variables, e, ;/, v

w?j,

mg,

m, t,p,

of these variables,

yUj,

Uo,
are

//.

These are

all

that exist, for

evidently independent.

Now

upon

these relations depend a very large class of the properties of the

compound

considered,

we

may

say

in

general,

all

its

thermal,

mechanical, and chemical properties, so far as active tendencies are

concerned, in cases in which the form of the mass does not require
consideration.

single equation from

which

all

these relations

may

142

W.

J.

Equillhrmm of Heterogeneous

G'lbhs

we

Substances.

fundamental equation for the substance in

more general form of the fundamental equation for solids, in which the pressure at any point is not
supposed to be the same in all directions. But for masses subject only
/ is
to isotropic stresses an equation between , ;/, v, m^,m,
be deduced

will call a

We shall

question.

hereafter consider a

which possess

Tliere are other equations

a fundamental equation.

same property.*

this

Let

t=:e-t

(87)

;/,

we

then by differentiation and comparison with (86)

(If
then,

If,

find

known

is

//'

p, Ml, /'},

1/,

substitute for

we

pdv +

//dt

//'

^2

-|-

t,

our original equation

-f-

v,

f^'^2

+/'f.c?>yi.

^^ ni.^,

terms of the same variables.

/'n ill

in

dm^

as a function of

have again n

shall

//,

obtain

its

m,
If

we can
we then

value taken from eq. (87),

independent relations between the same

as before.

2n -\- 5 variables
Let

X=e+pv,
then by

V, /^j,

t,

tdif

dp

X be known

then,

If,

(89)

(86),

dx
find

(88)

/.i^,

/<!

(7m

/'g ^^'"2

as a function of
.

//

?/,

p,

m^,

tn^,

we can
By elimi-

?;?,

terms of the same variables.

in

(90)

/' ^^"^n-

nating Xi we may obtain again n + 3 independent relations between

the same 2n + 5 variables as at first.

Let
K

then,

by

d'Q=~If,

then,

=s-

t,j

+pv,

(91)

(86)

'C,

is

i]dt

-\-

known

dp

-{

/^i

dm^

-f-

as a function of

j-i2dm
p.,

#,

m^,

-f-

m.^,

/'f?wv
.

(92)

we can

* M. Massieu (Comptes Rendus, T. Ixix, 1869, p. 858 and p. 1057) has shown
all the properties of a fluid " which are considered in thermodynamics" may be

how

deduced from a single function, which he calls a characteristic function of the fluid
In the papers cited, he introduces two different functions of this kind

considered.
viz.,

a function of the temperature and volume, which he denotes by

which

in our notation

would be

and pressure, which he denotes by

p

_i,

jj'y

of the

rp',

tr/

or

the value of

and a function of the temperature

the value of which in

our notation would be

In both cases he considers a constant quantity (one kilogram)

which

ip,

tp

or -7-.
t

fluid,

is

regarded as invariable in composition.

yWn ^n,

144

J. W^.

Gtbhs Equilibrmiii of Heterogeneous Substances.

'

the subscript numerals refer, (but not excluding the case in which

1 and the composition of the body is invariable,) there is a relabetween the quantities enumerated in any one of the above sets,
from which, if known, with the aid only of general principles and
relations, we may deduce all the i-elations subsisting for such a mass
between the quantities 6,
iii, t, jy, ji^, pi.^,
//, y, ni^^ m.^,
j,
//

tion

i:,

//-,

i-i.

define

^',

It

j,

and

between these

be observed that,

will

one

thei-e is

c,

besides

equations which

the

finite equation, (93),

which subsists

independently of the form of the fundamental

q^^antities

equation.

might of course be added which possess

mentioned on
account of the important properties of the quantities i/\ j,
and
Other

the

sets of quantities

same property.

The

sets (100), (101), (102) are

'Q,

because the equations

(90),

(88),

(92), like (86), afford

convenient

definitions of the potentials, viz.,

etc.,

=im

=(m

;,,=(*)

where the subscript

letters

constant in the differentiation,

=(/L)

(104)

denote the quantities which remain

being written for brevity for

all

the

}n except the one occurring iu the denominator.

m^, r/ig,
It will be observed that the quantities in (103) are all independent
of the quantity of the mass considered, and are those which must, in
general, have the same value in contiguous masses in equilibrium.
letters

On
The quantity

//'

the quantities

ip,

x,

'i-

has been defined for any homogeneous mass

equation

//'

by

the

(105)

ttj.

between
e, ?7, ,

m,, m2,

with one between

e,

V,

t,

m,,

m.2,

m.

As. by (86),

^= il)
the second equation

may

evidently be derived from the

first.

But the

first

equation

cannot be derived from the second; for an equation between

e>

is

(^)

V,

TO,,

m,,

TO

equivalent to one between

ldv\

[del vm

^. ^'

"^M 2!

^n-

'

which

is

evidently not sufficient to determine the value of

variables.

//

in

terms of the other

W. Gibbs

J.

Equilibrium

of Heterogeneous Substances.

145

We may extend this definition to any material system whatever

which has a uniform temperature throughout.
If we compare two states of the system of the same temperature,
we have
(106)
f-,l"=e-e''-t(v'~>j").
If we suppose the system brought from the first to the second of

these states without change of temperature and

which

cess in

by a reversible prowork done and Q the heat received by the

the

is

system, then

t"-W- Q,
= Q.
t{7i" ~
-

e'

and
Hence
and

{101)

(108)

]/)

f-f' = W',

for an

infinitely small

reversible

(109)

change

the

in

system, in which the temperature remains constant,

state of the

we may

write

-dip = dW.
Therefore,

That

is, if

we

the force function of the system for constant

is

//'

temperature, just as

(110)

consider

is

//'

the force function for constant entropy.

as a function of the temperature

and the

variables which express the distribution of the matter in space, for

every different value of the terapei-ature

required

function

by the system

if

//'

is

the diffei-ent force

maintained at that special

temperature.

From

this

we may conclude

when a system has

that

a uniform

temperature throughout, the additional conditions which are necessary

and

sufficient for

equilibrium

may

be expressed by

W).^o.*

(Ill)

* This general condition of equilibrium might be used instead of

(2) in

such prob-

lems of equiUbrium as we have considered and others which we shall consider hereafter with evident

advantage in respect to

expressed by the subscript

rately,

<

tlie

brevity of the formulae, as the limitation

in (111) applies to

every part of the system taken sepa-

and diminishes by one the number of independent variations in the state of

these parts which

we have

to consider.

paper has been chosen, among

The more cumbersome course adopted

otlier reasons, for the

sake of deducing

all

in this

the particular

conditions of equilibrium from one general condition, and of having the quantities

mentioned
defined

in this general condition

and because

such as are most generally used and most simply

in the longer formulas as given, the reader will easily see in

case the form which they would take

tion of equilibrium,
for granted,

and

which would be

to seek only the

treated on pages 116

(15),

ff.,

we should adopt

in effect to take the

III.

For example,

in the

problem

obtain from (111) by (88) a condition precisely like

tSri', t^r)", etc.

Trans. Conn. Acad., Vol.

each

(111) as the general condi-

thermal condition of equilibrium

remaining conditions.

we would

except that the terms

if

would be wanting.
19

January, 1876.

146

J.

When

TK Gibhs

Equilibrivui of Heterogeneous Substances.

not possible to bring the system from one to the other

it is

of the states to which

and

//;'

altering the temperature,

'/;"

rehite

by a

reversible process without

be observed that

will

it

it is

not necessary

for the validity of (107)-(109) that the temperature of the

system

should remain constant during the reversible process to which

TFand

relate,

provided that the only source of heat or cold used has the

same temperature
external bodies

system

as the

may be

ing the condition of reversibility,

dition at the close of the process

if

It

maybe

tions (111)
in the

show
when applied

(2)

given state

is

restored to their original con-

may

be restored to the

directly the equivalence of the condito a

system of which the temperature

uniform throughout.

any variations

If there are

Any
aifect-

has been taken.

it

interesting to

and

in

nor does the limitation in regard

to the use of heat apply to such heat as

source from which

final state.

any way not

in its initial or

used in the process

in the state of such a

system which do

not satisfy (2), then for these variations

(^6

If the

and

temperature of the system

we may evidently
by supposing heat

And

<

increase
to

its

6t; :=. 0.

not uniform,

in its varied state is

entropy without altering

pass from

the

warmer

to

the state having the greatest entropy for the energy

For

necessarily be a state of uniform temperature.

its

energy

the cooler parts.

f -|- (Jf

will

this state (regarded

as a variation from the original state)

S<Q
Hence, as we

may

and

(SjjX).

diminish both the energy and the entropy by cool-

ing the system, there must be a state of uniform temperature for

which (regarded as a variation of the original state)

6e<0
From

this

we may conclude

and

djj

that for systems of initially uniform tem-

perature condition (2) will not be altered

to such as

0.

if

we

limit the variations

do not disturb the uniformity of temperature.

Confining our attention, then, to states of uniform temperature,

we

have by differentiation of (105)

6

Now

t6t/=z6f-]-t/6t.

(112)

there are evidently changes in the system (produced

by heating

or cooling) for which

- t6?j=0

and therefore

rh/-

-f

?/ f)7

0,

(113)

W. Gibhs

J.

Equilibrium of Heterogeneous Substances.

This consideration

neither 6)j nor St having the value zero.

cient to

show that the condition

de

and that the condition (111)

(2) is

147

is suffi-

equivalent to

tdi]^0.

is

(114)

equivalent to

6il^-{-if6t^0

and by (112) the two

In such cases as

(115)

last conditions are equivalent.

we have

considered on pages 115-137,

the form and position of the masses of which the system

is

is

in

which

composed

immaterial, uniformity of temperature and pressure are always

necessary for equilibrium, and the remaining conditions,

are satisfied,

may be

by means

conveniently expressed

when

these

of the func-

C, which has been defined for a homogeneous mass on page 142,

and which we will here define for any mass of uniform temperature
and pressure by the same equation

tion

= e tt]-\-pv.

For such a mass, the condition of

(Ii6)

(internal) equilibrium is

m,p^^That

(iiv)

this condition is equivalent to (2) will easily ap[)ear

from con-

siderations like those used in respect to (111).

Hence,

it is

necessary for the equilibi'ium of two contiguous masses

identical in composition that the values of

quantities of the

two masses should be

as determined for equal

t,

equal.

Or,

when one of three

contiguous masses can be formed out of the other two,

for equilibrium that the value of

should be equal to the

sum

for

it is

any quantity of the

of the values of

necessary
first

mass

for such quantities of the

second and third masses as together contain the same matter.

Thus,

composed of <i i)arts of water and b

contact with vapor of water and crystals of

for the equilibrium of a solution

parts of a salt which

the

salt, it is

is in

necessary that the value of

solution should be equal to the

ties

a of the vapor and b of the

true in

more complicated

cases.

for the quantity ((-\-b oi the

sum of the values

salt.

of

'Q

for the quanti-

Similar propositions will hold

The reader

will easily

deduce these

conditions from the particular conditions of equilibrium

page

In like

manner we may extend the

definition of x to any mass or

which the pressure is everywhere the same,
for the energy and v for the volume of the whole and setting

combination of masses
using

given on

128.

in

as before

X=t-\-pv.

(118)

48

If

J.

we

W.

Gihhi^

denote by

Equilibrium of Heterogeneous Substances.

by the combined masses from

the heat received

is

not varied,

the system

by accents

external sources in any process in which the pressure

and

disting-iiisli tlie initial

we have

x"

and

= ^"

x'

final states of

f'

('""

+i>

"')

= Q-

(iif)

This function may therefore be called the heat function for constant
pressure (just as the energy might be called the heat function for
constant volume), the diminution of the function representing in all
cases in which the pressure

system.

In

all

not varied the heat given out

is

cases of chemical action in which no heat

to escape the value of

is

by

the

allowed

I'emains michanged.

POTENTIALS.
In the definition of the potentials

homogeneous mass was considered

/z^,

/y,,

etc.,

the energy of a

as a function of its entropy, its

volume, and the quantities of the various substances composing it.

Then the potential for one of these substances was defined as the differential coefficient of the

energy taken with respect to the variable

expressing the quantity of that substance.

Now,

as the

manner

in

which we consider the given mass as composed of various substances

is in some degree arbitrary, so that the energy may be considered as
a function of various different sets of variables expressing quantities
of component substances, it might seem that the above definition

does not

the value of the potential of any substance in the given

fix

mass, until

we have

fixed the

sidered as composed.

by

manner

For example,

in
if

which the mass is to be conwe have a solution obtained

dissolving in water a certain salt containing water of crystalliza-

tion,

we may

hydrate and

consider the liquid as composed of

w?-

m^ weight-units

of the

of water, or as composed of m, of the anhydrous

It will be observed that the values of m., and

salt and m of water.
m, are not the same, nor those of m. and ?,, and hence it might
seem that the potential for water in the given liquid considered as

composed

of the hydrate

and water,
ds

viz.,

Xdinjylr/,

would be
sidered as

V,

ms

from the potential for water in the same liquid concomposed of anhydrous salt and water, viz.,

different

dmjr),

V,

m.

./.

W. Gihbs

The value
m^-

is

c?m,

of the

EquilihrluTn of Heterogeneous Substances.

two expressions

not equal to

m,^.,

we may

and then the numerators

however, the same,

is,

for,

dni,

in the

two

fractions will also be equal,

we may

when

the

added without altering the entropy

Precisely the same considerations will

of water

and volume of the liquid.

apply to any other case.
In fact,

although

of course suppose dm^- to be equal to

as they each denote the increase of energy of the liquid,

quantity dm^y or

149

is

give a definition of a potential which shall not pre-

suppose any choice of a particular set of substances as the components

of the homogeneous mass considered.

If to any homogeneous mass we suppose an infinitesiDefinition.

mal quantity of any substance to be added, the mass remaining
homogeneous and its entropy and volume remaining unchanged, the
increase of the energy of the mass divided by the quantity of the
substance added is the potential for that substance in the mass con-

(For the purposes of this definition, any chemical element or

in given proportions may be considered a

sidered.

combination of elements

substance, whether capable or not of existing by itself as a homoge-

neous body.)
In the above definition we may evidently substitute for entropy,
volume, and energy, respectively, either temperature, volume, and
the function
or entropy, pressure, and the function j or tempera?/ ;

and the function

(Compare equation (104).)
In the same homogeneous mass, therefore, we may distinguish the
potentials for an indefinite number of substances, each of which has a'
perfectly determined value.

ture, pressure,

'Q.

Between the potentials

for different substances in the

same homo-

geneous mass the same equations will subsist as between the units

That

of these substances.

is, if

are components of anj^ given

i^

a, 6, etc.,

/^

(Bk, S;, etc.

the substances,

aS', aS',

etc.,

aS^.,

/S'

etc.,

homogeneous mass, and are such that

+ etc. =

(5;.

+ A ,

-|- etc.,

20)

denoting the units of the several substances,

denoting numbei-s, then if /<, //, etc., /z^, //,,

and

a,

etc.

denote the potentials for these substances in the homogeneous

etc., h, A, etc,

/J,

mass,

a /<

4-

fJ

//,,

+ etc. =

/ii

//,

+ etc.

(121)

we will suppose the mass considered to be very large.

number of (121) denotes the increase of the energy of
the mass produced by the addition of the matter represented by the
first member of (120), and the second member of (121) denotes the

To show

this,

Then, the

first

150

W. Gihbs

J.

Equilibrium of Heterogeneous Substances.

increase of energy of the

same mass produced by the addition of the

matter represented by the second member of (120), the entropy and

A^olume of the mass remaining in each case unchanged. Therefore, as

members of
20)
two members

the two

{ 1

But

represent the same matter in kind and

must be equal.
must be understood that equation (120)

quantity, the
it

of (121)

intended to

is

denote equivalence of the substances represented in the mass conin other words, it is supsidered, and not merely chemical identity
posed that there are no passive resistances to change in the mass
;

considered which prevent the substances represented by one

of (120) from passing into those represented

example,

in respect to a

by the

For

mixture of vapor of water and free hydrogen

we may

and oxygen

(at

but water

to be treated as an independent substance,

is

member

other.

ordinary temperatures),

not write

and no neces-

sary relation will subsist between the potential for water and the
potentials for

The reader

hydrogen and oxygen.

by equations

will observe that the relations expressed

(which are essentially relations between the potentials for actual components in diffei-ent parts of a mass in a state of
equilibrium) are simply those which by (121) would necessary sub-

and

(43)

sist

(51)

between the same potentials in any homogeneous mass containing

components all the substances to which the potentials

as variable
relate.

In the case of a body of invariable composition, the potential for

is equal to the value of C for one unit of the

the single component

body, as appears from the equation

'

r=j.im

(122)

Therefore, when n =. 1, the funto which (96) reduces in this case.

quantities
in the set (102) (see page
damental equation between the
143) and that between the quantities in (103) may be derived either
from the other by simple substitution. But, with this single excep-

an equation between the quantities in one of the sets (99)-(103)

cannot be derived from the equation between the quantities in
another of these sets without differentiation.

tion,

Also

in the case of a

body of

variable composition,

when

all

the

quantities of the components except one vanish, the potential for

for one lanit of the body.
that one will be equal to the value of
may make this occur for any given composition of the body by
'C,

We

J.

W. Gibhs

Equilihrium of Heterogeneous Substances.

151

choosing as one of the components the matter constituting the l)ody

for one unit of a body may always be
Hence the relations between the values of
for contiguous masses given on page 14Y may be regarded as relations between potentials.
The two following propositions afford definitions of a potential
which may sometimes be, convenient.
The potential for any substance in any homogeneous mass is equal
to the amount of mechanical work required to bring a unit of the
substance by a reversible process from the state in which its energy
and entropy are both zero into combination with the homogeneous
mass, which at the close of the process must have its original volume,
and which is supposed so large as not to be sensibly altered in any
All other bodies used in the ])rocess must by its close be
part.

itself,

so that the value of

t.

considered as a potential.
t,

state, except those used to supply the

work, which must be used only as the source of the work. For, in

restored to their original

a reversible process,
altered, the entropy

when

But the

not be altered.

the entropies

original entropy of the substance

therefore the entropy of the mass

substance.

of other bodies are not

of the substance and mass taken together will

is

is

zero

not altered by the addition of the

Again, the work expended will be equal to the increment

of the energy of the mass and substance taken together, and therefore
equal, as the original energy of the substance

is

zero, to the

increment

of energy of the mass due to the addition of the substance, which

the definition on page 149

The

is

by

equal to the potential in question.

potential for any substance in any

homogeneous mass

to the work required to bring a unit of the substance

by

is

equal

a reversible

which
and the temperature is the same
as that of the given mass into combination with this mass, which at
the close of the process must have the same volume and temperature
as at first, and which is supposed so large as not to be sensibly
altered in any part.
A source of heat or cold of the temperature
of the given mass is allowed, with this exception, other bodies are
to be used only on the same conditions as before.
This may be
process from a state

in'

ij:

shown by applying equation

(109) to the

mass and substance taken

together.

The

last proposition enables us to see

the potential

is

affected

very

easily,

how

the value of

by the arbitrary constants involved

in the

energy and the entropy of each elementary subFor we may imagine the substance brought from the state

definition of the

stance.
in

which

//'

=:

and the temperature

is

the

same

as that of the given

152

W. Gibbs

J.

mass,

first

any

to

Equilibrium

of Heterogeneous Substances.
same temperature, and then

specified state of the

into combination with the given mass.

cess the

work expended

is

In the

first

part of the pro-

evidently represented by the value of

denoted by

and

'/',

work expended

in

let

/<

denote the potential

ju z=z

arbitrary,

we may

//''

JC,

of
t

'/,

-[-

as aforesaid

W the

then

W.

(123)

all

6=0

and

//

is

zz:

or e

by any constant C, and the

by any constant IT.
any state would then be increased by

possible states

f //,

in

for

all

possible states

denoting the temperature of the

in (123)

and

simultaneously increase the energies of the unit of

entropies of the substance

The value
to

mass

as the state of the substance for which

the substance in

C^

in question,

bringing a unit of the substance from the specified

state into combination with the given

Now

ip

Let this be

for the unit of the substance in the state specified.

and observing that the

last

state.

term

Applying

in this

this

equation

is

independent of the values of these constants, we see that the potential

would be increased by the same quantity C ( K, t being the temperature of the mass in which the potential

is

to be determined.

ON COEXISTENT PHASES OF MATTER.

In considering the different homogeneous bodies which can be
formed out of any set of component substances, it will be convenient
to have a

term which shall refer solely to the composition and therstate of any such body without regard to its quantity or

modynamic

We

form.

may

call

such bodies as differ in composition or state

dif-

which
examples of the same

ferent phases of the matter considered, regarding all bodies

only in quantity and form as different

Phases which can exist together, the dividing surfaces being

differ

phase.

plane, in an equilibrium

ances to change,

we

which does not depend upon passive

resist-

shall call coexistent.

homogeneous body has n independently variable components,

body is evidently capable of n. -}- 1 independent variA system of r coexistent phases, each of which has the same
ations.
r varian independently variable components is capable of n -{- 2
For the temperature, the pressure, and the potentions of phase.
tials for the actual components have the same values in the different
phases, and the variations of these quantities are by (97) subject to
Therefore, the numas many conditions as there are different phases.
If a

the phase of the

ber of independent variations in the values of these quantities, i. e.,

the number of independent variations of phase of the system, will be

n+2

-r.

./.

Or,

W. GibbsEquilihrhtm of Heterogeneous

when the

if

we

still

153

have not the same independently

r bodies considered

variable components,

Substances.

denote by n the number of independ-

ently variable components of the r bodies taken as a whole, the

number

of independent variations of phase of which the system

capable will

be n-\-2 r.

still

In this case,

consider the potentials for more than

and

(51)

substances.

shall

have by

Let

(97), as

between the variations of the temperature, of the

before, r relations

relations

We

is

be necessary to

will

n component

the number of these potentials be n-\-h.

pressure,

it

and of these n + h potentials, and we shall also have by (43)

h relations between these potentials, of the same form as the
which subsist between the units of the

different

component

substances.

Hence,

if

r z= w

istent) is possible.

2,

no variation

the phases (remaining coex-

in

does not seem probable that r can ever exceed

It

+ 2. An

example of n =z 1 and r z=. 3 is seen in the coexistent solid,

and gaseous forms of any substance of invariable composition.
It seems not improbable that in the case of sulphur and some other
simple substances there is more than one triad of coexistent phases
71

liquid,

but

it is

entirely improbable that there are four coexistent phases of

An example

any simple substance.

of

7i

=2

and r:=4

seen in a

is

solution of a salt in water in contact with vapor of water and

two

different kinds of crystals of the salt.

Concerning n

We

-\- I

Coexistent Phases.

now seek the differential equation which expresses the

between the variations of the temperature and the pressure
in a system of w -f 1 coexistent phases ( denoting, as before, the
number of independently variable components in the system taken as
will

relation

a whole).

In this case

we have

>i

equations of the general form of (97)

we may distinguish

(one for each of the coexistent phases), in which

the quantities
accents.

the same

But
is

//,

v,

mj, m^,

and^

true of

different equations.

relating to the different phases by

have the same value throughout, and

etc.

will each

//j, //g, etc.,

If the total

so far as each of these occurs in the

number

of these potentials

is

+ A,

there will be h independent relations between them, corresponding to

the h independent relations between the units of the component substances to which the potentials relate,

by means

of

which we

may

eliminate the variations of h of the potentials from the equations of

the form of (97) in which they occur.

Trans. Conn. Acad., Vol.

III.

20

January, 1876.

154

W. Gihhs

J.

Equilibrium of Heterogeneous Substances.

Let one of these equations be

v'

dp=z

7/ dt

+ mj

and by the proposed elimination

dj.!^,

let it

m,'

be observed that

//,

etc.,

(124)

become

W dp=:zif dt + A^' dfi^ + A2' d).i2

It will

df-ij,

-\-A,!df.i.

(125)

for example, in (124) denotes the poten-

which may or may not

AS'2, etc. to which the
potentials in (125) relate.
Now as the equations between the potentials by means of which the elimination is performed are similar to
those which subsist between the units of the corresponding substances, (compare equations (38), (43), and (51),) if we denote these
units by , j, etc., i, 3, etc., we must also have
tial in

the mass considered for a substance

be identical with any of the substances

^?\'a

But the

*S

y8j,

+ ''6'A+etc. = ^/ 1 + ^12' 2

first

member

+^^n'. (126)

of this equation denotes (in kind and quantity)

the matter in the body to which equations (124) and (125) relate.

we may regard

the same must be true of the second member,

body

as

quantity

AJ

which
\i'

We

of the substance S2, etc.

will then

dp=L

rf

dt

m^\

will therefore, in accordetc. for

A ^\ ^2?

^^' ^"

become

-^^

m^ d}.i^

-{ rn^

dj-i^,

But we must remember that the components

etc.

As
same

composed of the quantity A^' of the substance S^, with the

ance with our general usage, write m^'

(125),

this

-{

to

rnj

(12V)

djJ^.

which the m/, mg',

of this equation relate are not necessarily independently variable,

as are the

(97)

and

may be reduced

to a

components to which the similar expressions

(124) relate.

The

rest of the

71

equations

in

similar form, viz.,

v"

dp

= if dt

7n^"

df.1^

^m.^'dj-i^

-^m^'dpt^,

(128)

etc.

By elimination
V

of

<:?yu,, df.i^t

dj.4

from these equations we obtain

W. Gibhs

J.

When

.Equilihrium of Heterogeneous Substmices.

11-=. 1,

(/' v'
or, if

we make

ni'

=.

- rn' v")
1

which

dp

{m"

if

tn"

1,

v'-v"

t{v"

(130)

ui' ,/') (7t,

= we have the usual

^=3'^:^=:^^and

dt
in

155

formula
(131)

-v'Y

'

denotes the heat absorbed by a unit of the substance in

passing from one state to the other without change of temperature or

pressure.

Concerning Cases in ^vhlch the Number of Coexistent Phases

than n-\- 1.

When

7i>

1, if

the quantities of

are proportional in

the components 8y,

all

-Sg,

is less

S^

two coexistent phases, the two equations of the

be

sufficient

for the elimination of the variations of all the potentials.

In fact,

form of (127) and (128) relating to these phases

will

the condition of the coexistence of the two phases together with the
condition of the equality of the n

with the n
ji>

ratios of */', "iJ',

as a function of

to
if

if

ratios of

w/,

mg',

the fundamental equation

known

is

may

differential equation in this case

?'

determine

wi" is sufficient to

for each of

be expressed

form of (130), m' and m" denoting either the quantities of any
components or the total qiiantities of matter in the bodies

in the

one

The

the phases.

of the

which they

relate.

Equation (131) will also hold true

the total quantity of matter in each of the bodies

this case differs

the heat

from the preceding

in that the

is

in this case,

unity.

But

matter which absorbs

passing from one stat^ to another, and to which the other

in

formula relate, alt^iough the same in quantity,

letters in the

is

not in

general the same in kind at different temperatures and pressures.

Yet the case

will often occur that one of the phases

invariable in composition, especially

when

and

tlie

i)i

this case the

matter to which

it

is

essentially

a crystalline body,

is

letters in

(131) relate will

not vary with the temperature and pressure.

When n =
ature

is

two coexistent phases are capable, when the temperBut as (130) will
this case when m^' m^
m/' ni^'^ it follows that for
2,

constant, of a single variation in phase.

hold true in

constant temperatui-e the pressure

imum when

is

the composition of the

maximum

in general a

two phases

is

manner, the temperature of the two coexistent phases

maximum

or a minimiam, for constant pressure,

or a min-

identical.
is in

In like

general a

when the composition

two phases is identical. Hence, the series of simultaneous

values of t and p for which the composition of two coexistent phases
of the

156

Gibhs

TF.

Equilibrium of

Ffeterogeiieoiis Substa7ices.

identical separates tliose sii)iultaneous values of

is

and

which

2^ foi"

no coexistent phases are possible from those for which there are two
This may be applied to a liquid having
pair of coexistent phases.
two independently variable components in connection with the vapor
which it yields, or in connection with any solid which may be formed
in

it.

When

we have

z=. 3,

for three coexistent phases three equations

of the form of (127), from which

m
m

m,

Now

rf

dp=.\?f

we may

m^

m^

tn^"

tn^'

obtain the following,

""1

df-

m,"

dM^. (132)

}}'" )/l^"' Dl.j'"

the value of the last of these determinants will be zero,

the composition of one of the three phases

by combining the other

is

when

such as can be produced

Hence, the pressure of three coexistent

two.

maximum or minimum for constant temtemperature a maximum or minimum for constant

phases will in general be a

perature, and the

when the above condition in regard to the composition of

the coexistent phases is satisfied. The series of simultaneous values
pressure,

which the condition is satisfied separates those simultaneous values of t and /> for which three coexistent phases are not
possible, from those for which there are two triads of coexistent
These propositions may be extended to higher values of ?i,
phases.
of

and

and

2^ foi"

by the

illustrated

solutions of

71

boiling temperatures and pressures of saturated

2 diiferent solids in solvents

having two independ-

ently variable components,

INTERNAL

We

will

HOMOGENEOUS FLUIDS
FUNDAMENTAL EQUATIONS.

STABILITY OF

now

envelop which

AS INDICATED BY

consider the stability of a fluid enclosed in

is

a rigid

non-conducting to heat and impermeable to

all

the

components of the fluid. The fluid is supposed initially homogeneous

in the sense in which we have before used the word, i. e., uniform in
/She
every respect throughout its whole extent. Let S^, S.j,
we may then consider every
the idtimute components of the fluid
body which can be formed out of the fluid to be composed of /S'j, /Sg,
m denote
Let m^, m^,
that in only one way.
;S', and
the quantities of these substances in any such body, and let f, //, v,
.

denote
for

us

its

energy, entropy, and volume.

compounds
all

of S^, S^,

aS',

if

The fundamental equation

completely determined, will give

possible sets of simultaneous values of these variables for

oeneous bodies.

homo-

W. Gibbs Equilibriwn of Heterogeneous

J.

Now, if
M^, M2,

possible to assign

is

it

157

Substances.

such values to the constants T, P,

that the value of the expression

Tt]-\-

Pv ~ J/, mj - M2 m^

3fm

(133)

and shall be positive for every other

shall be zero for the given
phase of the same components, i. e., for every homogeneous body*
fluid,

not identical in nature and state with the given fluid (but composed
entirely of

aS\,

/S'g,

/S),

the condition of the given fluid will be

stable.

For,

any condition whatever of the given mass, whether or not

in

homogeneous, or

fluid, if

the value of the expression (133)

negative for any homogeneous part of the mass,

its

is

not

value for the

whole mass cannot be negative; and if its value cannot be zero for
any homogeneous part which is not identical in phase with the mass
in its given condition, its value cannot be zero for the whole except
when the whole is in the given condition. Therefore, in the case
supposed, the value of this expression for any other than the given
(That this conclusion cannot be
condition of the mass is positive.
invalidated by the fact that it is not entirely correct to regard a
composite mass as made up of homogeneous parts having the
same properties in respect to energy, entropy, etc., as if they were
parts of larger homogeneous masses, will easily appear from considerations similar to those adduced on pages 131-133.)
If, then, the
value of the expression (133) for the mass considered is less when it
is in the given condition than when it is in any other, the energy of
the mass in its given condition must be less than in any other condition in which it has the same entropy and volume.
The given con(See page 110.)
dition is therefore stable.
Again,

if it is

possible to assign such values to the constants in

(133) that the value of the expression shall be zero for the given
fluid mass,

and

shall not

be negative for any phase of the same com-

ponents, the given condition will be evidently not unstable.

page

110.)

It will

be stable unless

it is

(See

possible for the given matter

volume and with the given entropy to consist of homofor all of which the value of the expression (133) is zero,
but M^hich are not all identical in phase with the mass in its given condition.
(A mass consisting of such parts would be in equilibrium, as
we have already seen on pages 133, 134.) In this case, if we disre-

in the given

geneous parts

gard the quantities connected with the surfaces which divide the
*

A vacuum is throughout this

extremely rarified body.

vacuum

We

discussion to be regarded as a limiting case of an

maj^ thus avoid the necessity of the specific mention of a

in propositions of this kind.

158

W. Gibhs

J.

homogeneous

Equ'dihfium of Heterdgeneous
we must regard

parts,

But

neutral equilibrium.

Siibstances.

the given condition as one of

regard to these homogeneous parts,

in

which we may evidently consider to be all diiFerent phases, the fol(The accents distinguish the
satisfied.
letters referring to the different parts, and the unaccented letters
lowing conditions must be

whole mass.)

refer to the

rf

+ if + etc. =

v'

?Mj'

v"

-\- etc.

/^,

V,
I

+ m/' -|- etc.

=/>!',,

etc.

Now

the values of

mass

fluid

^-,

etc.

in its

>,

v,

//,

m^, m2,

are determined

coexistent phases of which the

(134) as

,,

etc.,

in fact, tlie

j-.

jj-.

between

v',

whole

set of

we may regard

Flence,

latter is one.

linear equations

Now

(The values of

v" , etc.

one solution of these equations must give us the

given condition of the

fluid

and

it is

not to be expected that they

be capable of any other solution, unless the number of different

homoo-eneous parts, that

is o-reater

than n

is,

the

We

2.

not probable that this

is

mass

will

be

in neutral

of the substances,

if

number of different coexistent

phases,

have already seen (page 153) that

it

is

ever the case.

We may, however, remark

fluid

etc. are also subject to the condition that none of them can be

negative.)

will

the phases of the various

They form,

the phase of the fluid as given.

v",

by

of

But the phases of these parts are evidently determined by

parts.

v'

by the whole

are determined

etc.

given state, and the values

etc., etc.,

(134)

)^

that in a certain sense an infinitely large

equilibrium in regard to the formation

such there are, other than the given

fluid, for

which the value of (133) is zero (when the constants are so determined that the value of the expression is zero for the given fluid,
and not negative for any substance) for the tendency of such a formation to be reabsorbed will diminish indefinitely as the mass out of
;

which

it is

When

formed increases.

the substances S^,

xS'g,

S are

all

independently vari-

evident from (86) that the

conditions that the value of (133) shall be zero for the mass as given,
and shall not be negative for any phase of the same components, can
able components of the given mass,

only be

fulfilled

when

it is

the constants T, F, M^,

M^,

are equal

to the temperature, the pressure, and the several potentials in the given

J.

mass.

W. Gihbs Equilihrhirn of Heterogeneous

If

we

159

Substances.

give these values to the constants, the expression (133)

have the value zero for the given mass and we sliall only

will necessarily

have to inquire whether

But when S^,

1S2,

value

its

S are not

positive for

is

nents of the given nuiss, the values which

to the constants in

it

tions connecting J/,, Jf^,

When

it

but

properties of the given mass;

as

other phases.

will

it

be necessary to give

(133) cannot be determined entirely from the

temperature and pressure, and

mass

all

independently variable compo-

all

and

must be equal to

be easy to obtain as

will

many

its

eqiia"

with the potentials in the given

contains independently variable components.

it is

not possible to assign such values to the constants in

(133) that the value of the expression shall be zero for the given

and either zero or positive for any phase of the same compowe have already seen (pages 129-134) that if equilibrium
subsists without passive resistances to change, it must be in virtue of
properties which are peculiar to small masses surrounded by masses
of different nature, and which are not indicated bj' fundamental
fluid,

nents,

equations.

we

In this case, the fluid will necessarily be unstable, if

extend this term to embrace

all

cases in which an initial disturbance

confined to a small part of an indefinitely large fluid mass will cause

an ultimate change of state not indeflnitely small

out the whole mass.

in

degree through-

In the discussion of stability as indicated

fundamental equations

it

be convenient to use the term

will

by

in this

sense.*
*

If

we wish

to

know the

when exposed to a
we have only to suppose

stability of the given fluid

perature, or to a constant pressure, or to both,

constant temthat there is

enclosed in the same envelop witli the given fluid another body (which cannot combine

with the

Pv.
which

which the fundamental equation

fluid) of

as the case
of course

may

(Tand

be,

must be those

110 to the whole system.

P denoting

of the given fluid,)

When

it is

is e

Ty, or

= ~ Fv.

or

T>)

the constant temperature and pressure,

and

to apply the criteria of

page

possible to assign such values to the constants

in (133) that the value of the expression shall

be zero for the given

fluid

and

positive

every other phase of the same components, the value of (133) for the whole system
will be less when the system is in its given condition than when it is in any other.

for

(Changes of form and position of the given

Hence the

fluid is stable.

When

it

is

fluid are of

course regarded as immaterial.)

not possible to assign such values to the con-

stants that the value of (133) shall be zero for the given fluid

any other phase, the

fluid

is

of course unstable.

and zero or positive for

In the remaining case,

when

it is

possible to assign such values to the constants that the value of (133) shall be zero
for the given fluid

and zero or positive for every other phase, but not without the

value zero for some other phase, the state of equilibrium of the fluid as stable
or neutral will be determined by the possibUity of satisfying, for any other than

the given condition of the

fluid,

equations like (134), in which, however, the

or the second or both are to be stricken out, according as

we

first

are considering the

60

W. Gihbs

.7.

Equilibrium of Hetero\)eneous Substayices.

In determining for any given positive values of

and

and any

M whether the expression

given values whatever of 31^, M2,
(133) is capable of a negative value for any j^hase of the components
.

*S', and
if not, whether it is capable of the value zero
any other phase than that of which the stal)ility is in question, it
is only necessary to consider phases having the temperature T and
pressure P.
For we may assume that a mass of matter represented
mis capable of at least one state ot
by any values of w^j, w^,
not unstable equilibrium (which may or may not be a homogeneous
It may easily be shown
state) at this temperature anrl pressure.
that for such a state the value of f T7}-\- Pv must be as small as
The same will therefore be
for any other state of the same matter.

/Sj, JS^,

for

true of the value of (133).

Therefore

if this

expression

is

capable of

any mass whatever, it will have a negative value

And if this
for that mass at the temperature T and pressure P.
mass is not homogeneous, the value of (133) must be negative for at
So also, if the expression (133) is
least one of its homogeneous parts.
any phase of the comj)onents,
of
negative
value
for
capable
a
not
value
zero
must have the temperature
any phase for which it has the
a negative value for

and the pressure P.

may easily be shown that the same must be true in the limiting
and Pz= 0. For negative values of P, (133)
cases in which 7'=
is always capable of negative vahies, as its value for a vacuum is Pv.
For any body of the temperature T and pressure P, the expression
(133) may by (91) be reduced to the form
It

We

J/i m, J/2

have already seen

^"'2

3/m.

(pages 131, 132)

(135)

that an expression like

M and v have any given finite

P, 3/,, ll^,
values, cannot have an infinite negative value as applied to any real
body. Hence, in determining whether (133) is capable of a negative
jS, and if not,
value for any phase of the components >S',, S^^
(133),

when

T,

whether it is capable of the value zero for any other phase than that
of which the stability is in question, we have only to consider the
Any
least value of which it is capable for a constant value of v.
body giving this value must satisfy the condition that for constant

volume
de

Teh/

J/j

drn^

J/^

din.,

...

3fdm^

0,

(136)

stability of the fluid for constant temperature, or for constant pressure, or for both.

The number

of coexistent phases will

sometimes exceed by one or two the number of

the remaining equations, and then the equilibrium of the fluid will be neutral in
respect to one or

two independent changes.

Gibbs

J. TT.

or, if

we

Equilibrium of Heterogeneous Substances.

substitute the value of

(Is

161

taken from equation (SO), nsing sub-

g for the quantities rehiting to tlie actual corai)onents

the body, and subscript h
k for those relating to the possible,
script

t di]

yM

dm,,

...

Tdi]

Jfj

yM

of

dm,,

dm^

-f-

/</,

dm,,,

M2 dm^

...

dm,^

/^^.

- Mdm^

0.

(137)

body must be equal to T, and the

components must satisfy the same conditions as if it
were in contact and in equilibrium with a body having potentials
M. Therefore the same relations must subsist between
Mj, M2,
yu
Jf as between the units of the corresponding
//, and M^
That

is,

the temperature of the

potentials of

its

substances, so that
m^.lA^.

and as we have by

-j- m,^ /x^

= m^

M-^^

-{-

mM;

(138)

(93)

E=.t

7]

pv

-\- /A

m ...-}-

yu,,

body

the expression (133) will reduce (for the

m^,

(139)

or bodies for which

it

has the least value per unit of volume) to

[P-p)v,

(140)

the value of which will be positive, null, or negative, according as

the value of

is

(141)

positive, null, or negative.

Hence, the conditions

regard to the stability of a

in

fluid of

which

all

the ultimate components are independently variable admit a very simple expression.

If the pressure

of the fluid

is

greater than that of any

other phase of the same components which has the same temperature

and the same values of the potentials

fluid is stable

without coexistent phases

for its actual

;

if its

components, the

pressure

is

not as great

some other such phase, it will be unstable if its pressure is

as great as that of any other such phase, but not greater than that
of every other, the fluid will certainly not be unstable, and in all
probability it will be stable (when enclosed in a rigid envelop which
is impermeable to heat and to all kinds of matter), but it will be one
of a set of coexistent phases of which the others are the phases which
have the same pressure.
The considerations of the last two pages, by Avhich the tests
as that of

relating to the stability of a fluid are simplified, apply to such bodies

as actually exist.

But

if

we should form

arbitrarily

any equation as

a fundamental equation, and ask whether a fluid of which the properTrans. Conn. Acad., Vol.

III.

21

January, 1876.

162

J.

Wl Gibbs

Equilibrium, of Heterogeneous Substances.

were oiven by that equati<in would be stable, the tests of stabilitylast given would be insufficient, as some of our assumptions might

ties

The

by the equation.

not be fultilled

(pages 156-159) would in

liowever, as tirst given

test,

cases be sufficient.

all

Stability in respect to

Goutbiuous Changes of Phase.

may

In considering the changes which

take place

in

any mass, we

have already had occasion to distinguish between infinitesimal changes

new

phases, and the formation of entirely

in existing

phase of a

may be

fluid

and unstable

in regard to the latter.

In this case

changes

is

it

may

But a phase which

of discontinuous changes.

in regard to continuous

be capable

which prevent the com-

of continued existence in virtue of properties

mencement

phases.

stable in regard to the former kind of change,

is

unstable

evidently incapable of permanent

existence on a large scale except in consequence of passive resistances

We

change.

to

will

now

consider the conditions of stability in

respect to continuous changes of phase, or, as

may

it

We may

stability in respect to adjacent phases.

also

eral test as before, except that the expression (133) is to

only to phases which difier infinitely

the stability

is

in question.

In

tliis

little

from

tlie

be

called,

same gen-

use the

be applied

phase of which

component substances

case the

to be considered will be limited to the independently variable com-

and the constants

'^tc. must have the

components in the given fluid. The
constants in (133) are thus entirely determined and the value of the
expression for the given phase is necessarily zero. If for any infi-

ponents of the

fluid,

il/'j,

J/g?

values of the potentials for these

nitely small variation of the phase, the value of (133) can

negative, the fluid will be unstable

but

variation of the phase the value of (133)

will

be stable.

The only remaining

if

become

for every infinitely small

becomes positive, the fluid

which the phase can be

case, in

varied without altering the value of (133) can hardly be expected to

occur.

The phase concerned would

adjacent phases.

It will

bility (in respect to

be

in

such a case have coexistent

sufficient to discuss the condition of sta-

continuous changes) without coexistent adjacent

This condition, which for brevity's sake we will

may be written in the form

call the

condition

of stability,

e"

in

in

t'

if

jo'

v"

-/</;,"...-

/4'

m"

> 0,

(142)

which the quantities relating to the phase of which the stability is

question are distinguished by single accents, and those relating to

J.

W. Gibbs

the otlier phase

Equilibrmtn of Heterogeneous l^bstances.

by double

This condition

accents.

103

by

(93) equiva-

> 0,

(143)

> 0.

(144)

is

lent to

e"^t'if^p'v"-~n,'m,"

f'4-

w'

'//-/

'm/

-{-/<,

//'m"

-j-

j-i'

m'

and to
^t'7f-\-p'v" -fi.'m,"

t"

yf

The condition

- p" v" +

(143)

A'

may be

x"

we use

the character

m,"

~/^:m"

/."

mj'

expressed more briefly

Ae.>tAn~iy^v +
if

to

i^i^J)ii^

in the

form

-{-jjzlm,

(1^5)

signify that the condition, although

relating to infinitesimal differences,

is

not to be interpreted in accord-

ance with the usual convention in respect to differential equations

with neglect of infinitesimals of higher orders than the

first,

but

is

to be interpreted strictly, like an equation between finite differences.

In fact,

when

a condition like (145) (interpi-eted strictly)

for infinitesimal difierences,

which

it

it

must be possible

shall hold true of finite differences.

bered that the condition

/Iff, Av, Ani^,
change of phase.

of

(If

is

is

satisfied

to assign limits within

But

it

is

to be

remem-

not to be applied to any arbitrary values

Am, but only

to such as are determined

by a

only the quantity of the body which determines

the value of the variables should vary and not

phase, the value of

its

would evidently be zero.) We may free

ourselves from this limitation by making v constant, which will
cause the term p Jv to disappear. If we then divide by the constant v, the condition will become

the

first

member

of (145)

A->tA--\-i.i.J~^
in

which form

we may

it

+yuJ

(146)

will not be necessary to regard v as constant.

As

obtain from (86)

d-=itd^ 4- /.i,d^
we

see that the stability

-4-u^d-^,

of any phase in regard

depends upon the same conditions in regard

the density

to

(147)

continuous changes

to the

second

and higher

of energy regarded as a function

of
of the density of entropy and the densities of the several components,
which would maJce the density of energy a minimum, if the necessary

differential coefficients

conditions in regard to the first differential coefficients were fulfilled.

When n -rz 1, it may be more convenient to regard ui as constant

164

TK Gihhs

fZ

in (145)

than

Equilibrium of Heterogeneous Substances.

m a constant, it appears

Regarding

v.

depends upon the same conditions

of a phase

energy of a unit of mass

differential coefficients of the

and higher

that the stability

regard to the second

in

entropy and volume, which would make

regarded as a function of

its

the energy a minimum,

the necessary conditions in regard to the

if

were

first differential coefficients

to

which

sufficient condition of

matter, or of
of

any two

tlie

evidently the necessary and

is

it

stability of all phases of certain kinds of

phases within given limits, that (144) shall hold true

all

infinitesimally differing phases within the

may

as the case
collective

But

relate.

etc.

/>',

t',

fulfilled.

(144) expresses the condition of stability for the phase

The formula

For the purpose,

be, in general.

may

determinations of stability, we

same

neglect the distinction

between the two states compared, and write the condition

1}

Jt-{- V

Jp

m^

...

J/Y J

limits, or,

therefore, of such

in the

form

- m^ J// > 0,

(148)

4-^-^/V

(149)

or

Jp>ljt+'^J,i,
Comparing
bility in

we

(98),

see that

it is

necessary and sufficient for the sta-

regard to continuous changes of

the phases within any

all

given limits, that within those limits the same conditions should be
the second and higher differential coefficients of

fulfilled in respect to

the pressure regarded as a function of the temperature and the sev-

which would make the pressure a minimum,

eral potentials,

necessary conditions with respect to the

were

first

if

the

differential coefficients

fulfilled.

By

equations (87) and (94), the condition (142)

may

be brought to

the form

^f
For the
and

t'

if

p'

v' -\- )A^'

m^'

true of any

+//';/'>
limits

when v'=

it is

differ infinitely little.

y", //</

/></',

m^

=z

t'

(150)

necessary

This evidently

?",

f -f+{t" -t'),/'>i);
and that when

0.

within the same limits this condition shall hold

two phases which

requires that

any given

stability of all phases within

sufficient that

(151)

t"

f ~ p'

r'

-\- fi

^'

These conditions may be written

^'

in the

-\-

form

jjj

mj > 0.

(152)

W. Gihhs

J.

Equilibrium of Heterogeneous Substances.

+ vAt\^<0,

[Atl.^

- |X^Am^

[/iil:-\-2)^'0

in

(153)

// Z/>?i],

> 0,

letters indicate the quantities

which the subscript

165

(154)

which are to be

m.
standing for all the quantities
regarded as constant,
If these conditions hold true within any given limits, (150) will also
hold true of any two infinitesimally differing phases within the same

To prove

limits.

by

we

this,

t'"

= v",

v"'

Now

by

(155)

t\

= m,",

m,"'

consider a third phase, determined

will

the equations

and

m"'

= m".

(156)

(153),

'/'"-'/"+(^"'-O'/"<0;
and by

(157)

(154),

f"

//''

J^ p' v'"

j^v'

-i-//,'/n/

-p'

t'" //"

1^1

v'

m^'"

^'

//

'

m/

-/V >/''"
-\-

>0.

^aJ tnj

(158)

> 0,

//' ///'

(159)

which by (155) and (156) is equivalent to (150). Therefore, the conditions (153) and (154) in respect to the phases within any given
limits are necessary

and

sufficient for the stability of all the

phases

be observed that in (153) we have the

condition of thermal stability of a body considered as unchangeable
within those limits.

It will

and in volume, and in (154), the condition of mechanand chemical stability of the body considered as maintained at a
Comparing equation (88), we see that the
constant temperature.

in composition
ical

condition (153) will be satisfied,

cific

heat for constant volume)

the composition of the body

evidently not be altered,

if

if

is

is

-^ <0,

i.

e.,

if-/

When

positive.

or

/^:=

^
1,

invariable, the condition

we regard

as constant,

i.

(thespee.,

when

(154) will

by which the

condition will be i-educed to

{Af

+ p Av\,>().

This condition will evidently be satisfied

d7)

v-~-

when

(the

elasticity for

n> 1, (154)

may

if

(160)

-^
>0,
dv^

constant temperature)

i.

e.,

if

L
dv

is

positive.

qy

But

be abbreviated more symmetrically by making

V constant.

Again, by (91) and

the form

(96), the condition

(142)

may

be brought to

166

J\

W. Gihhs

Equilibrium of Heter
-

j^t",f-p"v"

^"

-t'

-l;'

+y

if

ix.'m,"

0(1 eneous

-lA^m:

+/<///... +

v"

Therefore, for the stability of

Substances.

/'n'

ra:

> 0.

(161)

phases within any given limits

all

it is

necessary and sufficient that within the same limits

[Jl;-]-

7/Jt

V /lp],,<0,

(162)

and

[JC-yU,^mi
may

as

The

easily be

first

-ywJm],,,>0,

(163)

proved by the method used with (153) and (154),

of these formulae expresses the thermal and mechanical con-

body considered as unchangeable in compoand the second the conditions of chemical stability for a body
considered as maintained at a constant temperature and pressure. If
m^,
n z=. 1, the second condition falls away, and as in this case C
ditions of stability for a
sition,

condition (162) becomes identical Avith (148).

The foregoing

discussion will serve to illustrate the relation of the

general condition of stability in regard to continuous changes to

some of the principal forms of fundamental equations. It is evident
that each of the conditions (146), (149), (154), (162), (163) involve
in general several particular conditions of stability.

<^

=:

t' 7}

+p

We

now

will

Let

ofive our attention to the latter.

^^' m^

/V>^n,

(164)

the accented letters refei-ring to one phase and the unaccented to

It is by (142) the necessary and sufficient condition of the
another.
stability of the first phase that, for constant values of the quantities

relating to that phase

and of

when the second phase

(164), we have by (86)

d^={t -

t')

ch]

is

v,

the value of

shall

identical with the

{p -p') dv +

(/ij

/f,')

be a minimum
Differentiating

dm^

... Therefore, the above condition requires that

first.

if

(//

^')dm.

we regard

v,

(165)

m^,

having the constant values indicated by accenting these letters,

t shall be an inci-easing function of ;/, when the variable phase differs
But as the fixed phase may be any
sufficiently little from the fixed.

as

one within the limits of

1/

(within these limits)

This condition

may

stability,

for

must be an increasing function of

m.
v, m^,

any constant values of

be written

1^)

>0.

(166)

W. Gibbs

J.

Wlien
of

y,

Equilibrium of Heterogeneous Substancefi.

this condition

is

will

?/',

value of

satisfied, the

for

(Z>,

any given values

And

be a minimum when t=.t'.

167

therefore, in

applying the general condition of stability relating to the value of

we need only consider the j)hases for which t = t'.

see again by (165) that the general condition requires that
rn as having the constant values indicated
if we reo-ard t, v, m^,
(f ,

We

when

be an increasing function of m^,

letters, //, shall

by accenting these

the variable phase difters sufficiently

may be any

as the fixed phase

from the

little

must be an increasing function of m^ (within these

That is,
m.
w, mo,
constant values of
.

;;,

imum
and

V, m.2

>0.

yu,

any constant values of

A<j'; so that in

(167)

this condition is satisfied, as well as (166),

value, for

//

any

limits) for

(-p-X
\nm^!t,

When

l)ut

fixed.

one within the limits of stability,

v,

m^,

will
.

',

have a min-

when

t'

applying the general condition of stability

t' and /<, = yw/we need only consider the phases for which t
particular conditions
following
the
obtain
also
In this way we may

of stability

(P)
\Zlm2ft,
\JmJt.

When

the n-\-

>0,
V,

m,,

m;5,

(168)

?n

>0.

(169)

V,

conditions (166)-(169) are

of 0, for any constant value of

v, will

be a

all

satisfied,

minimum when

the value
the tem-

perature and the potentials of the variable phase are equal to those

The

of the fixed.
will

be entirely

will

be completely

pressures will then also be equal and the phases

Hence, the general condition of stability

identical.
satisfied,

when

the above particular conditions are

satisfied.

which these particular conditions have been

m^
we may interchange in them ?;, m^,
in any way, provided that we also interchange in the same way

From

the

derived,

^,

yUj,

it is

manner

in

evident that

/J.

In this

way we may

obtain difierent sets of

conditions which are necessary and sufficient for stability.

tity V

might be included

in

the

first

of these

lists,

and

?i

The quan-

in the

second, except in cases when, in some of the phases considered, the

entropy or the quantity of one of the components has the value zero.

168

W. Gihhs

fZ.

Eqidlibrium of Heterogeneous Substances.

the condition that that quantity shall be constant would create

Tlieii

a I'estriction iipoii the variations of

the phase, and cannot be substi-

tuted for the condition that the volume shall be constant in the state-

ment of the general condition of

minimum

stability relative to the

value of ^.

To indicate more distinctly all these particular conditions at once,

we observe that the condition (1^4), and thei'efore also the condition
obtained by interchanging the single and double accents, must hold
two intinitesimally difiering phases within the
Combining these two conditions we have

true of any
stability.
(t"

t') (;/"

+ (/^i"
which

may

//')

(/' -i>')

y"i') h'^x"

W-

''H')

limits of

v')

/^')

'-m')>0,

(170)

be written more briefly

+ Jfx^/lm^

^tJjj /ip^v

+z/yuz/m>0.

(iVl)

This must hold true of any two infinitesimally difiering phases within
If, then, we give the value zero to one of the
the limits of stability.

term except one, but not so as to make the phases

difierences in every

completely identical, the values of the two differences in the remaining term will have the same sign, except in the case of Jp and Jv,

which

will

have opposite

hold true even on

signs.

J)

in

both states are stable this will

Therefore, within the

the limits of stability.)

limits of stability, either of the

sio-n

(If

two

quantities occurring (after the

any term of (171) in an increasing function of the other,

when we regard as
v, of which the opposite is triie,

except p and

constant one of the quantities occurring in each of the other terms,

but not such as to make the phases identical.
If

we

always

write

^?

for

we obtain conditions which are

we also substitute ^ for >, we

in (166)-(169),

/}

sufficient for

stability.

obtain conditions which

ai-e

If

dt

dy

df]

du.

dt
+ dm
dm

when

When

reo-arded as independent variables.

dt=z

-z

d^x^

r^,

dv =:

0,

m^,

we

shall

are

have

v,

dt
d)n
+ am

Let us consider

necessary for stability.

the form which these conditions will take

du

(172)

d^

dfi

d^^=-^-dv\-^^^drn,

d^

+^fm

W. Gibhs

J.

Eqrdlihrinm of Heterogeneous Stihstances.

Let us write -S+i for the determinant of the order n

dm

d^E

d-^e
d.T]

d)n

dm

d^E
di]

d^e
^

(173)

dm. dm.

d'^E

dm

dm

dm, j

of which the constituents are

by

'

dm,'^

(86) the

same

as the coeificients in

minors obtained by erasing

Rn^t,
column and row in the original determinant and in the minors

equations (172), and

the last

i?,

t-'tc.

H^

successively obtained, and

Then if dt,
by (172)

df-i.^,

f?/'_i,

for the

remaining constituent.
have the value zero, we have

the last

for

and dv

Ii dpi,

that

dm djj

'

'

'

dy}

-\- 1

d^E

d^e

d^8
drf

169

all

= ^+i dni,

(174)

is,

/^\
In like

=^-K

(175)

manner we obtain

\dm_Jt,v,ii,,

f^n^Z^

(176)

etc.

Therefore, the conditions obtained

by writing d

for /} in (166)-(169)

are equivalent to this, that the determinant given above with the

minors obtained from

it

d^ E
constituent -j-^ shall

all

as

above mentioned and the

be positive.

Any

]^hase for

remaining

last

which

this con-

dition is satisfied will be stable, and no phase will be stable for

which any of these quantities has a negative vahie. But the conditions (166)-(169) will remain valid, if we interchange in any way
W2j,

Tf,

m, (with

Hence the order

in

responding rows

in

corresponding interchange of

^,

/ij,

//).

which we erase successive columns with the corthe determinant is immaterial.

Therefore none

of the minors of the determinant (173) which are formed

by erasing

corresponding rows and columns, and none of the constituents of the

principal diagonal, can be negative for a stable phase.

We will now
of

stability

consider the conditions which characterize the limits

(i. e.,

the limits which divide stable from unstable phases)

Trans. Conn. Acad., Vol.

III.

22

January, 1876.

170

W. Gibhs Equilibrium of Heterogeneous

tT.

Substances.

with respect to continuous changes.* Here, evidently, one of the

conditions (166)-(169) must cease to hold true. 'Therefore, one of the
differential coefficients

formed by changing

into

bers of these conditions must have the value zero.

mem-

in the first

(That

it

the

is

numerator and not the denominator in the differential coefficient

which vanishes at the limit appears from the consideration that the
denominator

each case the differential of a quantity which

in

is

is

necessarily capable of progressive variation, so long at least as the

phase

capable of variation at

is

by the subscript
ferential

way

under the conditions expressed

all

The same

letters.)

will hold true of the set of dif-

obtained from these by interchanging in any

coefficients

m, and simultaneously interchanging t, /x^,

m,,
/u^
same way. But we may obtain a more definite result than this.
to m_^ or /*_i, and to v,
Let us give to ?/ or t, to m^ or /^j,
Then
the constant values indicated by these letters when accented.
.

/;,

in the

by

(165)

d^ =

{pt

- /tj)dm.

(177)

Now
(")

""-"-(.Irj'c""-"'-')

approximately, the differential coefficient being interpreted in accord-

ance with the above assignment of constant values to certain variables,

and

its

value being determined for the phase to which the

accented letters

refer.

and

Therefore,

The

[<^l-'A'r(4/7,

1
i

rn,

quantities neglected in the last equation are evidently of the

same order
different

as {vi

according as we have made

made

i/i^

or

pi^

Now

mj)^.

differential

(the

this value of

/;

constant, etc.

or

letters,

be

but since, within the limits of stability,

the value of 0, for any constant values of ?n and

//_, have the values indicated
when t,p,/iXi
.

will of course

having a different meaning)

constant, and according as we have

coefficient

v, will

be the least

by accenting these

the value of the differential coefficient will be at least as small

* The limits of stability with respect to discontinuous changes are formed by phases
which are coexistent with other phases. Some of the properties of such phases have
See pages 152-156.
already been considered.

W. Gibbs

J.

when we give

Equilibrium of Heterogeneous Substances.

these variables these constant values, as

adopt any other of the suppositions mentioned above

And

quantities remaining constant.

way

interchange in any

way t, /Vj,
when we choose
.

?/,

w,,

in

m,

any one of the

dt

du.

-J-,
d}]

-f^,
dm^

when we

regard to the

we may

all

these relations

we

interchange in the same

within the limits of stability,

It follows that,

/./.

for

if

in

171

diiferential coefficients
dj.in

-7

(181)
^

d>n

'

the quantities following the sign d in the numerators of the others

together with v as those which are to remain constant in differentiathe differential coefficient as thus determined will

tion, the value of

be at

as when one or more of the constants in differenfrom the denominators, one being still taken from

least as small

tiation are taken

each fraction, and v as before being constant.

Now we
the limit

have seen that none of these

differential coefficients, as

any of these ways, can have a negative value within

of stability, and that some of them must have the value zero

determined

in

Therefore, in virtue of the relations just established

at that limit.

one at least of these differential coefficients determined by considerinoconstant the quantities occurring in the numerators of the others

have the value

But

together with

y, will

value zero,

such will in general have the same value.

all

\drnjt^

V, fii,

for example, has the value zero,

component S^ without altering

higher orders than the

by

first)

zero.

if

one such has the

For

nn-i

(98),

the temperature or the potentials, and

without altering the pressure.

;^,

//.

'

we may change the density of the

(if we disregard infinitesimals of

That
change the phase without altering any of the quantities
therefore,

if

is,
/->,

we may
yUj,

(In other words, the phases adjacent to the limits of stability

exhibit approximately the relations characteristic of neutral equili-

Xow this change of phase, which changes the density of

one of the components, will in general change the density of the

brium.)

others and the density of entropy.

tial coefficients

the fractions in

formed

Therefore,

all

the other differen-

analogy of (182), i. e., formed from

(181) by taking as constants for each the quantities in
after the

the numerators of the others together with y, will in general have

the value zero at the limit of stability. And the relation which
characterizes the limit of stability
setting

any one of these

may

be expressed, in general, by

differential coefficients equal to zero.

Such

172

J.

W. Gihhs

Equilibrium of Heterogenous Substances.

is known, may be
reduced to the form of an equation between the independent variables

an equation, when the fundamental equation

of the fundamental equation.

Again, as the detei'minant (173) is equal to the product of the

differential coefficients obtained by writing d for A in the first

members

of (160)-(169), the equation of the limit of stability

expressed by

the differential equation as thus expressed will

interchange of the expi-essions

by

may be

The form of
not be altered by the

determinant equal to zero.

setting this

?;,

?,,

m^, but

it

will be altered

the substitution of v for any one of these expressions, which will

be allowable whenever the quantity for which it is substituted has

not the value zero in any of the phases to which the formula is to be
applied.

The condition formed by

is

setting the expression (182) equal to zero

evidently equivalent to this, that

r

d^A

=0,
fJ-n

that

is,

(183)

that

drV

(184)
i,

or

by

(98), if

we regard

if,

yw^,

jWn^l

F-\

yw

as the independent variables,

td^\_
(185)

XdiJ^^I

In like manner

we may obtain
d^p
~dP

Any

d^p

d^p

(186)

one of these equations, (185), (186), may be regarded, in genWe may be certain
the equation of the limit of stability.

eral, as

that at every phase at that limit one at least of these equations will

hold true.

GEOMETRICAL ILLUSTRATIONS.
Surfaces in lohich the Composition of the
Constant.
In vol.

ii,

p.

Body

382, of the Trans. Conn. Acad., a

represented

method

is

is

described of

representing the thermodynamic properties of substances of invariable

composition by means of surfaces.

The volume, entropy, and energy

J.

W. Gibhs

Equilibrium of Heterogeneous Substances.

of a constant quantity of a substance are represented

This method corresponds to the

co-ordinates.

mental equation described on pages 140-144.

first

173

by rectangular
kind of funda-

Any

other kind of
fundamental equation for a substance of invariable composition will
suggest an analogous geometrical method. Thus, if we make m con-

any one of the sets (99)-(103) are reduced to

which may be represented by rectangular co-ordinates. This
will, ho\vever, afford but four different methods, for, as has already
(page 150) been observed, the two last sets are essentially equivalent

stant, the variables in

three,

when n =. \.
The method

described in the preceding volume has certain advan-

tages, especially for the purposes of theoretical discussion, but

it

may

more advantageous to select a method in which the properties represented by two of the co-ordinates shall be such as best serve
to identify and describe the difi*erent states of the substance.
This
condition is satisfied by temperature and pressure as well, perhaps, as
by any other properties. We may represent these by two of the
co-ordinates and the potential by the third.
(See page 143.)
It
will not be overlooked that there is the closest analogy between these
often be

three quantities in respect to their parts in the general theory of

equilibrium.

energy.)

If

(A

we

similar analogy exists

give

between volume,

entrojjy,

and

the constant value unity, the third co-ordinate

C, which then becomes equal to //.

Comparing the two methods, we observe that in one

will also represent

vz=zx,

i]

= y,

z,

174

W. Gibhs

J.

The

Equilihriuni of Heterogeneous Suhstatices.

surfaces detined

guished as the

which they
In the

v-7]-e

by equations
and the

surface,

(187)

and (189) may be

t-p-t surface,

distin-

of the substance to

relate.

t-2>'C

surface a line in which one part of the surface cuts

another represents a series of pairs of coexistent states.

point

through which pass three different parts of the surface represents a

triad of coexistent states.
Through such a point will evidently pass

by the intersection of these sheets taken two

The perpendicular projection of these lines upon the p-t
plane will give the curves which have recently been discussed by ProThese curves divide the space about the projecfessor J. Thomson.*
the three lines formed

by two.

tion of the triple point into six parts

Let

follows:

C^'',

?*^\

C^"^'

may

which

be distinguished as

denote the three ordinates determined for

and

by the three

the same values of

2>

triple point, then in

one of the six spaces

sheets passing through the

^(n<KX)<^(S)^
in the

(191)

next space, separated from the former by the line for which
^(r)<^(.?)<^(X)^

(192)

the third space, separated from the last

in

by the

line

for

^(S)<^(r)<^W

which
(193)

< ?(^> < C^''^

in the fourth

^^^

in the fifth

^(^)<?(^><?(^

(195)

in the sixth

?(<^(^) <?(*).

(196)

The

sheet which gives the least values of

(194)

'C,

is

represents the stable states of the substance.

in each case that

From

which

this it is evident

that in passing around the projection of the triple point we pass

through lines representing alternately coexistent stable and coexistent

But the

unstable states.
values of

by
of

t,

may

states

by

represented

the intermediate

be called stable relatively to the states represented

the highest.

work obtained

The

differences

^^^^

?^''>,

etc.

in bringing the substance

represent the

by

amount

a reversible process

from one to the other of the states to which these quantities relate,
in a medium having the temperature and pressure common to the
two states. To illustrate such a process, we may suppose a plane
perpendicular to the axis of temperature to pass through the points
* See the Reports of the British Association for 1871 and 1872

Magazine,

vol. xlvii. (1874), p. 447.

and Philosophical

J.

Wl Gibhs Equilibrium of Heterogeneous

Substances.

175

representing the two states.

This will in general cut the double line

formed by the two sheets to which the symbols (X) and ( V) refer.
The intersections of the plane with the two sheets will connect the
double point thus determined with the points representing the
initial

and

The geometrical

may be

and thus form a

final states of the process,

body between those

for the

relations

easily obtained

reversible

path

any

state

states.

which indicate the

stability of

by applying

to the case in which there

is

the principles stated on pp. 156 ff.

but a single component. The expres-

sion (133) as a test of stability will reduce to

e

t' 1]

-\- 2)'

ji'

rn^

(197)

the accented letters referring to the state of which the stability

question, and the unaccented letters to any other state.

If

is in

we

con-

sider the quantity of matter in each state to be unity, this expression

may

be reduced by equations (91) and (96) to the form

'Q-'Q'-[-{t-t')n-{2y-p')v,

(198)

which evidently denotes the distance of the point {t',p\ C') below the
tangent plane for the point {t,p, t), measured parallel to the axis of
t,.

Hence

if

the tangent plane for every other state passes above the

point representing any given state, the latter will be stable.

If

any

of the tangent planes pass below the point representing the given
state, that state will

be unstable.

Yet

it is

not always necessary to

consider these tangent planes.

For, as has been observed on page

160, we may assume that (in the case of any real substance) there
will be at least one not unstable state for any given temperature and
pressure, except

represented

plane p=.Q

when the

latter

negative.

is

Therefore the state

by

a point in the surface on the positive side of the

will be unstable only when there is a point in the surface

which t and jo have the same values and a less value. It follows
from what has been stated, that where the surface is doubly convex
upwards (in the direction in which
is measured) the states reprefor

t,

'Q

gented will be stable in respect to adjacent states.

directly from (162).

But where the

surface

is

This also appears

concave upwards in

either of its principal curvatures the states represented will be unstable in respect to adjacent states.

When

the number of component substances is greater than unity,

not possible to represent the fundamental equation by a single
surface.
have therefore to consider how it may be represented

it is

We

number of surfaces.
natural extension of either of
the methods already described will give us a series of suifaces in

by an

infinite

176

W. Gibhs

J.

which every one

Equilibrium of Heterogeneous Substances.

is

the

surface, or every one the

^7-;/-f

t-jy-t

surface for

a body of constant composition, the proportion of the components

varying as we pass from one surface to another. But for a simultaneous

view of the properties which are exhibited by compounds of two or
three components without change of temperature or pressure, we may
more advantageously make one or both of the quantities t ov p constant in each surface.

Surfaces
sented

When

and Curves in
Variable and

there are three components, the position of a point in the

^-I^ plane may

mg

mj, mg,

body most simply,

indicate the composition of a

haps, as follows.
tities

the Composition of the Body repreTemperature and Pressure are Constant.

v:ihich
its

is

The body

is

nis of the substances S^,

plane, which are not in the

equal to w?,, m2,

m3

/S'g,

/Sg,

the value of

Let Pj, P2, Pg be any three points

ni^ being unity.

per-

supposed to be composed of the quan-

same straight

If

line.

m,

-f

in the

we suppose masses

to be placed at these three points, the center of

gravity of these masses will determine a point which will indicate

the value of these quantities.

If the triangle

is

equiangular and has

the height unity, the distances of the point from the three sides will

be equal numerically to m^^ mg, ni^. Now if for every possible

phase of the components, of a given temperature and pressure, we
3^ plane which represents the compolav off from the point in the JTsition of the

Z and
(when m^ -j- "'2 "h^s ^= 1)5 ^^ points
form a surface, which may be designated as the

phase a distance measured parallel to the axis of

representing the value of

thus determined will

m^-m2-"^3-? surface of the substances considered, or simply as their

In like manner,
m-'Q surface, for the given temperature and pressure.

two component substances, we may obtain a

X-Z plane. The coordinate y
may then represent temperature or pressure. But we will limit our-

when

there are but

curve, which

we

will suppose in the

selves to the consideration of the properties of the

n =r 3, or the m-'C curve for n r= 2, regarded as a

which varies with the temperature and pressure.
As by (96) and (92)

and

(for constant

we imagine

relate,

surface for

temperature and pressure)

dt,=:

if

ni-i;.

surface, or curve,

/.i^

dm^

-f /U2

dm^ +

yWg

dm^,

a tangent plane for the point to

and denote by

'q'

which these

the ordinate for any point in

letters

the plane,

TK Gibbs Equilibrium

J.

oj'

Heterogeneous Substances.

177

/,', /^a? "^3? the distances of tlie foot of this ordinate from
the three sides of the triangle P^ Po P3, we may easily obtain

and by

= yWjm,' +

'Q'

which

may

Ave

fx

m'

(199)

-f //g w^a',

There-

regard as the equation of the tangent plane.

fore the ordinates for this ])lane at P^, P2,

and P3 are equal respect-

^^^ ^" general, the ordinate

^^^ ^^^^ A'sfor any point in the tangent plane is eqvial to the potential (in the

ively to the potentials

//j,

phase represented by the point of contact) for a substance of which

the composition

page

S^, there

indicated

is

Among

149.)

by the

position of the ordinate.

the bodies which

may be some which

may be formed

of S^,

jS^,

(See

and

are incapable of variation in composi-

which are capable only of a single kind of variation. These

by single points and curves in vertical planes.
Of the tangent plane to one of these curves only a single line will be
fixed, which will determine a series of jDotentials of which only two
tion, or

will be represented

will

The phase represented by

be independent.

determine only a single potential,

of the body

The
a

itself,

which

will

viz.,

a separate point will

the potential for the substance

be equal to

'Q.

points representing a set of coexistent phases have in general

common

But when one of these points

tangent plane.

is

situated

on the edge where a sheet of the surface terminates, it is sufiicient if

Or,
the plane is tangent to the edge and passes below the surface.
when the point is at the end of a separate line belonging to the surface, or at

an angle

in the

edge of a

sheet, it is sufficient if the plane

pass through the point and below the line or sheet.

surface

lies

If

no part of the

below the tangent plane, the points where

it

meets the

plane will represent a stable (or at least not unstable) set of coexistent phases.

The surface which we have considered represents the relation

between
and m^, m^, m^ for homogeneous bodies when t and p
have any constant values and m^ -j- mg
It will often be
^^5 =: 1.
useful to consider the surface which represents the relation between
t.

the same variables for bodies which consist of parts in different but
coexistent phases.

We may

suppose that these are stable, at least

in

regard to adjacent phases, as otherwise the case would be devoid of

interest.

body

The

point which

will evidently

represents the state of the composite

be at the center of gi-avity of masses equal to

the parts of the body placed at the points representing the phases of

Hence from the surface representing the properties of

homogeneous bodies, which may be called the primitive surface, we

these parts.

Trans. Conn. Acad., Vol.

III.

23

January, 1876.

ITS

J.

W. Gihhs

Equilihrium of Heterogeneous Substances.

easily construct the surface representing the properties of bodies

may

which are

in equilibiium but not

the secondary or derived

various portions or sheets.

tion of tAVO phases

may

homogeneous.

surface.

The

will

It

This

consist,

may be
in

called

general, of

sheets which represent a combina-

be formed by rolling a double tangent plane

upon the primitive surface the part of the envelop of its successive
positions which lies between the curves traced by the points of con:

When

tact will belong to the derived surface.

the primitive surface

has a triple tangent plane or one of higher order, the triangle in the

tangent plane formed by joining the points of contact, or the smallest

polygon without re-entrant angles which includes all the points of

contact, will belong to the derived surface, and will represent masses

more phases.
surface as thus constructed for any
thermodynamic
Of the whole
pressure,
that part is especially imporpositive
any
temperature and
value
of
for
any given values of m,, mg,
least
?
tant which gives the
represented
by a point in this part of the
The state of a mass
m^.of
energy would be possible if
surface is one in which no dissipation
impermeable both to
envelop
the mass were enclosed in a rigid
matter and to heat and the state of any mass composed of S^, S^, S^
in any proportions, in which the dissipation of energy has been comconsisting in general of three or

(i.
e., under the
above supposed,) would be

pleted, so far as internal processes are concerned,

limitations imposed

by such an envelop

as

represented by a point in the part which

m-'C,

we

are considering of the

surfece for the temperatvire and pressure of the mass.

We may

therefore briefly distinguish this part of the surface as the surface

dissipated energy.

It is

evident that

projection of which upon the A'^

it

Y plane coincides

Pg P3, (except when the pressure

constructed

is

states

which

for

negative, in which case there

enero"y,) that
it

The general

it

with the triangle

which the

m-'C,

surface

is

no surface of dissipated
nowhere has any convexity upward, and that the
is

represents are in no case unstable.

properties of the

ni-'Q

lines for

two component sub-

stance? are so similar as not to require separate consideration.

now

of

forms a continuoiis sheet, the

We

proceed to illustrate the use of both the surfaces and the lines

by the discussion

of several particular cases.

Three coexistent phases of two component substances may be

is
represented by the points A, B, and C, in figure 1, in which
from
PjPg,
toward
the
left
top
of
the
page
the
toward
measured
>'^i
from P2Q25 ^"^^^ ^2 toward the right from P,Q^. It is supposed
Portions of the curves to which these points belong
1.
that PjPjj
'Q

J.

W. Gihhs

Equilibrium of Heterogeneous Substances.

are seen in the figure, and will be denoted

We

(C).

may,

179

by the symbols (A),

(B),

speak of these as separate curves,

for convenience,

without implying anything in regard to their possible continuity in

The
parts of the diagram remote from their common tangent AC.
line

of dissipated energy includes the straight line AC and portions

and (0). Let us first consider how the
diagram will be altered, if the temper-

of the primitive curves (A)

Q..

ature

is

varied while the pressure

re-

mains constant. If the temperature

receives the increment dt, an ordinate
of which the position is fixed will
receive the increment
b
Fig.

If

dt.

(The reader

dt)j j)^
\ai

'^^'

''^'

will easily con-

1.

vince himself that this

AC,

ordinates for the secondary line

Now

the primitive curves.)

if

is

true of the

as well as of the ordinates for

we denote by

//

the entropy of the

phase represented by the point B considered as belonging to the

curve (B), and by if the entropy of the composite state of the same

matter represented by the point

tangent to the curves (A) and (C),

considered as belonging to the

t (//'

If this quantity

of these states.

is

denote the heat

jf) will

yielded by a unit of matter in passing from the

first to

the second

positive, an elevation of temper-

ature will evidently cause a part of the (;urve (B) to protrude below
the tangent to (A) and (C), which will no longer form a part of the
line of dissipated energy.

This line will then include portions of the

three curves (A), (B), and (C), and of the tangents to (A) and (B)

and

to (B) and (C),

On

the other hand, a lowering of the tempei'a-

ture will cause the curve (B) to

and

(C), so that

imstable.

If

all

{if

lie

entirely

above the tangent to (A)

the phases of the sort represented

rf) is negative, these eifects will

by (B)

will

be

be produced by

the opposite changes of temperature.

The

effect of a

constant
tion of

change of

may be found

any ordinate

in a

will

be

pi-essui-e

manner

while the temperature remains

entirely analogous.

dp or V

dp.

The

Therefore,

variaif

the

volume of the homogeneous phase represented by the point B is

a greater than the volume of the same matter divided between the
the phases represented by A and C, an increase of pressure will give
diagram indicating that all phases of the sort represented by curve
(B) are unstable, and a decrease of pressure will give a diagram indi-

80

J.

W. Gibbs

Equilibrium of Heterogeneous Substances.

eating two stable pairs of coexistent phases, in each of which one of

the pliases

When

of the sort represented by the curve (B).

is

the

volumes is the reverse of that supposed, these results

will be produced by the opposite changes of pressure.
rehition of the

When we have four coexistent phases of three component substances,

there are

two

cases which

must be distinguished.

In the hrst, one of

the points of contact of the primitive surface with the quadruple

tangent plane
three

in

lies

within the triangle formed

the second, the four points

quadrilateral withoiit re-entrant

projection upon the

X-

Y plane

may

which

the other

Figure 2 represents the

angles.

(in

by joining

be joined so as to form a

^?^,,

mg, m^ are measured)

when one of the points

formed by the other three A, B,

of a part of the surface of dissipated energy,

of contact
C.

falls

within the triangle

This surface includes the triangle

l^lane,

ABC

in the

quadruple tangent

portions of the three sheets of the primitive surface which

touch the triangle at

its vertices,

EAF, GBH, ICK, and

the three developable surfaces formed

upon each pair of these

Fig.

sented in the

sheets.

2.

figui-e

Fig.

by ruled

surfaces, the lines indicating the direc-

represents a mass of which the matter

three or four different phases, in a

the position of a point.

if

portions of

a tangent plane rolling

These developable surfaces are repre-

tion of their rectilinear elements.

such that

by

point within the triangle

is

ABC

divided, in general, between

manner not

entirely determined

(The quantities of matter

by

in these phases are

placed at the corresponding points. A, B, C, D, their

center of gravity would be at the point representing the total mass.)

J.

W. Gihhs

Equilihrium of Ileterogeneoxis Substances.

181

Such a mass, if exposed to constant temperature and pressure, would

be in neutral equilibrium. A point in the developable surfaces repre-

mass of which the matter is divided between two coexisting

by the extremities of the line in the
figure passing through that point,
A point in the primitive surface
represents of course a homogeneous mass.
To determine the effect of a change of temperature without change
of pressure upon the general features of the surface of dissipated
energy, we must know whether heat is absorbed or yielded by a
mass in passing from the phase represented by the point D in the
sents a

phases, which are represented

primitive surface to the composite state consisting of the phases A,

B, and
case,

C which

is

represented by the same point.

If the first

an increase of temperature will cause the sheet (D)

sheet of the pi-imitive surface to which the point

(i.

is

the

e.,

the

belongs) to sep-

arate from the plane tangent to the three other sheets, so as to be

and a decrease of temperature, will cause

a part of the sheet (D) to protrude through the plane tangent to
situated entirely above

the other sheets.

it,

These

effects will

changes of temperature, when heat

be produced by the opposite

is

yielded by a mass passing

from the homogeneous to the composite state above mentioned.

In like manner, to determine the effect of a variation of pressure

without change of temperature, we must know whether the volume

for the

homogeneous phase represented by

is

greater or less than

the volume of the same matter divided between the phases A, B, and
C.

If the

homogeneous phase has the greater volume, an increase of

pressure will cause the sheet (D) to separate from the plane tangent to

the other sheets, and a diminution of pressure will cause a part of the
sheet (D) to protrude below that tangent plane.
will

And

be produced by the opposite changes of pressure,

neous phase has the

less

volume.

if

these effects

the homoge-

All this appears from precisely the

same considerations which were used in the analogous case for two
component substances.
Now when the sheet (D) rises above the plane tangent to the other
sheets, the general features of the surface of dissipated

not altered, except

by the disappearance

of the point D.

energy are

But when

the sheet (D) protrudes below the plane tangent to the other sheets,
the surface of dissipated energy will take the form indicated in figure

3.

It will include portions of the four sheets of the primitive surface,

poi-tions of the six developable sui-faces

formed by a double tangent

by two, and portions of

plane rolling upon these sheets taken two

three triple tangent planes for these sheets taken

(D) being always one of the three.

by

threes, the sheet

182

J.

W. Gihbs

Equilibrium of Heterogeneous Substances.

But wlieu the points of contact with the quadruple tangent plane
which represent the four coexistent phases can be joined so as to
form a quadrilateral

ABCD

(fig.

without reentrant angles, the

4)

surface of dissipated energy will include this plane quadrilateral,

portions of the four sheets of the primitive surface which are tangent
to

and portions of the four developable surfaces formed by double

it,

Fig. 4.

Pig.

5.

tangent planes rolling upon the four pairs of these sheets which corres-

pond

eral effect of a variation of temperature

energy,

let

these states (which

there

heat

is

first
is

by

the point

diagonals of the quadrilateral.

Among

all relate to

the same kind and quantity of matter)

is composed of the phases

composed of the phases B and D.

one which

is

which

of these states

is

the gen-

upon the surface of dissipated

us consider the composite states represented

I at the intersection of the

the

To determine

to the four sides of the quadrilateral.

and C, and another

if the entropy of

Now

greater than that of the second,

given out by a body in passing from the

state at constant temperature

and

pressure,)

first

which we

(i.

e., if

to the second

may

suppose

without loss of generality, an elevation of temjjerature while the

pressure remains constant will cause the triple tangent planes to
(D),

(B),
triple

and (A), and

tangent

planes

to

to

(B),

(A),

(D), and

(C),

to

and

(B),

and

(C),

rise

to

above the
(A),

(C),

and (D), in the vicinity of the point I. The surface of dissipated

energy will therefore take the form indicated in figure 5, in Avhich
there are two plane triangles and five developable surfaces besides
portions of the four primitive sheets.
will give a difierent

sipated energy.
into

diminution of temperature

but entirely analogous form to the surface of

The

quadrilateral

ABCD

two triangles along the diameter

lU).

will

The

in

this case

effects

dis-

break

produced by

J.

W. Gihhs

Equilibriutn of Heterogeneous Substances.

183

variation of the pressure while the temperature remains constant will

of course be similar to those described.

of

volume instead of tlie

sented

by

By considering

difference of entropy of the

the difference

two

the point I in the quadruple tangent plane,

states repre-

we may

distin-

guish between the effects of increase and diminution of pressure.

It

should be observed that the points of contact of the quadruple

tangent plane with the primitive surface

curves belonging to the

So

latter.

may be

at isolated points or

also, in the case

of two component

may be at
Such cases need

substances, the points of contact of the triple tangent line

isolated points belonging to the primitive curve.

not be separately treated, as the necessary modifications

in the pre-

ceding statements, when applied to such cases, are quite evident.

And

remaining discussion of this geometrical method,

in the

generally be

left to

the reader to

make

it

will

the necessary limitations or

modifications in analogous cases.

The necessary condition

in

regard to simultaneous variations of

temperature and pressure,

in

order that four coexistent phases of

two components, shall

remain possible, has already been deduced by purely analytical pro-

three components, or three coexistent phases of

cesses.

(See equation (129).)

We will

next consider the case of two coexistent phases of identi-

cal composition,

The

and

first,

when the number

coexistent phases, if each

represented

is

of components

is

two.

variable in composition, will be

by the point of contact of two

curves.

One

of the

above the other except at the point of contact therefore, when the temperature and pressure remain constant,
one phase cannot be varied in composition without becoming unstable
curves will in general

lie

while the other phase will be stable

if the proportion of either comvarying the temperatui'e or pressure, we

cause the upper curve to protrude below the other, or to rise

ponent

may

is

(relatively)

increased.

entirely

By

above

it.

(By comparing the volumes or the

entropies of the two coexistent phases,

we may

easily determine

which result would be produced by an increase of temperatiire or

of pressure.) Hence, the temperatures and pressures for which two
coexistent phases have the same composition form the limit to the

temperatures and pressures for which such coexistent phases are possible.
It will be observed that as we pass this limit of temperature

and pressure, the pair of coexistent phases does not simply become
unstable, like pairs and triads of coexistent phases Avhich we have
considered before, but there ceases to be any such pair of coexistent
The same result has already been obtained analytically on
phases.

W. Gibhs

184

J.

page

155.

Equilihrmm of Heterogeneous Substances.

But on that

phases are possible,

the saniJ values of

be two

thei-e will

and

which the coexistent

side of the limit on

pairs of coexistent phases for

p, as seen in figure

If the curve

6.

and the curve BB'

sents vapor,

(represented by)

B may

AA'

repre-

liquid, a liquid

exist in contact with

same temperature and

pressure) a liquid B' in contact with a vapor
If we compare these phases in respect to
A'.
a vapor A,

and

(at the

their composition,
Fig.

6.

vapor

component, and
are

made

see that in one case the

in the other case poorer.

Therefore,

if

these liquids

to boil, the effect on their composition will be opposite.

the boiling

is

approach each other in composition, and the curve

will rise relatively to the curve

to each other,

If

continued under constant pressure, the temperature will

rise as the liquids

BB'

we

richer than the liquid in a certain

is

when the two

liquids

the vapors which they yield.

AA', until the curves are tangent

become identical in nature, as also

In composition, and in the value of

But

unit of mass, the vapor will then agree with the liquid.

per

if

the

curve BB' (which has the greater curvature) represents vapor, and

AA'

represents liquid, the effect of boiling will

and A'

differ

more

make

the liquids

In this case, the relations indi-

in composition.

cated in the figure will hold for a temperature higher than that for

which (with the same pressure) the curves are tangent to one another.
When two coexistent phases of three component substances have
the same composition, they are represented

two

at the point of contact, the case

just considered.

The upper

represents unstable phases.

is

by the point

of contact of

do not intersect
very similar to that which we have

sheets of the primitive surface.

If these sheets

sheet except at the point of contact

If the temperature

or pressure are so

varied that a part of the upper sheet protrudes through the lower, the
points of contact of a double tangent plane rolling upon the two
sheets will describe a closed curve on each, and the surface of dissi-

pated energy will include a portion of each sheet of the primitive surface united by a ring-shaped developable siirface.
If the sheet

having the greater curvatures represents

liquid,

and

the other sheet vapor, the boiling temperature for any given pressure
will be a maximum, and the])ressure of saturated vapor for any given
temperature will be a minimun, when the coexistent liquid and vapor

have the same composition.

But if the two sheets, constructed for the temperature and pressure
of the coexistent phases which liave the same composition, intersect

J. TT.

Gihhs

Equilibrium of Heterogeneous Substances.

at the point of contact, tlie

below

whole primitive

sui-face as

85

seen from

will in general ])resent four re-entrant furrows, radiating

the point of contact, for each of Avhich a developable suriace

from

may he

formed by a rolling double tangent plane. The different parts of the

surface of dissipated energy in the vicinity of the point of contact are

ATB, ETF are parts of one sheet ol the

7.
CTD, GTH are parts of the other. These are
developable surfaces BTC, DTE, FTG, HTA. Now

represented in tigure
primitive surface, and

united by the

we may make
the other

either sheet of the primitive sui'face sink relatively to

by the proper

variation of tempei'ature or pressure.

ATB, ETF

sheet to which

belong

is

If the

that which sinks relatively, these

parts of the surface of dissipated energy will

be merged

in one, as well as the

developable

BTC, DTE, and also FTG, HTA.

(The lines CTD, BTE, ATF, HTG will

surfaces

separate from one another at T, each forming

a continixous curve.)

But

if

the sheet of the

primitive surface which sinks relatively

these parts will

face of dissipated energy, as will be the developable surfaces

ATH, and
It is

also

evident that this

minimum

is

not a case of

maximum

or

minimum tem-

maximum

pressure for coexistent phases at constant temperature.

Another case of interest

coexistent phases

two.

BTC,

DTE, FTG.

perature for coexistent phases under constant "pressure, or of

or

is

and GTH belong, then

be merged in one in the sur-

CTD

that to which

is

is

when

the composition of one of three

such as can be produced by combining the other

In this case, the primitive surface must touch the same plane

in three points in the

same straight

line.

Let us distinguish the parts

of the primitive surface to which these points belong as the sheets (A),
(B),

The

and (C), (C) denoting that which

sheet (C)

upon (A) and

is

is

intermediate in position.

evidently tangent to the developable surface formed

(B).

It

may

or

it

may

not intersect

it

at the point of

above the developable surare unstable in regard

face, (unless it represents states which
changes,) and the surface of dissipated energy
to continuous
will include parts of the primitive sheets (A) and (B), the developcontact.

If

it

does not,

able surface joining them,

in

which

it

it

must

lie

and the single point

meets this developable surface.

ture or pressure

is

varied so as to

Trans. Conn. Acad., Vol.

III.

make
24

of the sheet (C)

Now,

if

the tempera-

the sheet (C) rise above the

Februaby, 1876.

186

J.

W. Gihbs

Equilibrium of IIetero(/eneous Substances.

developable surface formed on the sheets (A) and (B), the surface of
dissipated energy will be altered in its general features only by the

removal of the single point of the sheet

or pressure

is

altered so as to

make a

But

(C).

if

the temperature

part of the sheet (C) protrude

through the developable surface formed on (A) and (B), the surface
of dissipated energy will have the
b
form

indicated in figure
include two

will

ABC

8.

Tt

plane triangles

and A'B'C, a part of each of

the sheets (A) and (B), represented

in the figure
left

right of the line bBB'b', a small

\
^''^-

"

^-

by the spaces on the

and on the

of the line aAA'a'

part

CC

of the sheet (C), and de-

velopable surfaces formed upon these sheets taken by pairs ACC'A',

BCC'B', aABb, a'A'B'b'. the

two being

last

different portions of the

same developable surface.

But

if,

when

the

primitive

temperature and pressure that

surface
it

the same plane in the same straight

the middle

constructed for such a

is

has three points of contact with

line,

the sheet (C) (which has

position) at its point of contact

with the triple tangent

plane intersects the developable surface formed upon the other sheets

(A) and (B), the surface of dissipated energy will not include this
develojjable surface, but will consist of portions of the three primi-

two developable

tive sheets with

on (B) and (C).

surfaces formed on (A) and (C) and

These developable surfaces meet one another at

the point of contact of (C) with the

tri2)le

tangent plane, dividing the

portion of this sheet which be-

longs to the sxxrface of dissipated

energy into two pai'ts. If now

the temperature or pressure are
vai'ied so as to
((')

sink

make

the sheet

relatively to the

de-

velopable surface formed on (A)

and

(B), the only alteration in

the general features of the surof dissipated energy will

be that the developable surfaces

face
Fig.

9.

formed on (A) and (C) and on (B) and (C) will separate from
one another, and the two parts of the sheet (C) will be merged in
one.

But a contrary variation of temperature or pressure

will give a

J.

W. Gihbs

Equllihriunh of Heteror/eneous

surface of dissipated energy such as

taining two plane triangles

is

187

f'iuhstances.

represented in figure (9), conbelonging to triple tangent

ABC, A'B'C

planes, a portion of the sheet (A) on the left of the line aAxV'a', a por-

two separate

tion of the sheet (B) on the right of the line bBB'b',

portions

cCy and c'C y'

of the sheet (C), tAVo separate portions

aACc

and a'A'C'c' of the developable surface formed on (A) and (0), two
separate portions bBC;^ and b'B'C';/' of the developable surface
formed on (B) and (C), and the portion A'ABB' of the developable
surface formed on (A) and (B).

From

these geometrical relations

it

temperature of three coexistent phases

appears that
is

(in

maximum

or

general) the

minimum

for

constant pressure, and the pressure of three coexistent phases a maxi-

mum

or

minimum

for constant temperature,

the three coexistent phases

is

when the composition

of

such that one can be formed by com-

This result has been obtained analytically

bining the other two.

on page 150.

The preceding examples

are

of the m-'Q surfaces and curves.

amply sufficient to illustrate the use

The physical properties indicated by

the nature of the surface of dissipated energy have been only occasionally mentioned, as they are often far

more

the diagrams than they could be in words.

distinctly indicated

It will

by

be observed that

a knowledge of the lines which divide the various dilFerent portions

of the surface of dissipated energy and of the direction of the rectilinear elements of the developable surfaces, as projected

upon

X-Y^ plane without

surface in

space,

is sufficient for

a knowledge of the form of the

tn-'C,

the

the determination (in respect to the quantity

and composition of the resulting masses) of the combinations and

separations of the substances, and of the changes in their states of
aggregation, which take place when the substances are exposed to
the temperature and pressure to which the projected lines relate,
except so far as such transformations are prevented by passive
sistances to change.

re-

CRITICAL PHASES.
It

has been ascertained by experiment that the variations of two

coexistent states of the same substance are in

some cases limited

in

one direction by a terminal state at which the distinction of the

coexistent states vanishes.*
This state has been called the critical

Analogous properties may doubtless be exhibited by compounds of variable composition without change of temperature or

state.

* See Dr. Andrews

''

On

the continuity of the gaseous and liquid states of matter."

Phil. Trans., vol. 159, p. 575.

188

W. Glbbs

J.

For

pressure.

if,

Equilibrium of Heterogeneous Substances.

at

any given temperature and pressure, two

are capable of forming a stable mixture in any ratio ni

mg

liquids

than

less

and in any greater than h, a and b being the values of that ratio
for two coexistent phases, while either can form a stable mixture with
a third liquid in all proportions, and any small quantities of the first
and second can unite at once with a great qiiantity of the third to
form a stable mixture, it may easily be seen that two coexistent mix,

may

tures of the three liquids

be varied in composition, the tempera-

ture and pressure remaining the same, from initial phases in each of

which the quantity of the third liquid is nothing, to a terminal phase

which the distinction of the two phases vanishes.
In general, we may define a critical phase as one at which the distinction between coexistent phases vanishes.
We may suppose the
in

coexistent phases to be stable in respect to continuous changes, for

although relations in some respects analogous might be imagined to

hold true

in

regard to phases which are unstable in respect to con-

tinuous changes, the discussion of such cases would be devoid of

But

interest.

if

the coexistent phases and the critical phase are

unstable only in respect to the possible formation of phases entirely

from the

different

changes

will in

and adjacent phases, the liability to such

between the critical and

critical

no respect

affect the relations

adjacent phases, and need not be considered in a theoretical discussion

of these relations, although

it

tion of the phases considered.

may

prevent an experimental realiza-

F'or the sake of brevity, in the follow-

ing discussion, phases in the vicinity of the critical phase will generally be called stable, if they are unstable only in respect to the

formation of phases entirely different from any in the vicinity of the

critical phase.

Let us

first

consider the

number of independent

a critical phase (while remaining such)

the

number

is

capable.

variations of which
If

we denote by

of independently variable comjjonents, a pair of coexis-

n independent variations, which may be

tent phases will be capable of

expressed by the variations oi n of the quantities

If

we

limit these variations

by giving

to n

t,
/j.
p^ i.i^, /j^,
of the quantities the

constant values which they have for a certain

critical

If

we now vary

n l quantities, we shall
stant a

new

is

first series,

we

by the

infinitesimally the values of these

for the

new

set

of values considered con-

linear series of pairs of coexistent phases.

pair of phases in the

* This term

have

phase,

obtain a linear* series of pairs of coexistent phase's terminated

critical phase.

Now

for every

there must be pairs of phases in the

used to characterize a series having a single degree of extension.

W. Glbbs EquiUhriuni of Heteroffttieoiis Substances.

J.

second series differing infinitely

from the pair

little

and
must be

in the first,

vice versa, therefore the second series of coexistent phases

terminated by a critical phase which

little,

from the

the values of any

mined by a

We

first.
;/

of the quantities

critical phase,

differs,

but

we

^,jtj, /^
j,

//g?

infinitely

differs

we vary

see, therefore, that if

189

arbitrarily

/^n,

as deter-

obtain one and only one critical phase

for each set of varied values

e.,

i.

a critical phase

capable of

is

n~-l independent variations.

The quantities t, p, /v^, fj.2,

A'n, have the same values in
coexistent phases, but the ratios of the quantities i],v,m^,m^,,

two

m,

two phases. Or, if for convenience we

compare equal volumes of tlie two phases (which involves no loss of
generality), the quantities r/, m^, m,2,
ni will in general have
different values in two coexistent phases.
Applying this to coexisare in general dift'erent in the

we

tent phases indefinitely near to a critical phase,

immediate vicinity of a
ties

t,

p,

/<,, //g,

critical phase, if

Mn, are

see that in the

the values of n of the quanti-

regarded as constant (as well as

variations of either of the others will be infinitely small

with the variations of the quantities

dition, whicli

we may

?/,

This con-

m.

the

write in the form

=0,

(-j
we have

characterizes, as

m^, mg,

v),

compared

(200)

seen on page 171, the limits which divide

stable from unstable phases in respect to continuous changes.

In fact,

if

we give

values determined

by

to the quantities

^,

yWj, yUg,

/<_i

constant

a series

a pair of coexistent phases, and to

of values increasing from the less to the greater of the values which

we determine

has in these coexistent phases,

it

a linear series of phases

connecting the coexistent phases, in some part of which

yM

since

it

has the same value in the two coexistent phases, but not a uniform
value throughout the series (for
probable,

all

function of

these phases

^,

or of m,

if it

had, Avhich

would be coexistent)
if

v also

is

is

theoretically im-

must be a decreasing

supposed constant.

Therefore,

the series must contain phases which are unstable in respect to con-

tinuous changes.
phases

may

(See page

68.)

And

as such a pair of coexistent

be taken indefinitely near to any

critical

phase, the

unstable phases (with respect to continuous changes) must approach

indefinitely near to this phase.

190

./.

W. Gibbs

Equilibrium of Heterogeneous Substances.

have similar properties with reference to stability

For as every
stable phase which has a coexistent phase lies upon the limit which
separates stable from unstable phases, the same must be true of any
Critical phases

as determined with regard to discontinuous changes.

(The same may be said of

stable critical phase.

which the

in respect to

The
ties

^,

critical

phase

fX2->

t.he

Mn

'

leave out of

unstable.)

is

linear series of phases determined

jo, yUj,

we

kind of discontinuous change

liability to the particular

account the

phases which

critical

are unstable in regard to discontinuous changes if

by giving to n

ol the quanti-

constant values which they have in any

pair of coexistent phases consists of unstable phases in

either direction
is

it

consists of stable phases.

Hence,

if

varied in such a manner thatn of the quantities t,p,

remain constant,

it

will remain stable in respect

Therefore,

to discontinuous changes.
rn

when

any

t,

v, jj^, ^Iq,

pin-i

But

critical phase.

yu is

part

the

beyond these phases

between the coexistent phases, but in the part

in

a critical phase
/x^, /U2,

J-^n

both to continuous and

an increasing function of

have constant values determined by

as equation (200) holds true at the critical

phase, the following conditions must also hold true at that phase

=0,

(^'-^1

\dm^Jt,

'

(20,)

^0.

(202)

V,

If the sign of equality holds in the last condition, additional conditions,

concerning the differential coefficients of higher orders, must be

satisfied.

Equations (200) and (201)

of critical phases.

It is

may

in general be called the equations

evident that there are only two independent

equations of this character, as a critical phase

is

capable of

n1

inde-

pendent variations.
We are not, however, absolutely certain that equation (200) will

always be

satisfied

denominator

in

by a

critical phase.

the fraction

may

For

it

is

possible that the

vanish as well as the numerator for

an infinitesimal change of phase in which the quantities indicated

are constant.
refer to

some

tial coefficient

we may siippose the subscript n to

component substance, or use another differenof the same general form (such as are described on
In such a case,

different

page 171 as characterizing the

limits of stability in respect to con-

making the corresponding changes in (201) and

We may be certain that some of the formulae thus formed
(202).
But for a perfectly rigorous method there is an advanwill not fail.

tinuous changes),

Gihhs

J. TT^

tage

in the use of

Eqidlihrium of Ileteroge^ieoris Suhstances.

//,

mj,*^,,

quantities

t,

ii^, //o,

...//

may be

condition that the phase

which Rn+x

^^enotes the

The

independent variables.

as

varied without altering any of the

then be expressed by the equation

will

i?+t=^.
in

101

(203)

same determinant

as

To
we observe
when varied

on page 169.

obtain the second equation characteristic of critical phases,

that as a phase which

is

cannot become unstable

critical

so that n of the quantities

^,

/>, //j, //g,

volume,

differential of i?^_j for constant

"n+ldtf^^I^^l dm.

dm^

dt}

A'n

remain constant, the

viz.,

_j_

dli^,
^j^^^

'
'

(204)

dtrir,

cannot become negative when a of the equations (172) are satisfied.

Neither can it have a positive value, for then its value might become
negative by a change of sign of

Therefore the expres-

dm,^^ etc.

c?//,

sion (204) has the value zero, \in of the equations (172) are satisfied.

may be

This

expressed by an equation
aS'=0,

which

(205)

which the constituents are the

same as in 7?+,, except in a single horizontal line, in which the
differential coefliicicnts in (204) are to be substituted.
In whatever
line this substitution is made, the equation (205), as well as (203),

in

aS

denotes a determinant

in

will hold true of every critical phase without exception.

If

we

write

choose

TJ for

^,

/),

Wj, Wg,

wi as

independent variables, and

the determinant

^2r

dH_

^?^?_

c?m,2

dm^dm^

dm^_^dm,^

dn
dm 2^

dm,^_^dm^

dn
dnt-ydm,^

dn

dH

d^^

(206)

_dH

drn^dm

and

V for the determinant

formed from

this

by substituting

for the

constituents in any horizontal line the expressions

dU

dU

dtn^

dm?^

dU
dn/in^^

''

the equations of critical phases will be

U=

0,

F=

0.

(208)

immediately from the definition of a critical phase, that

an infinitesimal change in the condition of a mass in such a phase
It results

192

J.

may

W. Gihhs

Equilibrhi'in of Heterogeneous Substances.

cause the mass, if

it

remains in a state of dissipated energy

(i.

a state in which the dissipation of energy by internal processes

in

complete), to cease to be homogeneous.

e.,

is

In this respect a critical phase

resembles any phase which has a coexistent phase, but differs from

such phases in that the two parts into which the mass divides when
it ceases to be homogeneous differ infinitely little from each other and

from the original phase, and that neither of these parts is in general
If we consider a change in the mass to be deterinfinitely small.

mined by the values of

(///,

dm^,

dv,

dm 2,

dm,

it

evident

is

that the change in question will cause the mass to cease to be homo-

geneous whenever the expression

^^1 a,j+

^i^^i
dv

d?]

dv+

^"-' dm,,

dm

c7m
+ ^^^
dm

(209)

For if the mass should remain homogeneous,

would become unstable, as Hn-^i ^voukl become negative. Hence,
in general, any change thus determined, or its reverse (determined by
dm the same values taken negagiving to c?//, dv, dm,, dm2,
The condithe
mass
to
cease
to be homogeneous.
will
cause
tively),
satisfied
with
reference
to
dt^,
dm,, dm^,
must
be
dv,
which
tion
neither
the
change
indicated,
nor the
order
that
in
dm,
of
homogeneity
the
mass,
is
expressed
by
destroy
the
reverse, shall
zero.
expression
to
equating the above
But if we consider the change in the state of the mass (supposed to
remain in a state of dissijiated energy) to be determined by arbitrary
has a negative value.
it

values of n-\-\ of the differentials dt, dp, dfA,, d}x^,

will
it

be entirely

For,

different.

will consist of

two

if

d^^, the case

the mass ceases to be homogeneous,

coexistent phases, and as applied to these only

be independent.

There-

n of the

quantities

fore, for

arbitrary variations of n-^\ of these quantities, the mass

t-,pi j^i-, P-2-)

/^n

will

must in general remain homogeneous.

But if, instead of supposing the mass to remain in a state of dissipated energy, we suppose that it remains homogeneous, it may easily
be shown that to certain values of w -j- 1 of the above differentials
there will correspond three different phases, of which one is stable
with respect both to continuous and to discontinuous changes, another
is stable with respect to the former and unstable with respect to the
latter,

and the third

is

unsta})le with respect to both.

In general, however,
or

if

n of the quantities p,

t,

/.i

arbitrary functions of these quantities, have the

//,
j-i.^,
same constant
.

values as at a critical phase, the linear series of phases thus deter-

mined

will be stable, in the vicinity of the critical phase.

But

if less

J.

W. Gibhs

Equilihriuyn of Heterogeneous Substances.

193

than n of these quantities or functions of

tlie same together with cerm^,

m,, or arbitrary functions of
quantities, have the same values as at a critical phase, so

tain of the quantities

the latter

v, ni^,

//,

as to determine a linear series of phases, the difterential of -K+j in

such a series of phases will not

in

general vanish at the critical phase,

so that in general a part of the series will be unstable.

We

may

by considering separately the

n=zl and n
2.
If a mass of invariable composition is in a critical state, we may keep its volume constant, and
destroy its homogeneity by changing its entropy (i. e., by adding or
subtracting heat probably the latter), or we may keep its entropy
illustrate these relations

cases in which

constant and destroy

we keep

its

homogeneity by changing

its

pressure constant

we cannot destroy

volume but if
homogeneity by

its

its

any thermal action, nor if we keep its temperature constant can we

destroy its homogeneity by any mechanical action.
When a mass having two independently variable components is in
a critical phase, and either its volume or its pressure is maintained
constant, its homogeneity may be destroyed by a change of entropy
or temperature.

Or,

if

either its entropy or its temperature

is

main-

homogeneity may be destroyed by a change

of volume or pressure.
In both these cases it is sup^^osed that
the quantities of the components remain unchanged.
But if we
suppose both the temperature and the pressure to be maintained constant, the mass will remain homogeneous, however the proportion of
tained constant,

its

the components be chilnged.

phases, one of which

is

Or,

if

a mass consists of

two coexistent

a critical phase having two independently

variable components, and either the temperature or the pressure of

the mass

is

maintained constant,

or thermal means, or

it

will not

by changing the

be possible by mechanical

quantities of the components,

to cause the critical phase to change into a pair of coexistent phases,

whole mass. The stateparagraph and of the preceding have reference only to

so as to give three coexistent phases in the

ments of

this

infinitesimal changes.*
*
of a

A brief

came

abstract (which

memoir by M. Duclaux,

found in Comptes Bendus,

"

to the author's notice after the

Sur

la

above was in type)

separation des liquides melanges, etc." will be

vol. Ixxxi. (1875), p. 815.

Trans. Conn. Acad., Vol.

III.

25

February, 1876.

194

W. Gihhs

.7.

Equilihriimi of Heterogeneous Substances.

ON THE VALUES OF THE POTENTIALS WHEN THE QUANTITY OF ONE

OF THE COMPONENTS IS VERY SMALL.
If

we apply equation

homogeneous mass having two indeaS'j, and make <, jo, and mj

(97) to a

pendently variable components S^ and

constant,

we

obtain

,ip\

+,Jp)

^0.

(2,0)

Therefore, for ^21=0, either

='
(P)
\am2/t,p, m,

>)
(21
^
'

or
(212)

ydm^Jt,

p,

m,

Now, whatever may be the composition of the mass considered,

we may always so choose the substance S-^ that the mass shall consist
any other variable comequation
But
^2=0.
(212) cannot hold
thus applied. For it may easily be shown (as has

solely of that substance,

ponent
true

we

/Sg,

shall

general as

irt,

and

in respect to

have

been done with regard to the potential on pages 148, 149) that the
value of a differential coefficient like that in (212) for any given mass,

when

^S', (to which m^ and }.i relate) is determined, is

independent of the particular substance which we may regard as the

the substance

other component of the mass; so that,

when

the substance denoted

must hold true without such a

be the

if

equation (212) holds true

by S^ has been
restriction,

so chosen that ???2=0,

it

which cannot generally

case.

In fact,

it

is

easy to prove directly that equation (211) will hold

any phase which is stable in regard to continuous changes

and in which ^3=0, if nn.^ is capable of neggiive as well as positive
For by (171), in any phase having that kind of stability, /<,
values.
is an increasing function of m^ when t^ p, and m^ are regarded as
Hence, /<j will have its greatest value when the mass conconstant.
true of

sists

wholly of

/6'j, i.

e.,

when mo^O.

Therefore,

if

of negative as well as positive values, equation (211)

for

m^ = 0.

mg

is

capable

must hold true

(This appears also from the geometrical representation

See page 177.)

But if m^ is capable only of positive values, we can only conclude
from the preceding considerations that the value of the differential
of potentials in the m-C curve.

coefficient in (211)

cannot be positive.

cal significance of this case, viz., that

Nor,

if

we

consider the physi-

an increase of m,^ denotes an

Gihbs

TV.

./.

Equilibrivm of Heterogeneous Substances.

195

addition to the mass in question of a substance not before contained

in

does any reason appear for supposing that this differential

it,

To

cient has generally the value zero.

that

*S^j

denotes water, and 82 ^

The addition

ular hydrate).

*^'^^t

our ideas,

fix

(either

let

coeffi-

us suppose

anhydrous or any

partic-

of the salt to Avater, previously

in a

state capable of equilibrium with vapor or with ice, will destroy the
possibility of such equilibrium at the

The

brought
that

will dissolve the

liquid

//,

ice,

same temperature and

pressure.

or condense the vapor, which

is

under such circumstances, which shows

(the potential for water in the liquid mass) is diminished by
with

in contact

the addition of the

salt,

Now

it

when

the temperature and pi'essure are main-

there seems to be no

a priori reason for

supposing that the ratio of this diminution of the potential for water
to the quantity of the salt which is added vanishes with this quantity.
tained constant.

We

should rather expect that, for small quantities of the salt, an

kind would be proportional to its cause, i. e,, that the

effect of this

differential coefficient in (211)

an infinitesimal value of mg.

would have a finite negative value for

That this is the case with respect to

numerous watery solutions of

salts is

distinctly indicated

by the

experiments of Wtillner* on the tension of the vapor yielded by such

solutions, and of Riidorfff on the temperature at which ice is formed

them; and unless we have experimental evidence that cases are

numerous in which the contrary is true, it seems not unreasonable

in

to assume, as a general law, that

when mg has the value

zero and

is

incapable of negative values, the differential coefficient in (211) will

have a finite negative value, and that equation (212) will therefore

hold

true.

But

which mg

in

by

is

this case

must be carefully distinguished from that

capable of negative values, which also

a solution of a salt in water.

For

may

be

illus-

let

denote a hydrate of the salt which can be crystallized, and let

denote water, and let us consider a liquid consisting entirely of

trated

this

purpose

IS.y

and of such temperature and

pi'essure as to be in equilibrium with

In such a liquid, an increase or a diminution of the
quantity of w^ater would alike cause crystals of S^ to dissolve, which

crystals of

>S,.

requires that the differential coefficient in (211) shall vanish at the

particular phase of the liquid for which m^
0.

Let us return to the case

in

and examine, without other

* Pogg. Ann., vol.
f

Pogg. Ann.,

ciii.

(1858j, p.

which m^'m incapable of negative values

restriction in regard to the substances
529;

vol. cxiv. (1861), p. 63.

vol. cv. (1858), p.

85; vol. ex. (I860),

p.

564.

196

J.

W. Gibbs

Equilibrium of Heterogeneous ISubstances.

denoted by S^ and S^, the relation between

and pressure and

stant temperature

the differential coefficient in (211)

constant value as

changed.

we

If

0,

and

that

as having the

same

of

for such small values

may be regarded
the values of

t,

any con-

tor

p, and

being un-

denote this value of the differential coefficient by

1 the value of ^4 will

Then

when m^

ia

be positive, and will be independent oi m^.

for small values of

we have by

(210), approximately,

m
1.

e.,

(214)

If

we

write the integral of this equation in the form

/^2=^4
j5 like

will

1og-^,

(215)

have a positive value depending only upon the temperaAs this equation is to be applied only to cases in

ture and pressure.

which the value of ^2

regard

is

very small compared with

when temperature and

as constant,

ni^,

we may

pressui-e are constant,

and write
/i2

= ^log-^,

(216)

C denoting a positive quantity, dependent only upon the temperature

and pressure.
We have so far considered the composition of the body as varying
only in regard to the proportion of two components. But the argument will be in no respect invalidated, if we suppose the composition
of the

body

tities

to be capable of other variations.

and

6'

be functions not only

will

In this case, the quan-

temperature and

of the

pressure but also of the quantities which express the composition of

the substance of which together with

/S^

the body

the qiiantities of any of the components besides

(relatively to the quantities of others),

that the value of

nearly the same as

/a^,

if

it

is

iS^

composed.

If

are very small

seems reasonable to assume

A and C, will be

and therefore the values of

these components were absent.

W. GihbsEquilihrium of Heterogeneous

J.

Hence,
/S,

as

if

197

Snbstances.

the independently variable components of any

body

are

the quantities of the latter being very small

and S,,^
compared with the quantities of the former, and are incapable of
.

negative values,

/S'^.,

we may

express approximately the values of the

by equations (subject of course to the uncerof the assumptions which have been made) of the form

potentials for S,
tainties

S,i,

tS^.

/^;,=

(217)

198

JV.

(T.

these

may

cules

which

Gihbs

E(2Uilibrium of Heterogeneous Substances.

be more complicated.

Otlier cases are explained

by mole-

quantity of matter which they contain, but

differ in the

not in the kind of matter, nor in the proportion of the different kinds.
In

other cases, there appear to be different sorts of molecules,

still

which

kind nor in the quantity of matter which

differ neither in the

they contain, but only

in

the manner in which they are constituted.

What is essential in the cases referred to is that a certain number of

some sort or sorts of molecules shall be equivalent to a certain number
of some other sort or sorts in respect to the kinds and quantities of
matter which they collectively contain, and yet the former shall never
be transformed into the latter within the body considered, nor the
latter into the former, however the proportion of the numbers of the
may be

different sorts of molecules

varied, or the composition of the

thermodynamic state as represented by

temperature and pressure or any other two suitable variables, provided, it may be, that these variations do not exceed certain limits.
Thus, in the example given above, the temperature must not be
raised beyond a certain limit, or molecules of hydrogen and of oxygen

body

in other respects, or its

may be
The

transformed into molecules of water.

differences in bodies resulting

from such differences

in the con-

stitution of their molecules are capable of continuous variation, in

bodies containing the same matter and in the same thermodynamic

state as determined, for example, by pressure and temj^erature, as the

These
which depend upon the
which the molecules are combined to form sensible masses.

numbers of the molecules of the

different sorts are varied.

differences are thus distinguished from those

manner in
The latter do not cause an
fundamental equation

of which the function

is

increase in the

but they

may

number of

variables in the

be the cause of different values

sometimes capable for one

set of values

of

the independent variables, as, for example, when we have several

in, one
different values of ? for the same values of t, p, m^, in^,
.

perhaps being for a gaseous body, one for a liquid, one for an amorphous solid, and others for different kinds of crystals, and all being
invariable for constant values of the above mentioned independent
variables.
B\it

it

must be observed that when the

differences in the constitu-

tion of the molecules are entirely detei-mined

the different kinds of

express

its

thermodynamic

increase in the

any
For example,

if

by the

quantities of

matter in a body with the two variables which

number

state, these differences

will not involve

of variables in the fundamental eqnation.

we should

raise the temperature of the

mixture of

J.

W. Gihhs Equilihriw) of Heterogeneous

I

Substances.

199

vapor of water and free liydrogen and oxygen, which we have just
considered, to a point at which the numbers of the] different sorts of

molecules are entirely determined by the temperature and pressure

and the total quantities of hydrogen and of oxygen which are present,
the fundamental equation of such a mass would involve but four inde-

pendent variables, which might be the four quantities just mentioned.

The fact of a certain part of the matter present existing in the

form of vapor of water would, of course, be one of the facts which

determine the nature of the relation between and the independent
variables, which is expressed by the fundamental equation.
But in the case first considered, in which the quantities of the
different sorts of molecules are not determined by the temperature
and pressure and the quantities of the different kinds of matter in the
"Q

body

as determined

by

its

ultimate analysis, the components of which

the quantities or the potentials appear in the fundamental equation

must be those which are determined by the proximate analysis of the

body, so that the variations in their quantities, with two variations
relating to the thermodynamic state of the body, shall include all the
variations of which the body is capable.*
Such cases present no
especial

difliculty

there

indeed nothing in

is

the

physical

and

chemical properties of such bodies, so far as a certain range of experiments is concerned, which is different from what might be, if the

proximate components were incapable of farther reduction or transformation.

Yet among the the various phases of the kinds of matter

by the different sets of values of the variables

concerned, represented

which

fundamental

satisfy the

eqiiation, there is a certain class which

These are the phases for which the entropy
value for the same matter, as detei*mined by the

merit especial attention.

has a

maximum

ultimate analysis of the body, with the same energy and volume.
fix

our ideas

us call the proximate components

let

ultimate components S,

and

quantities of the former,

and

S,,\

?,

let

w^^j,

aS\,
.

S^

To

and the

m^ denote the

m^, the quantities of the latter.

homogeneous functions of the first

degree of r>^,,
7; and that the relations between the substances
aSj,
S might be expressed by homogeneous equations of the first
degree between the units of these substances, equal in number to the
difference of the numbers of the proximate and of the ultimate com-

It is evident that w?
.

m.,^

are

* The terms proximate or ultimate are not necessarily to be understood in an absoAll that is said here and in the following paragraphs will apply to many
cases in which components may conveniently be regarded as proximate or ultimate

lute sense.

which are such only

in a relative sense.

200

J.

W. Gibhs

Equilibrium of Heterogeneous Substances.

The phases

ponents.

^,

m,

jo,

ni,,

m,,.

tain the quantities

7n,,

or,

?;

as they

a maximum
may also be

is

minimum for constant values of ?;,

a minimum for constant values

is

w,

of

The phases which satisfy this condition may be

when the fundamental equation (which will conm^ or yUj,
m^,
Indeed it is
//,) is known.
.

we may

easy to see that

is

or for which

readily determined

m,

w,

f,

described, those for which

m,

those for which

in question are

values of

for constant

phases by substituting

express the conditions which determine these

yUj,

/<

for the letters denoting the units

of the corresponding substances in the equations which express the

equivalence in ultimate analysis between these units.

These phases

may

be called, with reference to the kind of change

That we
which we
have used a similar term before, with reference to a different kind of
changes, yet in a sense entirely analogous, need not create confusion.
are considering, phases of dissipated energy.

It is characteristic of these

of i

in

any

the mass as well as

ino-

real
its

phases that

mass

we cannot

alter the values

in such a phase, while the

volume of

matter remain unchanged, without diminish-

the energy or increasing the entropy of some other system.

if the mass is large, its equilibrium can be but slightly dis-

Hence,

turbed by the action of any small body, or by a single electric spark,

or by any cause which is not in some way proportioned to the effect
to be produced.

But when the proportion of the proximate compoits temperature and pressure

nents of a mass taken in connection with

is

not such as to constitute a phase of dissipated energy, it may be

mass by the contact of a very

possible to cause great changes in the

small body.
contact

may

Indeed

it is

possible that the changes produced

by such

only be limited by the attainment of a phase of dissipated

energy. Such a result will probably be produced in a fluid mass by

contact with another fluid which contains molecules of all the kinds
which occur in the first fluid (or at least all those which contain

the same kinds of matter which also occur in other sorts of molecules),
but which differs from the first fluid in that the quantities of the
various kinds of molecules are entirely determined by the ultimate
composition of the fluid and its temperature and pressure. Or, to

speak without reference to the molecular state of the fluid, the result
considered would doubtless be brought about by contact with another
fluid,

which absorbs

all

the

proximate

... S, (or all those betw^ien

components of the

which there

first,

exist relations of equiva-

lence in respect to their ultimate analysis), independently, and without passive resistances, but for which the phase is completely deter-

W. Gibbs

J.

mined by

Equilibriutn of Heterogeneous Substances.

temperature and pressure and

its

its

ultimate composition (in

By

respect at least to the particular substances just mentioned).

it

is

aS\,

8^ independently

equilibrium with another containing these substances,

by

possible

change of

An

the

and without
meant that when the absorbing body is in

absorption of the substances

passive resistances,

201

shall

it

be

infinitesimal changes in these bodies to produce the ex-

all

these substances in either direction and independently.

may of course be made for

prevented by the occurrence of
in other words, it is assumed that the

exception to the preceding statement

cases in which the result in question

is

some other kinds of change

two bodies can remain in contact preserving the properties which
;

have been mentioned.

The term

catalysis has been applied to such action as

When

sidering.

out limitation

phase of dissi]iated energy,

change,

it

we

are con-

body has the property of reducing another, withwith respect to the proportion of the two bodies, to a
a

may

be called

a.

in

regard to a certain kind of molecular

perfect catalytic agent with respect to the

second body and the kind of molecular change considered.

It seems not improbable that in some cases in which molecular
changes take place slowly in homogeneous bodies, a mass of which
the temperature and pressure are maintained constant will be finally

brought to a state of equilibrium which

is

entirely determined

temperature and pressure and the quantities of

nents,

its

by

its

ultimate compo-

while the various transitory states through which the mass

passes, (which are evidently not completely defined

by the

quantities

may

be completely defined by the quantities of certain proximate components with the temperature and pressure, and

just mentioned,)

may be brought by processes approximately

permanent states to these various transitory states.
In such cases, we may form a fundamental equation with reference to
all possible phases, whether transitory or permanent
and we may
also form a fundamental equation of different import and containinoa smaller number of independent variables, which has reference solely

the matter of the mass

reversible from

The latter are the phases of dissipated energy (with reference to molecular changes), and when the
more general form of the fundamental equation is known, it will be
to the final phases of equilibrium.

easy to derive from

it

the fundamental equation for these permanent

phases alone.

Now,

as these relations, theoretically considered, are independent

of the rapidity of the molecular changes, the question naturally arises

whether in cases in which we are not able to distinguish such trausiTrans. Conn. Acad., Vol.

III.

26

February, 1876.

202

J.

Equilibrhmi of Heterogeneous Substances.

W. Gihbs

tory phases, they

may

not

still

have a theoretical

significance.

may

the consideration of the subject from this point of view,

us, in

If so,
assist

such cases, in discovering the form of the fundamental equation

with reference to the ultimate components, which

required to express

all

is

the only equation

the properties of the bodies which are capable

of experimental demonstration.

Thus, when the phase of a body

is

completely determined by the quantities of n independently vari-

and pressure, and we have

composed of a greater number
?^'
of proximate components, which are therefore not independently variable (while the temperature and pressure remain constant),
it seems quite possible that tlie fundamental equation of the body
may be of the same form as the equation for the phases of dissipated energy of analogous compounds of n' proximate and n ultimate
components, in which the proximate components are capable of
able components, with the temperature

reason to suppose that the body

is

independent variation (without variation of temperature or pressure).

And if such is found to be the case, the fact will be of interest as
affording an indication concerning the proximate constitution of the

body.

Such considerations seem to be especially applicable to the very

case in which at certain temperatures and pressures, regarded
as constant, the quantities of certain proximate components of a
mass are capable of independent variations, and all the phases produced by these variations are permanent in their nature, while at other

common

temperatures and pressures, likewise regarded as constant, the quantities of these proximate components are not capable of independent

and the jDhase may be completely defined by the quantities

There
of the ultimate components with the temperature and pressure.
condipressures,
temperatures
and
a
may be, at certain intermediate
tion with respect to the independence of the proximate components

variation,

intermediate in character, in which the quantities of the proximate

components are independently \ariable when we consider all phases,

the essentially transitory as well as the permanent, but in which these
quantities are not independently variable when we consider the
permanent phases alone. Now we have no reason to believe that the
passing of a body in a state of dissipated energy from one to another
of the three conditions mentioned has any necessary connection with

any discontinuous change of

state.

Passing the limit which separates

one of these states from another will not therefore involve any discontinuous change in the values of any of the quantities enumerated
in (99)-(103)

on page 143,

if

m,, m^,

m,

/^j, /<2,

yWn

are

W. Gihbs

J.

Equilihriun)

of Heterogeneuus Substances.

203

understood as always relating to the ultimate components of the body.

if we regard masses in the different conditions mentioned
above as having different fundamental equations, (which we may suppose to be of any one of the five kinds described on page 143,) these

Therefore,

equations will agi-ee at the limits dividing these conditions not only
in the values of all the variables

which appear

in the equations,

but

also in all the differential coefficients of the first order involving these

We may

by supposing the values

which the quantities of the ultimate components are constant to be represented by rectilinear coordinates.

variables.

of

t,

and

I),

Where
by

for a

illustrate these relations

mass

in

the proximate composition of such a mass

and p, the value of

'Q

will not

is not determined
be determined by these variables,

and the points representing connected values of <, jo, and I will form
This solid will be bounded in the direction opposite to that
a solid.
is measured, by a surface which represents the phases of
in which
'Q

In a part of the figure, all the phases thus reprebe permanent, in another part only the phases in the

dissipated energy.

sented

may

bounding
figure

and

surface,

(for

in a third part there

any phases

of which the

demonstrable), but only a surface.

may be

existence

is

no such solid
experimentally

This surface together with the

bounding surfaces representing phases of dissipated energy in the

parts of the figure mentioned above forms a continuous sheet, without
discontinuity in regard to the direction of

its

normal

at the limits

dividing the different parts of the figure which have been mentioned.

(There may, indeed,

gaseous states,

etc.,

be

but

if

different

we

sheets

representing liquid

and

limit our consideration to states of one

of these sorts, the case will be as has been stated.)

We

shall hereafter, in the discussion of the

fundamental equations

of gases, have an example of the derivation of the fundamental equation for phases of dissipated energy (with respect to the molecular

changes on which the proximate composition of the body depends)

from the more general form of the fundamental equation.

THE CONDITIONS OF EQUILIBRIUM FOR HETEROGENEOUS MASSES UNDER

THE INFLUENCE OF GRAVITY.
Let US now seek the conditions of equilibrium for a mass of various
kinds of matter subject to the influence of gravity.

It will

be con-

venient to suppose the mass enclosed in an immovable envelop which

is

in

impermeable to matter and to heat, and in other respects, except

regard to gravity, to make the same suppositions as on pages 115,

116.

The energy

of the mass will

now

consist of

two

parts, one of

204

W. Gihbs

./

Equilihrmm of Heterogeneous Substances.

which depends upon

its

intrinsic

energy of

nature and state, and the other upon

its intrinsic

Ds the

Let JJm denote an element of the mass,

position in space.

this element,

and g the force of gravity

(when without sensible motions)

plane,

its

height aboAe a fixed horizontal

then the total energy of the mass

will

be expressed by the formula

fDe-\-fghJ)m,
in

which the integrations include

(219)

the elements of the mass

all

and

the general condition of equilibrium will be

d/De + dfg h Dm ^ 0,

(220)

These

the variations being subject to certain equations of condition.

must express that the entropy of the whole mass is constant, that the
surface bounding the whole mass is fixed, and that the total quantiWe shall supties of each of the component substances is constant.
equations
of
condition,
other
and that the
pose that there are no
independently variable components are the same throughout the
whole mass

and we

shall at first limit ourselves to the consideration

of the conditions of equilibrium with respect to the changes which

may be expressed by infinitesimal variations of the quantities which
define the initial state of the mass, without regarding the possibility

of the formation at any place of infinitesimal masses entirely difl:erent

from any initially existing in the same vicinity.

Dm denote the entropy of the element
Let Z>//, Z>y, 7>mj,
Z>m, its volume, and the quantities which it contains of the various
.

components.

Then

Dm = Dm^

Z>m,

(221)

+ SI>m.

(222)

and

dDm dBm^

Also, by equation (12),

6 Da

By

6I)ij

+ /ij SBm^

dJJv

-\- ,u

6J)m.

these equations the general condition of equilibrium

(223)

may be

reduced to the form

ft 6Dri

-fp 6Dv

+//', 6Bm^

Dm

SDm

Jrfg Sh

Now

it

affect

will

-\-/gh

/// SD^n^

J^fgh dDm ^ 0.

(224)

be observed that the different equations of condition

diflf'erent

parts of this condition, so that

we must

have, sepa-

rately,

ftSDtj^O,

if

fdDrf=Q;

(225)

../.

W. Gibbs

Equilibriuiii of Heterogentoiis

fSubstaitces.

-fp 6Dv -\-fg 6h Dm ^ 0,

if

the bounding surface

fl.1^

dihn

mivaried

is

+ fgh

dlJra^

205
(226)

^ 0,

/6Dm = U n

if

(227)

y> 6Dm^ + f<i h 6JJrn ^ 0, if J'6lJni = 0. )

From (225) we may derive the condition of thermal equilibrium,
t

= Const.

(328)

Condition (226) is evidently the ordinary mechanical condition of

equilibrium, and may be transformed by any of the usual methods.

We may,

lor example, apply the formula to such

motions as miglit

take place longitudinally within an infinitely narrow tube, terminated

both ends by the external surface of the mass, but otherwise

at

of indeterminate form.

we denote by

If

the mass, and

by

v the

volume, included in the part of the tube between one end and a
transverse section of variable position, the condition will take the

form

- fp 6dv + fg 6h dm ^ 0,

(229)

which the integi'ations include the whole contents of the tube.

Since no motion is possible at the ends of the tube,

in

fp 6dv + fdv dp =:fd{p

Again,

if

we denote by y

fg 6h dm =fg -^
By

f6v
is

{dp

-\-

may

(230)

(231

be reduced to the form

g y dh) ^ 0.

(232)

arbitrary in value,

dp=~gydh,
which

0.

Sv y dv =^fg y Sv dh.

these equations condition (229)

Therefore, since 6v

6v) =z

the density of the fluid,

will hold true at

any point

(233)

in the tube, the difierentials being

taken with respect to the direction of the tube at that point. Therefore, as the form of the tube is indeterminate, this equation must
hold true, without restriction, throughout the whole mass. It evidently requires that the pressure shall be a function of the height
and that the density shall be equal to the first derivative of

alone,

this function, divided

Conditions (227)
equilibrium.

To

by

g.

contain

all

that

is

satisfy these conditions

characteristic .of chemical

it is

necessary and sufiicient

that
/^i

+ ff^

Const.

Mn

+ 9^=.

Const.

(234)

206

The

J.

W. Gihhs

expressions

Equilibrium of Heterogeneous Substances.

pi^,

the potentials for the

//

we have called
and which are entirely
nature and state of the
confusion between these

denote quantities which

several components,

determined at any point in a mass by

"the

mass about that point. We may avoid, all

quantities and the potential of the force of gravity,
the former,
indicated

when

if

necessary, as Intrinsic potentials.

by equations

(234)

may

we distinguish
The relations

then be expressed as follows

W/ten a fluid mass is in equilibrium under the influence of gravity^

and has the same independently variable cotnpofients throughout, the
intrinsic potentials for the several components are constant in any
given

level,

ence of

and diminish uniformly

the values

of

as the height increases, the differ-

the intrinsic potential

for any component

at two

different levels, being equal to the work done by the force of gravity
xohen a unit of matter falls from the higher to the longer level.
The conditions expressed by equations (228), (233), (234) are

necessary and sufficient for equilibrium, except with respect to the

possible formation of masses

which are not approximately identical

in

phase with any previously existing about the points where they may
be formed. The possibility of such formations at any point is evidently

independent of the action of gravity, and

is

determined entirely by

the phase or phases of the matter about that point. The conditions
of equilibrium in this respect have been discussed on pages 128-134.

But equations (228), (233), and (234) are not entirely independent.
For with respect to any mass in which there are no surfaces of discontinuity (i. e., surfaces where adjacent elements of mass have finite
diiFerences of phase), one of these equations will

the others.

which

Thus by

will hold true of

(228)

and (234), we

be a consequence of
obtain from (97),

may

any continuous variations of phase, the equa-

tion

vdp-g {m

dp= - gy dh

or

+ m) dh

(235)
(236)

which will therefore hold true in any mass in which equations (228)
and (234) are satisfied, and in which there are no surfaces of discon-

But the condition of equilibrium expressed by equation

of discontinuity;
(233) has no exception with respect to surfaces
will be necessary
occur,
it
surfaces
therefore in any mass in which such
by equations
expressed
relations
for equilibrium, in addition to the
tinuity.

(228)

and (234), that there

shall

be no discontinuous change of pressure

at these surfaces.

This superfluity in the particular conditions of equilibrium which

we have found, as applied to a mass which is everywhere continuous

./.

W. Gihhs

EquUihrium of Heterogeneoxis Substances.

due to the

in phase, is

fact that w^e liave

made

207

elements of volume

tlie

variable in position and size, while the matter initially contained in

these elements

Now,

not supposed to be confined to them.

is

as the

components may move in different directions when the

state of the system varies, it is evidently im])Ossible to define the
elements of volume so as always to include the same matter; we
different

must, therefore, suppose the matter contained in the elements of

volume to vary
elements fixed

and therefore

by

to vary, not only

it

will

to

make

these

mass has no surfaces of discon-

would be much the simplest

tinuity, this

surfaces of discontinuity,

mass

would be allowable

it

If the given

in space.

But

plan.

if

there are any

be possible for the state of the given

infinitesimal changes of phase in the fixed

elements of volume, but also by movements of the surfaces of discontinuity.

It woiild therefore

be necessary to add to

oixr

general con-

dition of equilibrium terms relating to discontinuous changes in the

volume about these

elements of

avoided

if

we

surfaces,

necessity

consider these elements movable, as

which

we can then

is

sup-

pose that each element remains always on the same side of the sui'face
of discontinuity.

Method of

treating the preceding problem, in xohich

tJie

elements of

volume are regarded as fixed.

It

may be

interesting to see in detail

of equilibrium

may

as fixed in position

be obtained

and

size,

if

we

how

the particular conditions

I'egard the elements of

and consider the

volume

possibility of finite as

well as infinitesimal changes of phase in each element of volume.

we

finite differences
sic

use the character

to denote the differences determined

of phase,

we may

energy of the whole mass

express the variation of the intrin-

in the

form

fdDe+fABE,
in

which the

first

finite

(237)

integral extends over all the elements which are

infinitesimally varied,

If

by such

variation.

and the second over

We may

all

those which experience

regard both integrals as extending

throughout the whole mass, but their values

will

be zero except for

the parts mentioned.

If

we do

not wish to limit ourselves to the consideration of masses

so small that the force

of gravity can be regarded as constant

we may use T to denote the potential of

the force of gravity, and express the variation of the part of the
energy which is due to gravity in the form
in direction

and

in intensity,

fT6DmfTADm.

(238)

208

W. Gibbs

J.

We

EquUibrinm of Heterogeneous Sabstances.

shall then have, for the general condition of equilibrium,

+ /ADe -J'TdDm - fTADrn ^

J'SDe

and the equations of condition

fSBi)

-\-fAI)i]

(240)

0,

f8Dm + fADm =
We

may

J'6I)m

0,

(239)

be

will

+ fADm^ =

(241)

0.

obtain a condition of equilibrium independent of these equa-

by subtracting these equations, multiplied each

by an indeterminate constant, from condition (239). If we denote
shall obtain
iff, we
these indeterminate constants by T^ Jfj,
tions of condition,

after arranging the terms

SDi

T 6Dm

T6Dt]

Jf, 6

Dm

fADE-TADm - TABij^M^ ADm^

The

variations, both infinitesimal

and

-lfdDm^o^

finite,

Jlf 6Dm^

in

(242)

this condition are

independent of the equations of condition (240) and (241), and ai'e

only subject to the condition that the varied values of De, Z>//,

Dm

I,

by a certain change
we do not suppose the same element to experiand an infinitesimal change of phase, we must have

Dnin.ioY each element are determined

But

of phase.

ence both a

as

finite

6IJ^ rSDiu -

T6I)ij - J/, 6I)m^ ...

- 3I6J)m^0,

(243)

- MADm^0.

(244)

and

ADe TADm - TABrj lf, ABm^

By
first

equation (12), and

of the necessary relation (222), the

in virtue

of these conditions reduces to

{tT)

SD,f

(yu,

- r M,) SBm^
+

for

...

which

it is

{/J

r-

M)

SDm ^

(245)

necessary and sufficient that

t

T,

(246)

V*

//-r=jf.

(247)

* The gravitation potential is liere supposed to be defined in the usual way.

But if
were defined so as to decrease when a body falls, we would have the sign + instead
of in these equations; i. e., for each component, the sum of the gravitation and
it

intrinsic potentials

would be constant throughout the whole mass.

W. Gihhs

J.

Condition (244)

liJquiUbriiim of Heterogeneous Substances.

may be reduced

form

to the

JZ>- TJDt] ~ {r-\-M,)Jnm,

and by (246) and (247)

(r+

J/) JX>y?^0; (248)

to

Ji>f - tJD)] -

/<,

JI)ni^ ...

/JJI)m^0.

determined subsequently to the change of })base

If values

209

(249)
ai-e

distin-

may be written
- //2>w'

guished by accents, this condition

Be' -

which

may

if

^'/^^

/'

(250)

0,

be reduced by (93) to

De'

Now

/^j Dm^ ...

DE-^tDi]-\- yu, Dm^

Dtf

tJJif

//,

7>>j, ...

Dv is

the element of volume

tinuity, let us suppose

Dt\

i-iJJniJ

+ pDv^O.

(251)

adjacent to a surface of discon-

Drf, lJm^\

J)m^

to be determined

same element of volume) by the phase existing on the other

As #,//,,.. // have the same
side of tlie surface of discontinuity.
values on both sides of this surface, the condition may be reduced by
(for the

(93) to

p'Bv +pBv^O.
That

(252)

the pressure must not be greater on one side of a surface of

is,

discontinuity than on the other.

Applied more generally, (251) expresses the condition of equilibrium

with respect to the possibility of discontinuous changes of phases at
Bv, the condition may also be written
any point. As Dv'

Ba'

- tBif +pBv' -

Z>m,', ...

yu,

u^BmJ^O,

(253)

yw have values determined

which must hold true when t, p, /u^,
BmJ have
by any point in the mass, and Be', By', Bv', Bm^',
.

by any possible phase of the substances of which

composed. The application of the condition is, however,

values determined

the mass

is

subject to the limitations considered on pages

128-134.

It

may

shown (see pages 160, 161) that for constant values of ^, /.i^,
//, and of Bv', the first member of (253) will have the least possiBm' are determined by a phase
ble value Avhen Be', />//, Bm^',
for which the temperature has the value t, and tlie potentials the
easily be
.

values //,,...

//.

It

will

be

sufficient, therefore, to

condition as applied to such phases, in which case

by

it

consider the

may be reduced

(93) to

p^p'^0.
That

is,

(254)

the pressure at any point must be as gieat as that of any

phase of the same components, for which the temperature and the
Tbans. Conn. Acad., Vol.

III.

27

April, 1876.

210

W. Gibhs

J.

Equilibrium of Heterogeneous Substances.

same values as at that point. We may also
by saying that the pressure must be as great

potentials have the

express this condition

as

consistent with equations

is

This condition with the

('240), (247).

when

will

be at

equations mentioned will always be sufficient for equilibrium

the condition

is

not satisfied,

e(|uilil)riuni

if

subsists,

it

least practically unstable.

Hence, the phase at any ])oint of a fluid mass, which is in stable

equilibrium under the influence of gravity (whether this force is due

mass

to external bodies or to the

itself),

and which has throughout

the same independently variable components,

is

completely deter-

any other point and the difference of the

values of the gravitation potential for the two points.

mined by the phase

at

FUNDAMENTAL EQUATIOXS OF IDEAL GASES AND GAS-MIXTURES.

For a constant quantity
the volume and pressure

of a perfect or ideal gas, the product of

is

proportional to the temperature, and the

variations of energy are proportional to the variations of tempera-

For a

ture.

unit of such a gas

2)

we may write

a and

^c

By

denoting constants.

=a

d8

t,

dt,

integration,

we

obtain the equation

=CJ+E,
in which
ate t and

E also denotes a constant.

})

from

(11),

by these equations we

If

elimin-

we obtain

de =i

f-^ di]
,

s-B

dv,

or

ds
c

The

integral of this equation

c log

dv
= di) a
-,

v^

may
z=i

be written

where ^denotes a fourth constant.

energy of a unit of the gas for ^=0

its

We may regard JS'as denoting

;

pressure in the latter state, or

c its specific heat at constant

of the equation to

volume.

the

//its entropy for ^=rl and i'=l

volume

its

for t=z\

and p=.\

We may extend the ajiplication

any quantity of the gas, without altering the

values of the constants,

tively.

form

H,

a log V

T)

in the

This will give

if

11

we substitute -

in

for

f,

//,

v. respec^

J.

W. Gihbs Biquilibrmm
e

c loo"^

This

Em
cm

Heterogeneous Suhstcmces.

oj^

H^^ ^

If

,-.

a loo-.

_v

(2o5)

"u

in

211

'

a fundamental equation (see pages 140-144) for an ideal gas of

is

invariable composition.

pearing

in

if we do not have
which forms the gas as ap-

be observed that

It will

to consider the ])roperties of the matter

any other form or combination, but

the gas in question

E and

generality give to

solely as constituting

we may without

a state of jiurity),

(in

loss of

11 the value zero, or any other arbitrary

But when the scope of our investigations is not thus limited,

we may have determined the states of the substance of the gas for

values.

which

60

and

components

for

the substance

or, if

which the

in

states of its

is

which f=:0 and ?/=0 may be already determined; so

^"and Zf cannot

that the constants

We

some other form

compound, the

Avith reference to

i)-=:0

substance appears,

be treated as arbitrary.

in general

obtain from (255) by ditferentiation

=
c^^
'Em

cte
f/f

:=
= man
^
ell]

/
- cE
+ \e~Em,
,^r-

civ
CIV

c+a
H

'/

m^ /

(tni,

(256)
^

'

whence, in virtue of the general relation expressed by (86),

Em,

p=ia
1.1=1

E^

may

III

s- (c

-\

m+

and

(87), (255),
//

and

= Em + c m
t

f.\ovt=

and eliminating
?/'

we have

i/,

= Em

+m

-\-

c log
"

ti<

Ie +

{-

-{

//-,

t,

v,

and

we have

^ //,

a log

H clog

we

a log

-^

the fundamental equation

Differentiating this equation,

m H

Eliminating

(257).

'

(259)
^

ii).

rii^

obtain the fundamental equation between

from equations

dih =^

(25S)

cv

We

Em

(257)
^

't

t -f

<i

'-^

log

(260)

|.

obtain

m/

IT

dv

cit

log

t -\-

a log

jdm
)

(261)

212

J.

W. Gihhs

Equilibrium of Heterogeneous Substance^.

whence, by the general equation

?7=

(88),

m (^+

clog^+alog j,

(262)

P = -,

(263)

c-\-a-JIc\ogt-^a\og
From

by

(260),

'C,

= Em

and

(87)

mt

-\-

we

(91),

and eliminathig v by means of

obtain
c log

we

(263),

(264)

\.

aT'?

a log

^^ v,

obtain the fundamental equa-

tion
?

From

= Em + m tic +
this,

by

differentiation

H - (c+a) log

a log

and comparison with

(265)

j.

(92),

we may

obtain the equations

?/=:m (^-f (c+) log

v= amt

if

log

(266)

),

/^

The

E+

tie

last is also a

-\-

^s

(267)

H-

((+ a) \og

fundamental equation.

It

a log

may

(268)

be written

in

the

form
log

or, if

^=

we denote by

+ ^^
a

=:

ae

+a

c
t

The fundamental equation between

easily obtained

fiE
(2<0)

j,

/;,

p, and

-^-//+log^,
logf^4^=
* {c+a)m
m
a

which can be solved with respect to j.

Any one of the fundamental equations
(271),

(269)
^

at

may

also

be

it is

{c+a)
^

and

t+'-~-,

the base of the Naperian system of logarithms,

Hca

log

'^

(271)

(255), (260), (265), (270),

which are entirely equivalent to one another, may be

./

W. Gihbs

Equilibrhim of IJeterogeneoits Substances.

regarded as defining an ideal gas.

213

be observed that most of

It will

by the use of diiferent conexample, a single constant might be used for

these equations might be abbreviated

(270), for

In

stants.

Hca

a
in

"

and another

~\~ O-

for

The equations have been

given

'

the above form, in order that the relations between the constants

occurring in the different e(iuations might be most clearly exhibited.

The sum

c+a is the

difierentiate (266)

We may

specific heat for constant pressure, as ap})ears if

if

we know

K we suppose that the density and the

gaseous, and in the liquid or solid state.

may

and the volume of

k.

specific

be regarded as constant quantities (for such

moderate pressures as the liquid experiences while

have for a unit of the

of a

the fundamental equations of the substance Ijoth in the

heat at constant pressure of the liquid

denote this specific heat by

we

as constant.*

between the temperature and pressure

easily obtain the equation

saturated vapor,

regarding^ and

in contact with the vapor),

a unit of the liquid

by

V.

we

and

shall

liquid

d?/

dt,

whence
?/

where H' denotes

= A-log

Also, from

a constant.
dfi

-(k

log

+ H',

tliis

equation and

(97),

+ H') dt+ Vdp,

whence
/n

where E' denotes another

in the liquid state.

= kt-M log

constant.

t-H'

This

is

If (268) represents the

t-i-Vp

+ E',

(A)

a fundamental equation for the substance

fundamental equation for the same sub-

stance in the gaseous state, the two equations will both hold true of coexistent liquid

and

gas.

Eliminatmg u we obtain
log

If

we

pa = HH' +a kca

neglect the last term, which

divided by the density of the liquid,

log

A, B, and

C denoting

state, the

If

EE'

logi!

V
a

at

p
^.
t

evidently equal to the density of the vapor

is

we may

i)=AB\og

constants.

substance in the solid

k~ca

write
-,

we make

similar suppositions in regard to the

equation between the pressure and temperature of

coexistent solid and gaseous phases will of course have the same form.

similar equation will also apply to the phases of

tent with

two

different kinds of solids,

tion of the gas

specific heat

an ideal gas which are coexis-

one of which can be formed by the combina-

with the other, each being of invariable composition and of constant

and density.

In this case
/I,

and

for tlie other

and

for the gas

fi.,

//;,

= k't-k'l
=

we may
log

write for one solid

t-H-t+

V'p-^

E,

k"t~k"t log t-H"t+ V"p + E",

= E+t(c + a H

(c

+ a)

log

+a

log

j.

214

W. Gihhs

./.

Equillhrium of Heterogeneous

Substances.

The' preceding fundamental equations all apply to g-Ases

composition, for which the matter

Now

if

entirely determined

is

a unit of the gas unites with the quantity

quantity

+/

of the second

it

will

of the

/I

first

of constant

by a

single

sohd to form the

be necessary for equilibrium (see pages 121, 122)

that

=(1

/":j+A//,

Substituting the values of fi,/i.2,

+>^)/I.2.

we

given above,

fi,,,

obtain after arranging the

terms and dividing by ai

^=^-

log

^+

C log ^ -

^,

when

^+^-g'- (l+^
A-

-g''-c-a-Afc' +

B (l+?i)k"-a Wca

(l

+ X)A;^-

E+lE'-{\+l) E"

(1+A)F"-AF'

We may

a.

conclude from this that an equation of the same form

an ideal gas in equilibrium with a liquid of which

component, when the

by

its

specific

it

may be

applied to

forms an independently variable

heat and density of the liquid are entirely determined

composition, except that the letters A. B,

C,

and

I)

must

in this case

be under-

stood to denote quantities which vary with the composition of the liquid.
consider the case more in detail,
"^

m
where

H'.

k,

u=kt-kt\os t-H't+

we may

k,

H, V, and

components of the

= kit-kHog /-H^ + ViJ + E,

Hence, by
,

dU.

dV

dm-i

arw,

to

which

the several

dE
P+ a?n,
T^

-jt+ -,

fflTO,

component

etc. (the quantities of

(92),

dk.
dk
= dm^
~jt' tlogt
^

If the

to

Vp + E',

denote functions of m,, mj,

liquid).

//,

.shall

But

(a)

write
C

where

by

for the liquid

E' denote quantities which depend only upon the composition of the

F,

Hence,

liquid.

we have

which

this potential relates is that

also forms the gas,

we

have by (269)
log

Eliminating

;"

,
i

we

^pa =r

Hca

+ a^
log

<

H-\E

+ '-i

at

obtain the equation

it

log-=^-51og<^+ D^,
a

in

which

A, B, C,

and

Z>

denote quantities which depend only upon the composition

of the liquid, viz

I I

^ dU

dk

dm^

dm

/f^k

B=l'
a dm
\

c-a).
,

\
I

J.

W. Gibbs

Equilibrmnt of Heteror/eneous Substances.

We may

variable (m).

obtain corresponding fundamental equations

which the proportion of the components

for a mixture of gases, in

shall

215

be variable, from the following considerations.

admits of a very general and in

It is a rule Avhich

exact experimental verification, that

if

many

cases very

several liquid or solid

sub-

stances which yield different gases or- vapors are simultaneously in

equilibrium with a mixture of these gases (cases of chemical action

between the gases being excluded,) the pressure

is

equal to the

sum

in the

gas-mixture

of the pressures of the gases yielded at the

same

temperature by the various liquid or solid sul)stanccs taken separately.

Now

the potential in any of the liquids or solids for the substance

which

it

form of gas has very nearly the same value

yields in the

when the
when it is

liquid or solid
in

equilibrum with the gas-mixture as

in

is

equilibrium with

its

own gas

The

alone.

difference of

the pressure in the two cases will cause a certain difference in the
values of the potential, but that this difference will be small, we may
infer

from the equation

i^

=('*)

(272)

which may be derived from equation (92). In most cases, there will
be a certain absorption by each liquid of the gases yielded by the
others, but as it is well known that the above rule does not apply to
cases in which sucli absorption takes place to any gi'eat extent, we

may

conclude that the

which we have

to

do

effect of this

is

circumstance in the cases with

of secondary importance.

slight differences in the values of the potentials

stances, the rule

may

If

due

we

neglect the

to these

circum-

be expressed as follows

The pressure in a mixture of different gases is equal to the sum of

of the different gases as existing each by itself at the
same temperature and with the same value of its potential.
To form a precise idea of the practical significance of the law as
thus stated with reference to the equilibrium of two liquids with a
mixture of the gases which they emit, when neither liquid absorbs the
gas emitted by the other, we may imagine a long tube closed at each
to contain in each of the descending
end and bent in the form of a
the pressures

With respect

may compare

to

some

am

a dm.

which have here been deduced, the reader

Ueber die Spannung des Dampfes von Mischungen

of the equations

Professor Kirchhoff "

aus Wasser und Schwefelsaure," Pogg. Ann., vol.

"On

Saturated Vapors,"

Pliil.

Mag.,

vol. xxxi.

civ. (185.-^), p. 6] 2

(1866), p. 199.

and Dr. Raukine

216

J.

W. Gibbs

Equilihriuni of Heterogeneous Substances.

loops one of the liquids, and above these liquids the gases which they

and the mixed

emit, viz., the separate gases at the ends of the tube,

We

gases in the middle.

may

suppose the whole to be in equilibrium,

the difference of the pressures of the gases being balanced by the

Now

proper heights of the liquid columns.

it is

evident from the

principles established on pages 203-210 that the potential for either

gas will have the same value

same

at the

level,

in

the mixed and in the separate gas

and therefore according to the rule

which we have given, the pressure

sum of the

in

the form

in the gas-mixture is equal to the

pressures in the separate gases, all these pressures being

measured at the same level. Now the experiments by which the rule
has been established relate rather to the gases in the vicinity of the
Yet, although the differences of level in these

surfaces of the liquids.

surfaces

may

be considerable, the corresponding differences of pres-

sure in the columns of gas will certainly be very small in

all

cases

which can be regarded as falling under the laws of ideal gases, for
which very great pressures are not admitted.
If we apply the above law to a mixture of ideal gases and distinguish by subscript numerals the quantities relating to the different

and denote by ^\ the sum of all similar terms obtained by

changing the subscript numerals, we shall have by (270)
gases,

a,

a,

p=^,

,<
]

\i

(273)

It will be legitimate to assume this equation provisionally as the

fundamental equation defining an ideal gas-mixture, and afterwards

to justify the suitableness of such a definition by the properties which

may be deduced from

it.

In particular,

will be necessary to show

when the proportion of its

it

that an ideal gas-mixture as thus defined,

components remains constant, has all the properties which have

already been assumed for an ideal gas of invariable composition it
will also be desirable to consider more rigorously and more in detail
the equilibrium of such a gas-mixture with solids and liquids, with
;

respect to the above rule.

By

differentiation

and comparison with (98) we obtain

I,

V
f

H,Cjaj

c,

fi^Ei

^1^

J.

W. Gibhs

EqulUhriiDii of Heterof/eneoiis Suhstauces.

217

H,
V

H9C9

(275)

H-i-E-i

V
etc.

Equations (275) indicate that the

between the temperature,

I'ehition

the density of any component, and the potential for that component,

not affected by

tlie

is

They may

presence of the other components.

also be written

/^i

= ^i^+^(^i+i-^A t'ilog + a,log'^j^

etc.

(276),

(276)

Eliminating

and

we

yw,, /'a? t^tc.

from

and (274) by means of (275)

(2 73)

obtain
(277)

ri= :S^^m,II, +m,Cilog t-\-m^a,\og ~j.

(278)

E(iuation (277) expresses the familiar principle that the pressure in a

gas-mixture

is

equal to the

gases would possess

if

the same temperature.

in

sum of

the pressures which the component

same volume at
Equation (278) expresses a similar principle
existing sepai'ately with the

regard to the entropy of the gas-mixture.

From

(276)

tion between

values of j(?,
ij)=
If

and (277) we may easily obtain the fundamental equat, v, m^, ni^, etc.
For by substituting in (94) the

1/:,

//,, /<2, etc.

taken from these equations,

2J^^m^-\-ni^t

Cj ^i-Cilog

-f

we

obtain

a^log

we regard the proportion of the various components

may be simplified by writing

j).

(279)

as constant,

this equation

for

^1 ^1,

for

am,

for

Em

for

losf /n

for

and

The values

Hm, - a m
of

c,

a,

E, and H,

the total quantity of gas.

Trans. Conn. Acad., Vol.

will

As
III.

(c,

m,),

^1 {H^ ni^a^ mj

then be constant and

log m,^).

m will

denote

the equation will thus be reduced to the

28

April. 1876.

218

W.

J.

form of

(xibhs

(260),

Equilibrium of Heterogeneous Substances.

it is

evident that an ideal gas-mixture, as defined by

when

components remains unwe have assumed for an

The
relations
composition.
between the specific
invariable
of
ideal gas
volume
constant
and
at
at
constant pressure
gas-mixture
of
the
heats
components
are
expressed
by the equations
its
of
heats
specific
and the
(273) or (279),

changed, will

have

the proportion of

its

the properties which

all

e=^^'^-\
ni

(280)

and
c'

+ a=^\''^-^^l^-^i.

(281;

We

have already seen that the values of t, v, m^, /.i^ in a gasr

mixture are such as are possible for the component G^ (to which

m, and

/<

Cj

j, Xi,

If we denote by p^, //j, ?/'j,

several quantities which the
connected
values
of
the
the
relate) existing separately.

determined for the gas G^ as thus existing sepa-

letters

indicate

rately,

and extend

have by

this notation

(273), (274),

P=^iPi,
whence by

'/=^i'U,

quantities p,

we

shall

t=^i'l\\

(282)

l-^^',;,.

(283)

and (91)

(87), (89),

f=^'ifn
The

to the other components,

and (279)

>/,

A'=^'iJi,
//,

f,

j,

'C,

relating to the gas-mixture )nay

therefore be regarded as consisting of parts which

may

be attrib-

uted to the several components in such a mannei- that between the

parts of these quantities which are assigned to any component, the
quantity of that component, the potential for that component, the
temperature, and the volume, the same relations shall subsist as

if

It is in this sense that we

component existed separately.
should understand the law of Dalton, that every gas is as a vacuum

that

to every other gas.

It is

to be

sible for a

remarked that these relations are consistent and pos-

mixture of gases which are not ideal gases, and indeed

without any limitation in regard to the thermodynamic properties of

They are all consequences of the law that the

the individual gases.

pressure in a mixture of different gases

is

equal to the

pressures of the different gases as existing each

by

sum

itself at

of the

the same

For let
temperature and with the same value of its potential.
relating
to the
be
defined
as
etc.;
etc.
P2i
Pii V\i ^1^ 'I'l^ Xn ^1
l

different

gases existing each

perature,

and potential

by

itself

with the same volume, tem-

as in the gas-mixture

= ^iPi,

if

W. Gibhs

J.

and

tlierefore,

by

Equilihriuni of Heterogeneous Suhstances.

(98), the quantity of

whence

dt

j/^i,

'\ dtj/i,

f^"

any component gas

gas-mixture, and in the separate gas to which p^,

the same and may be denoted by the same symbol

r/^,

nt

in the

relate, is

etc.

^.

219

Also

"

by (93)-(06),

also,

All the same relations will also hold true whenever the value of
for the gas-mixture

tion for the several

equal to the

is

component

sum

//

of the values of this func-

gases existing each by

itself

in

the same quantity as in the gas-mixture and with the temperature

For

and volume of the gas-mixture.

etc.

etc.

if />i, //j, fj,

are defined as relating to the

by themselves, we

Xn

'/';,,

?i

P2'>

components existing thus

have

shall

whence

/dif^\
Therefore,

by

mixture and

=(&1l\

(88), the potential //,

in the

gas

6r,

has the same value in the gas-

existing separately as supposed.

More-

over,

\dt

/ij^ ffi

dt

/v,

whence

Whenever different bodies are combined without communication of

work or heat between them and external bodies, the energy of the
body formed by the combination is necessarily equal to the sum of the
energies of the bodies combined.

when the
*

initial

subscript

after a differential coefficient relating to a

independently variable components

is

cate that each of the quantities m.

expression to which the suffix

entiation.

In the case of ideal gas-mixtures,

temperatures of the gas-masses which are combined

is

used here and elsewhere

,,

m.^, etc.,

applied, is to

unless

its

body having several

in this

paper

to indi-

differential occurs in the

be regarded as constant

in the differ-

220

W. Gihbs

tT.

Equilihriuni of Heterogeneous Substances.

are the same, (whether these gas-masses are entirely difterent gases,

or gas-mixtures differing only in the proportion of their components,)

the condition just mentioned can only be satisfied

ture of the resultant gas-mixture

is

when the temperaIn such com-

also the same.

binations, therefore, the final temperature

Avill

be the same as the

initial.

we

If

consider a vertical column of an ideal gas-mixture which

in equilibrium,

two

and denote the densities of one of its components at

by y and ;//, we shall have by (275) and (234)

different points

^^,

From

is

^''

=e

*''

(284)

which we may regard the quantities distinguished by accents as constant, it appears that the relation between
the density of any one of the components and the height is not
this equation, in

by the presence of the other components.

The work obtained or expended in any reversible

aflfected

process of com-

bination or separation of ideal gas-mixtures at constant temperature,

or

when

the temperatures of the initial and final gas-masses and of

the only external source of heat or cold which

will

is

used are

all

the same,

be found by taking the difference of the sums of the values of

and for the

for the initial,

final gas-masses.

evident from the form of equation (279) that this work

It is

to the

sum

of the quantities of

We

will

now

ip

(See pages 145, 146).

is

equal

work which would be obtained or

expended in producing in each different component existing separately
the same changes of density which that component experiences in
the actual process for which the work is sought.*
return to the consideration of the equilibrium of a

liquid with the gas

different gases,

which

it

emits as affected by the presence of

when the gaseous mass

in contact

with the liquid

may

be regarded as an ideal gas-mixtm-e.

It

may

first

be observed, that the density of the gas which

is

emitted by the liquid will not be affected by the presence of other

gases which are not absorbed by the liquid,
tected in any

This

may be

*This
It

will

way from

when the

liquid

is

pro-

the pressure due to these additional gases.

accomplished by separating the liquid and gaseous

result has been given

by Lord Eayleigh,

(Phil. Mag., vol. xlix, 18'75, p. 3J1).

be observed that equation (279) might be deduced immediately from this

principle in connection with equation (260)

assumed

for perfect gases.

which expresses the properties ordinarily

W. Gihhs

J.

Equilibrlvm of Heterogeneous Substances.

221

masses by a diaphragm which is permeable to the liquid. It will

then be easy to maintain the liquid at any constant pressure which is

The

not greater than that in the gas.

substance which

potential in the liquid for the

yields as gas will then remain constant,

it

fore the potential for the

same substance

in the

and

there-

gas and the density

of this substance in the gas and the part of the gaseous pressure

due to it will not be affected by the other components of the gas.

But when the gas and liquid meet under ordinary circumstances,
i.

e.,

a free plane surface, the pressure in both

in

same, as also the value of the potential for any

*S\.

Let us suppose the density of an insoluble component of the gas

and the temperature

to vary, while the composition of the liquid

remain unchanged.
the potential for S^

the index

(l)

If

we denote

by dp and

the increments of pressure and of

we

<?/<,,

have by (272)

shall

\dmjt,p,m

\d2)jt,m

denoting that the expressions to which

it is

affixed refer

(Expressions wdthout such an index will refer to the

to the liquid.

gas alone or to the gas and liquid in common.)

is

necessarily the

is

common component

Again, since the gas

an ideal gas-mixture, the relation between p^ and

component jS^ existed by

and therefore by (268)

as if the

(//<j

(^(

itself

log

at the

/ij is the same

same temperature,

/>j.

Therefore

(dv

\^^^

dp.
dmjt,p,m ^-;

This

may

be integrated at once

cient in the second

approximation.
so accurate, if

member

We may

we

j/^

we regard

as constant,

the differential

which

will be a very close

vrrite the

equation in the form

\^^'

denotes the density of the component

>S^

integrate regarding this quantity also as constant.

/

p,

and

(287)

ip-p')-

where p^' and p' denote the values of p^ and

component of the gas is entirely wanting. It
is

in the gas,

This wall give

dv Y^^

i^i-Pi riLT
I,
\uni^jt,

pp'

coeffi-

obtain a result more simple, but not quite

(dv
where

if

(285)

p when

the insoluble

will be observed that

nearly equal to the pressure of the insoluble component, in

the phase of the gas-mixture to which

j)y

relates.

is

not neces-

222

W. Gibbs

J.

sarily the only

Equilibriu

common component

we may

are others,

of Heterogeneous Substances.

in

of the gas and liquid.

If there

find the increase of the part of the pressure in the

gas-mixture belonging to any one of them by equations differing from

the last only in the subscript numerals.

Let us next consider the

ponent of the

We

liquid.

gas which

effect of a

and which must therefore

extent,

may commence by

absorbed to some

is

be regarded as a com-

in strictness

considering in general

the equilibrium of a gas-mixtiire of two components S^ and S^ with a

liquid

formed of the same components. Using a notation

we shall have by (98) for constant temperature,

like the

previous,

and
d})

;/\^^ d^i^-^-y'i'^

d^i^

whence

{yf^-Yx)

Now

if

the gas

d^'
u
,

is

dp,

a.t

=z

<^Ml

(/2-H'^O

^/'2-

an ideal gas-mixture,

^
-^ dp
,=.

^^

P,

dp
-^ , =
= a^t
-,

-,

and

//

r.

-^-^,

P2

72

therefore

^
We
liquid,

\\dp^=\\-^\

may now

suppose that

and

a gas which

S.^ is

In such cases

extent.

it is

/S',

(288)

the principal component of the

absorbed in the liquid to a slight

is

well

is

dp^.

known

that the ratio of the densities

of the substance S2 in the liquid and in the gas is for a given temperature approximately constant. If we denote this constant by ^,

we

shall

have

lU
It

Udp^={\- A)

would be easy to integrate

this

equation regarding

but as the variation in the value of

/>j

is

(28P)

dp,.
;/j

as variable,

necessarily very small

we

(L)

shall obtain sufficient

stant.

We

accuracy

if

we regard y^

as well as y^

as con-

shall thus obtain

(--'-l)(Pt-^i')=(l-^l)

P2^

('^90)

where ^j' denotes the pressure of the saturated vapor of the pure
It will be observed that when .4= 1, the
liquid consisting of S^.
presence of the gas

gas S^.

When

greater than

if

/S'g

will not affect the pressure or density of the

yl<l, the pressure and density of the gas S^ are

S.^ were absent, and when .i>l, the reverse is true.

J.

The

W. Gihbs Equilibrium of Heterogetieous Substances.

properties of

jui ide:il

223

gas-mixture (according- to the definition

which we have assumed) when

in equilibrium with liquids or solids

have been developed at length, because it is only in respect to these

properties that there is any variation from the properties usually
attributed to perfect gases.

vapor is usually given as a

gas calculated from

As

the pressure of a gas saturated with

than the

little less

sum of the

pressure of the

density and that of saturated vapor in a space

its

otherwise empty, while our formula^ would

make

it

little

more, when

would appear that in this respect our formula?

are less accurate than the rule which would make the pressure of the
gas saturated with vapor equal to the sum of the two pressures
mentioned. Yet the reader will observe that the magnitude of the
the gas

is

insoluble,

it

quantities concerned

is

not siich that any stress can be laid upon

this circumstance.
It will also be observed that the statement of Dalton's law Avhich we
have adopted, while it serves to complete the theory of gas-mixtures

(with respect to a certain class of properties), asserts nothing with

reference to any solid or liquid bodies.

But the common rule that

the density of a gas necessary for equilibrium with a solid or liquid
is not altered by the presence of a ditierent gas which is not absorbed

by the
in

solid or liquid, if construed strictly, will involve consequences

regard to solids and liquids which are entirely inadmissible. To

we

assume the correctness of the rule mentioned. Let

of the gaseous and liquid or solid
masses, and S2 the insoluble gas, and let quantities relating to the
gaseous mass be distinguished when necessary by the index (g), and

show

this,

denote the

aSj

will

common component

those relating to the liquid or solid

gas

is

in equilibrium

by the index

with the liquid or

(l).

solid, let

Now while the

the quantity which

contains of S2 receive the increment dm^,

its volume and the

contains of the other component, as well as the
temperature, remaining constant. The potential for S^ in the o-aseous

it

quantity which

mass

it

increment

will receive the

\dmj
and the pressure

dm 2

will receive the

/

increment

dp\^^^

\dm2lt,

Now

V.

t,

V,

^'

the liquid or solid remaining in equilibrium with the gas must

experience the same variations in the values of

dp/t,m

ju^

\dmjt,p,m'

and

/:>.

But by

(272)

224

IV.

T.

Gibhs

Equilihriuia of Heterogeneous Substances.

Therefore,

dm 2

ft, V,

dp yG)
Xdm^Jt,
It

be observed that the

will

first

V,

member

of this equation relates

and the second member solely to the

we may suppose the same gaseous mass to be capable of

solely to the liquid or solid,

Now

gas.

equilibrium with several different liquids or solids, and the

first

ber of this equation must therefore have the same value for
liquids or solids

which

which the liquid or

which

quite inadmissible.

is

solid

identical in

is

substance with the vapor

yields, it is evident that the expression in question denotes

it

equilibrium with one oi

is in

and liquid
water),

it

the same

when

states (as

Hence, Avhen a

components both

its

a moist gas

is

would be necessary that the

in equilibrium

solid

in the solid

with ice and

and liquid should have

density.

The foregoing

considerations appear sufficient to justify the defini-

tion of an ideal gas-raixture which

immaterial whether
(273), or

such

In the simplest case, in

the reciprocal of the density of the solid or liquid.

gas

mem-

all

by

we have

chosen.

It is of course

we regard the definition as expressed by equation

by any other fundamental equation which can

(279), or

be derived from these.

The fundamental equations

to (255), (265),

and (271)

by using inversely the

=7+
};

= 2jB,m^+

for an ideal gas-mixture corresponding

may

easily

be derived from these equations

substitutions given on page 217.

^\ (. -,

log^.^^^

m, (c,+,

They

are

-^,..,),

(292)

log

(293)

- ^,)
j

- ^\

(c,

m,

+ a,

The components

m,)

log

+^\

(a,

m,

^-^^^^).

to which the fundamental equations (273), (279),

We

may
(291) (292), 293) refer, may themselves be gas-mixtures.
binary
gas-mixture
equations
of
a
fundamental
the
apply
for example

W. Gibbs

J.

EqaUibriwn of Heterogeneous Sabstanres.

225

hydrogen and air, or to any ternary gas-mixture in

which the proportion of two of the components is fixed. In fact, the
form of equation (279) which applies to a gas-mixture of any particular number of components may easily be reduced, when the propor
tions of some of these components are fixed, to the form which applies
to a mixture of

to a gas-mixture of a smaller

The necessary
But the

number of components.

substitutions will be analogous to those given on page 217.

components must be entirely diiferent from one another with respect

which they are formed by mixture. We cannot, for
example, apply equation (279) to a gas-mixture in which the com-

to the gases of

ponents are oxygen and

It

air.

would indeed be easy to form a

fundamental equation for such a gas-mixture with reference to the

Such an equation might be derived

from (279) by the proper substitutions. Hut the result would be an
equation of more complexity than (279). A chemical compound,

designated gases as components.

however, with respect to Dalton's law, and with respect to

equations which have been given,
ent from

is

the

Thus, a mixture of hydrogen, oxygen, and

components.

its

vapor of water

all

to be regarded as entirely diifer-

is

to be regarded as a ternary gas-mixture,

three components mentioned.

This

compound gas and

is

certainly true

having the

when the

quanti-

components are all independently

variable in the gas-mixture, without change of temperature or presCases in which these quantities are not thus independently
sure.
ties of the

of

its

variable will be considered hereafter.

Inferences in regard to Potentials in Liquids

Such equations

as

potentials in pure or

(264),

(268),

(276),

and

Solids.

by which the values of

mixed gases may be derived from

capable of direct measurement, have an interest which

For

to the theory of gases.

is

quantities

not confined

as the potentials of the independently

variable components which are

common

to coexistent liquid

and gas-

eous masses have the same values in each, these expressions will
generally afford the means of determining for liquids, at least approximately, the potential for any independently variable component which

is

capable of existing in the gaseous state.

gaseous mass,
of the liquid
alone,

its

it

For although

not such as can exist in contact with a

will always be possible, when any of the components

every state of a liquid

are

is

volatile,

temperature and

a state for which there

is

Trans. Conn. Acad., Vol. Ill

to

bring

it

by a

change of pressure

composition remaining unchanged, to

a coexistent phase of vapor, in which
29

May,

1,s7<;.

226

J.

W. Glhbs

EfpdUbrium of Heterogeneous /Substances.

the values of the potentials of

may be
The

components of the liquid

volatile

tiie

estimated from the density of these substances in the vapor.

variations of the potentials in the liquid due to the change of

pressure

general be quite

in

Avill

trifling

as

compared with the

variations which are connected with changes of temperature or of

may moreover be

composition, and

equation (272).

The same

readily estimated

by means

of

considerations will apply to volatile solids

with respect to the determination of the potential for the substance

of the

solid.

As an

application of

in liquids,

let

absorption of

make
gases by
us

this

method of determining the potentials

Henry in regard to the

use of the law of

Let us consider the liquid as

denote the quantity of

m'-^^

between

liquids to determine the relation

the quantity of the gas contained in any liquid mass and

its potential.

equilibrium with the gas, and

in

gas existing as such,

the

ni^l'^

quantity of the same substance contained in the liquid mass,

potential for this substance
v^^^

common

to the gas

the volumes of the gas and liquid.

forms but a very small

i)art

and

When

of the liquid mass,

let

the

the

liquid, v^^^

and

/<

the absorbed gas

we have by Henry's

law
,y(L)
(L)

where

^1 is

and

be seen

equation

^^

,,(G)'
y

ni

is

(if

and by (-76)

J^+ (Mog-^,

(295)

Therefore

=S+6Mog A-,-;,,.
y(L)

(296)

we

'

(G)

also denoting functions of the tem})erature.

A.,

It will

'
'^

a function of the temperature

I<,

jB

disregard the difl'erence of notation) that this

equivalent in form to (216), which was deduced from

a priori considerations as a probable relation between the quantity

and the potential of a small component. When a liquid absorbs
several gases at once, there will be several equations of the form of
(296),

which

and which we may regard

The quantities A and ( in

will hold true simultaneously,

as equivalent to equations (217), (218).

were regarded
and pressure, but since the potentials

(216), with the corresponding quantities in (217), (218),

as functions of the temperature

in liquids are but little affected

by the

pressure,

we might

anticipate

that these quantities in the case of liquids might be regarded as functions of the temperature alone.

./ TV.

111

Gihhs

Equilihrhiin of Heterogeneous Suhstmices.

regard to equations (216),

we may now observe

(218),

(21'7),

227

that by (204) and (276) they are shown to liold true in ideal gases or
gas-mixtures, not only for components which form only a small

])art

of the whole gas-mixture, but without any such limitation, and not

only approximately but al)solutely.

It is noticeable

that in this case

and (J are functions of the tjmperature alone, and do

not even depend upon the nature of the gaseous mass, except upon
the particular component to which they relate.
As all gaseous bodies
quantities

when

are generally supposed to approximate to the laws of ideal gases

sufficiently rarefied,

we may regard

these equations as approximately

when the density

valid for gaseous bodies in general

When

small.

the density of the gaseous mass

the separate density of the component

question

in

tions will probal)ly hold true, but the values of

is
is

is

sufficiently

very great, but

small, the equa-

and

C may

not be

mass

entirely independent of the pressure, or of the composition of the

we have just

These equations

components.

in respect to its principal

also

will

components of Avhich the density in the licjuid is very small, whenever

these components exist also in the gaseous state, and conform to the
law of Henry. This seems to indicate that the law expressed by
apply, as

seen, to the potentials in liquid bodies for

these equations has a very general application.

of Entropy due
Mixture of Gases hy Diffusion.

Considerations relating to the Increase

From

may

we

equation (278)

easily calculate

the increase

entropy which takes place when two different gases

diffusion, at a constant

temperature and pressure.

to

ai'e

the

of

mixed by

Let us suppose

that the quantities of the gases are such that each occupies initially

one half of the total volume.

If

we denote

this

volume by

T^,

the

increase of entropy will be

ni^ j log V-\-

m^

a 2 log

T^

m,^ j log

w/g ^2 ^^g"

or

{ni

XT
JSlow

m,11
a.

=z

(/j -1-

P^

m^

(f^)

and1

2t

Therefore the increase of entropy

may

log

m^^

~?
z

z
2.

a,
^

= ~P^
It

be represented by the expres-

sion

pV
-.- log
It is noticeal)le that the

2.

(297)

value of this expression does not depend

upon the kinds of gas which are concerned,

if

as has been su[p()sed, except that the gases

which are mixed must be

the quantities are such

228

J.

W. Gihbs

EquUihriwn of Heterogeneous Substances.

If we should bring into contact two masses of the

same kind of gas, they would also mix, but there would be no increase of entropy.
But in regard to the relation which this case
bears to the preceding, we must bear in mind tlie following considerations.
When we say that when two different gases mix by diffusion,
as we have supposed, tlie energy of the whole remains constant, and

of diflferent kinds.

we mean

the entropy receives a certain increase,

that the gases could

be separated and brought to the same volume and temperature which

they had at first by means of certain changes in external bodies, for
example, by the passage of a ceitain amount of heat from a warmer

But when we say that when two gas-masses of the

same kind are mixed under similar circumstances there is no change
of energy or entropy, we do not mean that the gases which have been
mixed can be separated without change to external bodies. On the
to a colder body.

contrary, the separation of the gases

is

entirely impossible.

the energy and entropy of the gas-masses

We

call

when mixed the same

as

when they were unmixed, because we do not recognize any difference

So when gases of different kinds
in the substance of the two masses.
are mixed, if we ask what changes in external bodies are necessary to
bring the system to its original state, we do not mean a state in
shall occupy more or less exactly the same posisome previous epoch, but only a state which shall be
undistinguishable from the previous one in its sensible properties.

which each particle

tion as at

It is to states of

systems thus incompletely defined that the problems

of thermodynamics relate.

But

if

such considerations explain

why

the mixture of gas-masses

of the same kind stands on a different footing from the mixture of

gas-masses of different kinds, the fact

is

not less significant that the

increase of entropy due to the mixture of gases of different kinds, in

such a case as

we have supposed,

is

independent of the nature of the

gases.

Now we may

without violence to the general laws of gases which

are embodied in our eqixations suppose other gases to exist than such
as actually do exist, and there does not appear to be any limit to the
resemblance which there might be betAveen two such kinds of gas.
But the increase of entropy due to the mixing of given volumes of
the gases at a given temperature and pressure would be independent
We might
of the degree of similarity or dissimilarity between them.
should
be
absolutely
of
two
gases
which
the
case
identialso imagine
(sensible
and
molecular)
which
properties
come
all
the
into
cal in
gases
either
pure
or
mixed
with
each
exist
as
while
they
other,
play

J.

TT\

Glhhs

Equilibrium of Heterogeneous Substances.

229

but which shouM

differ in respect to tlie attractions between their

atoms and the atoms of some other substances, and therefore in tlieir
tendency to combine witli sucli substances. In tlie mixture of such
gases by diffusion an increase of entropy wovdd take ))hice, although

the pi'ocess of mixture, dynaniicallv considered, might be absohitely

identical in

its

minutest details (even with respect to the precise path

of each atom) with processes

wliicli

miglit take phice without

any

increase of entropy.

In sucli respects, entropy stands strongly con-

trasted with energy.

Again, Miien such gases have been mixed, there

is

no more impossibility of the separation of

two kinds of molecules

tlie

ordinary motions in the gaseous mass without any

in virtue of their

especial external influence, than there

is

of

separation of a homo-

tlie

geneous gas into the same two parts into Avhicli it has once been
divided, after these have once been mixed.
In other words, the
impossibility of an uncompensated

decrease of entropy seems to be

reduced to improbability.

There

is

perhaps no fact

molecular theory of gases so well

in the

number of molecules in a given volume at a

given temperature and pressure is the same for every kind of gas
when in a state to which the laws of ideal gases apply. Hence the
established as that the

pV
in

quantity -

(2f7)

must be entirely detei-mined by the number of

And

molecules which are mixed.

the increase of entropy

determined by the number of these molecules and

their dynamical condition

is

therefore

independent of

is

and of the degree of difference between

them.

The

result is of the

which are mixed

are mixed.

If

different kinds

ai'e

same nature when the volumes of the gases

not equal, and Avhen more than two kinds of gas

we denote by

-y^,

of gas, and by

increase of entropy

may be

if

we denote by

V-

where

Cm^

we

,,

denotes a constant.
V

2^ (m,

loguj.

shall
r,

Cm^

a^,

etc.,

Hence

V: '.m^a^: 2^{ni^ay)

and the increase of entropy

a^

numbers of the molecules of the

have

rj, r^, etc., the

several different kinds of gas,

r^

before the total volume, the

written in the form

^1 (mj aj) log

And

volumes of the

y^? *tc., the initial

V as

may be

r,

^',

?,

written

2,r^\og2,r, - ^\

(r,

log r,)
^

230

TK Gihhs

J.

Equitihrixmi of Heterogeneous Substances.

The Phases of Dissipated Energy of an Ideal Gas-mixture

(Joni2yo7ients which are Chemically Related.

We

will

now

loith

pass to the consideration of the phases of dissipated

page 200) of an ideal gas-mixtiare, in which the nnmber

of the proximate components exceeds that of the ultimate.
Let us first suppose that an ideal gas-mixture has for proximate
energy

(see

components the gases G ^, G^, and G^, the units of which are
denoted by @^, (S).^, 3, and that in ultimate analysis

@3
A

= A, ,

+A22,

(299)

and Ag denoting positive constants, such that Aj

Ag

1.

The

phases which we are to consider are those for which the energy of
the gas-mixture

is

minimum

for constant entropy

constant quantities of G^ and G2, as determined

For such phases, by

and volume and

in

ultimate analysis.

^'it^-^O.

(300)

(86),

4- /'o

yUj 6rti^

f^""'o

Ms

for such values of the variations as do not affect the quaaitities of

G^ and G^ as determined in ultimate analysis. Values of 6tn^,

Sm^, Sni^ proportional to A,, Ag,
1, and oidy such, are evidently

consistent with this restriction

A,

/<j

therefore

Ag

= Ms-

//2

(301)

we substitute in this equation values of /.i^, /<2, Ms taken from

(276), we obtain, after arranging the terms and dividing by t,
If

^1 i log

"^+ ^2 2

log

~-

(>s

log

'^

= A^B\ogt-j,

(302)

where

A=\^H^ + ^2^2 ^3 -

'^

^'
1

^ = A,r,

- ^^2^2 + ^3 - ^
-f Ag Cg

Czr Aj^j +A. ^2

If

we denote by p^ and

(d^

- ^ 32 + 35

C3,

(303)
(304)

^3.

(305)

the volumes (determined under stand-

ard conditions of temperature and pressure) of the quantities of

6^j and G^ which are contained in a unit of volume of the

the gases

gas

6^3,

we

shall

have
/i,

and (302)

will

= -^\

and

/:/,

=r

^,

(306)

reduce to the form

log

'

,3

^=r

_i_

logi5

(30/)

J.

W. Gibhs

Equilibrium of Heterogeneous Substances.

231

Moreover, as by (277)

= (i rn^

pv

we have on eliminating

^1
;/t3

m^

12

+ a^ m^)

m^

(308)

t,

"'2

m, H-

[a I

+ 3 Wg)

= ^ + ^^^^'-.71'
O

tC o

'-f'o

('*'')

t'

where

B'=X^

+ A3C2

C1

- <'3H-Aii

Agtt^

3.

(310)

be observed that the quantities /S^j, /^g will always be positive and have a simple relation to unity, and that the value of
/?j + /^2 * 1 will be positive or zero, according as gas 6^3 is formed
It will

of Gj and

G^ with

or without condensation.

we should assume,

If

according to the rule often given for the specific heat of compound

volume of any quantity

gases, that the thermal capacity at constant

of the gas

6^3

quantities which

would be

Gq

sum of the thermal capacities of the

equal to the

is
it

contains of the gases

The heat evolved

zero.

in

G^ and G2, the value of

and

6^35

without mechanical action,

+ A\)-\-X2

(cot

+ B.J

out of the gases

Ji

the formation of a unit of the gas

is

by

and (257)

(283)

A,

(^c,t

or

which

Avill

reduce to

specific heats

is

the second

Bt + C,
C when the above

satisfied.

evolved divided by a^

member

(c^t

E^),

relation in regard to the

In any case the quantity of heat thus

t^ will

be equal to the diiferential coefiicient of

of equation (307) with respect to

t.

Moreover,

the heat evolved in the formation of a unit of the gas G.^ out of the

gases 6rj and

which

is

G2 imder
t

4- 0-\- A

It

a,

-I-

is

-a^tB't-\- C,

equal to the differential coefiicient of the second

(309) with respect to

for

constant pressui'e

t,

multiplied

by

appears by (307) that, except

any given

finite

values of

;;/j,

a,^

in

m^^

member

of

t'^

the case
tn^,

and

when

y6^j

/ig

(infinitesimal values

being excluded as well as

infinite), it will always be possible to

assign such a finite value to v that the mixture shall be in a state of
Thus, if we regard a mixture of hydrogen, oxydissipated energy.

gen, and vapor of water as an ideal gas-mixture, for a mixture containing any given quantities of these three gases at any given tern-

232

J.

W. Gibbs

EqiiUihrium

peratiire there will

of Heterogeneous Substances.

be a certain volume at which the mixture will be

In such a state no such phenomenon

in a state of dissipated energy.

as explosion will be possible,

of platinum.

(If

and no formation of water by the action

the mass should be expanded beyond this volume,

the only possible action of a catalytic agent would be to resolve the

water into

its

components.)

temperatures, except

oxygen

is

It

may

indeed be true that at oi'dinary

the quantity either of hydrogen or of

very small compared with the quantity of water, the state

of dissipated energy
entirely

when
is

one of such extreme rarefaction as to

beyond our power of experimental

be noticed that a state of great rarefaction

condensation of the gases, that
action of platinum

short of

what

is

may

it is

is

lie

It is also to

verification.

so unfavorable to

any

quite probable that the catalytic

cease entirely at a degree of rarefaction far

But with

necessary for a state of dissipated energy.

respect to the theoretical demonstration, such states of great rarefac-

which we should suppose that the laws of

would apply most perfectly.
But when the compound gas G^ is formed of G^ and G^ without
condensation, (i. e,, when /?, + /io
1,) it appears from equation (307)
and
between
m^,
m^,
relation
/^g which is necessary for a
that the
by the temperature alone.
determined
energy
is
phase of dissipated
quantities
of the gases G^ and
total
if
regard
the
we
In any case,
of
the
gas-mixture), and
G2 (as determined by the ultimate analysis
of
these
gases which
also the volume, as constant, the quantities
tion are precisely those to
ideal gas-mixtures

appear uncombined in a phase of dissipated energy will increase with

the temperature, if the formation of the compound G^ without

change of volume is attended with evolution of heat. Also, if we

regard the total quantities of the gases G^ and G^, and also the
pressure, as constant, the quantities of these gases which appear uncombined in a phase of dissipated energy, will increase with the
temperature, if the formation of the compound G^ under constant
pressure

is

attended with evolution of heat.

If

^=

(a case, as

0,

has been seen, of especial importance), the heat obtained by the

formation of a unit of G^ out of G^ andtrg without change of volume
or of temperature will be equal to

and the

total quantities of the gases

have given

finite values, for

G.

If this

quantity

G^ and G2 and

an infinitesimal value of

is

positive,

also the
t

we

volume

shall

have

phase of dissipated energy) an infinitesimal value either of mj

or of 25 '^'^"^ ^^^'" ^" iiifiiiite value of t we shall have finite (neither inBut if we sui)pose
finitesimal nor infinite) values of m,, mg, and m^.
(for a

the pressure instead of the \'olume to liave a given finite value

(with

W. Gibbs

J.

Equilibrium of Heterogeneous Substances.

we

suppositions otherwise the same),

values of

have for infinitesimal

m.^, and for infinite

shall

an infinitesimal value either of m,^ or

values of
is

233

or infinitesimal values oi rn^ according as

finite

/ij -|- (i.^

equal to or greater than unity.

The

we have considered

case which

may

that of a ternary gas-mix-

is

ture,

but our results

fact,

whatever the number of component gases

easily

be generalized

this respect.

in

In

in a gas-mixture, if

there are relations of equivalence in ultimate analysis between these

may

components, such relations

tions of the

be expressed by one or more equa-

form
A,

+ A2o +

@,

A3

@3

etc.

(311)

0,

where @i, 2? ^^c. denote the units of the various component gases,
and A,, Ag, etc. denote positive or negative constants such that

^\

A,

0.

From

we may

(311) with (86)

derive for phases of dis-

sipated energy,
A,

/<,

Ag

-f

^lo

A3

/<3

:^\.(A, /^)

or

etc.

0,

(312)

0.

Hence, by (276),

^^(A.ilog'^) = ^ +B\ogt~

B and

where A,

(J

= 2,

(313)

by the equations

are constants determined

-4

-,

(Ai^x - A,c, - A,.),

(314)

B=z^,{\,c,\
G=2,{X,E,).
Also, since

^1

(A, i

j)

logw,)

- 2

v =^

(A^ a,)

H- ^^ (A

(315)

(316)
(a

nt

log^\

,) log

t,
^ )

(a,

m,)

p = A-\-B'\ogt--,

(317)

where

B'=2^ (A.c,+ A,aJ.

(318)

more than one equation of the form (311), we shall have

more than one of each of the forms (313) and (317), which will hold

If there is

ti'ue

simultaneously for phases of dissipated energy.

It will

be observed that the relations necessary for a phase of

dis-

sipated energy between the volume and temperature of an ideal gas-

mixture, and the quantities of the components which take part in

the chemical processes, and the pressure due to these components, are

not affected

by the presence

Trans. Conn. Acad., Vol.

III.

of neutral gases in the gas-mixture.

30

May,

1876.

-234

J.

From

W. Gibhs

Equilibrium of Heterogeneous Substances.

equations (312) and (234)

it

follows that

if

there

is

a phase

of dissipated energy at any point in an ideal gas-mixture in equili-

brium under the influence of gravity, the whole gas-mixture must

consist of such phases.

The equations
mixtui-e, the

of the phases of dissipated energy of a binary gas-

components of which are

paratively simple in form.

same

potential,

and

if

we

identical in substance, are

In this case the

com-

two components have the

ci

write

/i

for

(the ratio of the

volumes of

equal quantities of the tAvo components under the same conditions of

temperature and pressure), we shall have

log

m/
i

m^

where

131

_ A_
d

_^
.'

B
_ lop2^

;;

(J

<(2 f

W. Gihhs

J.

Eqiiilibriuut, of Heterof/eneous

235

Sv^hstance^.

In the first place, if we consider the case of a gas-mixture which

only differs from an ordinary ideal gas-mixture for which some of

components are equivalent

the

that there

in

is

perfect freedom

regard to the transformation of these components,

in

once from the general formula of equilibrium

brium

is

(l)

we have

only possible for such phases as

it

follows at

or (2) that equilicalled phases of

dissipated energy, for which some of the characteristic equations have

been deduced
Tf

in

the preceding pages.

should be urged, that regarding a gas-mixture which has

it

convertible components as an ideal gas-mixture of which, for some

we

reason, only a part of the phases are actually capable of existing,

might still suppose the particular phases which alone can exist to be
determined by some other j)rinciple than that of the free convertibility
of the components (as if, perhaps, the case were analogous to one
of constraint in mechanics), it may easily be shown that such a hypothesis is entirely untenable, when the quantities of the proximate
components may be varied independently by suitable variations of the
temperatui'e and pressure, and of the quantities of the ultimate components, and it is admitted that the relations between the energy,
entropy, volume, temperature, pressure, and the quantities of the
several proximate components in the gas-mixture are the

same as

for

an ordinary ideal gas-mixture, in which the components are not convertible.

Let us denote the quantities of the n' proximate components of a gas-mixture

by m^, m^,

ultimate components by nii, nig,

n'),
t,

and

let

etc.,

etc.

and the quantities of

{n denoting a

its

number less than

us suppose that for this gas-mixture the quantities

s, ?j,

v,

p, wij, ^2, etc. satisfy the relations characteristic of an ideal gas-

mixture, while the phase of the gas-mixture

the values of m-i, nig,

etc.,

is

entirely determined

with two of the quantities

6, 7,

by

v, t,p.

We

may evidently imagine such an ideal gas-mixture J^ having n'

components (not convertible), that every phase of ^ shall correspond
with one of J^ in the values of e, 7], v, t,p, m j m^, etc. Now let us give
,

to the quantities

mj,

1112, etc. in

and for the body thus defined

page 1 74) constructed likewise
;

the gas-mixture

us imagine the

let

any fixed values,

v-tj-s

surface (see

for the ideal gas-mixture

let

us

imagine the v-r/s surface constructed for every set of values of

m^, ^2, etc. which is consistent with the given values of m,, m^,
etc.,

i.

e.,

for every

body

of which the ultimate composition

expressed by the given vahies of

in2

etc.

It follows

would be

immediately

from our supposition, that every point in the v-rj-s surface relating to
A must coincide with some point of one of the v-t/-e surfaces relating

236

W. Glbbs

./.

B not only in

to

Jqullibrmiii.

of Heterogeneous Substances.

respect to position but also in respect to its tangent

plane (which represents temperature and pressure);

therefore the

must be tangent to the various y-r/- surfaces relating to B, and therefore must be an envelop of these surfaces.
P'rom this it follows that the points which represent phases
common to both gas-mixtures must represent the phases of dissipated
euergy of the gas-mixture B.
i)-t]-e

surface relating to ^1

The

an ideal gas-mixture which

properties of

are

assumed

in

regard to the gas-mixture of convertible components in the above

demonstration are expressed by equations (277) and (278) with the

equation
f

It is usual to

assume

= ^,

in

(c,

;//j

4-

/// ,

E^).

(324)

regard to gas-mixtures having convertible

components that the convertibility of the components does not affect

The same cannot be said of the equation (278).
But in a very important class of cases it will be sufficient
if the applicability of (277) and (324) is admitted.
The cases referred
to are those in which in certain phases of a gas-mixture the compothe relations (277) and (324).

nents are convertible, and in other phases of the same proximate

composition the components are not convertible, and the equations of

an ideal gas-mixture hold true.
If there is only a single

ponents,

(i. e.,

take place

degree of convertibility between the com-

only a single kind of conversion, with

if

among

the components,)

regard to the phases

in

it

will

be

its reverse,

sufficient to

can

assume, in

which con\ersion takes place, the validity of

equation (277) and of the following, which can be derived from (324)

by

differentiation,

and comparison

Avith

equation (11), which expresses

a necessary relation,

[tdtji^dv -

We

shall confine

:^^ (Cj

= 0*

m^)dt\,

our demonstration to this case.

that the physical signification of (325)

is

that

It will
if

(325)

be observed

the gas-mixture

is

subjected to such changes of volume and temjoerature as do not alter

its

proximate composition, the heat absorbed or yielded may be calby the same formula as if the components were not conver-

culated
tible.

Let us suppose the thermodynamic state of a gaseous mass J/, of

such a kind as has just been described, to be varied while within the
(The quanlimits within which the components are not convertible.
tities of

the proximate components, therefore, as well as of the

* This notation

is

intended to indicate that Wi, mj,

etc. are

ulti-

regarded as constant

J.

TT''.

Glbbs Kifit'dibri'Uii of Heterogeneous Suhst<mces.

supposed constant).

we use

the same

287

method of geome-

mate,

ai"e

trical

representation as before, the point representing the volume,

If

entropy, and energy of the mass will describe a line in the

v--q-B

sur-

face of an ideal gas-mixture of inconvertible components, the form

and position of
sition of

this surface being

determined by the proximate compo-

Let us now suppose the same mass to be carried beyond

M.

the limit of inconvertibility, the variations of state after passing the

limit being such

as not to alter its proximate

evident that this will in general be possible.

occur

when

composition

the limit
is

is

uniform.

same
component?

m\ist belong to the

composition.

It is

Exceptions can only

formed by phases in Avhich the proximate

The line traced in the region of convertibility
D-rf-s.

surface of an ideal gas-mixture of in-

continued beyond the limit of

components of ill/, since the variations of
volume, entropy and energy are the same as would be possible if the
components were not convertible. But it must also belong to the
v-r]-s. surface of the body J/, which is here a gas-mixture of conver-

convertible

as

before,

inconvertibility for the

tible

components.

Moreover, as the inclination of each of these

must indicate the temperature and pressure of the phases

through which the body passes, these two surfaces must be tangent
to each other along the line which has been traced.
As the w-//-
surface of the body
in the region of convertibility must thus be
surfaces

tangent to

all

the surfaces representing ideal gas-mixtxires of every

possible proximate composition consistent with the idtimate composition of

J!/,

continued beyond the region of inconvertibility,

alone their form and position

in

which

may

be capable of experimental demonstration, the former surface must be an envelop of the latter surfaces,

and therefore a continuation of the surface of the phases of dissipated

energy in the region of inconvertibility.

The foregoing considerations may give

a measure oi a priori probwhich are obtained by applying the ordinary

gas-mixtui'es to cases in which the components are conis only by experiments upon gases in phases in which

ability to the results

laws of ideal
vertible.

It

components are convertible that the validity of any of these

results can be established.
The very accurate determinations of density which have been made
for the peroxide of nitrogen enable us to subject some of our equaThat this substance in the gaseous state
tions to a very critical test.
their

is

properly regarded as a mixture of diiferent gases can hardly be

doubted, as the proportion of the components derived from

its

density

on the supposition that one component has the molecular formula

W. Gibhs

Eqii'dlhriiuu

238

J.

NO2

and the other the formuhx

of Heterogeneous

N^O^

is

l^ubstances.

the same as that derived

from the depth of the color on the supposition that th^ absorption of
due to one of the components alone, and is proportioned to
the separate density of that component.*
MM. Sainte-Claire Deville and Troostf have given a series of deter-

light is

minations of what

we

shall call the relative densities of peroxide of

nitrogen at various temperatures under atmospheric pressure.

use the term relative density to denote Avhat

chemistry to denote hy the term density^

it is

viz.,

We

usual in treatises on

the actual density of a

gas divided by the density of a standard perfect gas at the same

pressure and temperature, the standard gas being

air,

or

more

strictly,

an ideal gas which has the same density as air at the zero of the

centigrade scale and the pressure of one atmosphei*e.

test our equations

by these determinations,

it

In order to

be convenient to

will

transform equation (320), so as to give directly the relation between

the relative density, the pressure, and the temperatiire.

As

the density of the standard gas at any given temperature and

pressure

may by

(263) be expressed

density of a binary gasrmixture

I>=

Now

by

may

by

tiie

formula

the relative

be expressed by

(m, -i-mo)'^.

(326)

(263)

pV

By

successively the value zero in these equa-

giving to wig ^^^^ "*i

we obtain

tions,

i>i

= -,

1^2

(328)

when the gas consists

where D-^ and D2 denote the values of
wholly of one or of the other component. If we assume that
JJ.,

we

shall

= 2J\,

(329)

have

,=:22-

From

(326)

'

*Salet,
f

(330)

we have

"Sur

la coloration

Comptes Rendus,

J'

du peroxyde d'azote," Comptes Rendus,

vol. Ixiv, p. 237.

vol. Ixvii, p. 488.

J.

W. Gihbs Eqidlibrmrii of Heterogeneous

and from

(327),

by
2

and

(328)

m,

239

^^vbstances.

(330),

= Z>o ^- 2 i5, ^

hi.,

whence

m.

m,
By

(327), (331),

= (i>,

-i>)|^^,

(331)

= 2(i>-/J.)|^^.

(332)

and (332) we obtain from (320)

log
*=

= 2
^^
2 (Z) - Z> J
-r.\

log

(333)

a,

'--^

This formula will be more convenient for purposes of calculation

we

common

introduce

logarithms (denoted

by

log,^)

instead

hyperbolic, the temperature of the ordinary contigrade scale

of the absolute temperature

instead of

2^

a, to

instead

and the pressure in atmospheres pt

a rational system of units. If we also

t,

the pressure in

add the logarithm of

t,,

if

of

both sides of the equation, we obtain

'""%i~Jj- = ^ + I -S."

('

+-^)

- M^3-

('^'^

A and C denote constants, the values of which are closely con^ and C

where

nected with those of

From the molecular formuUie of peroxide of nitrogen N0 and

NoO^, we may calculate the relative densities

D,

14 4. 32
=z-

--

.0691

64
^ = 28 +
= 1.589, and B^
.0691 = 3.178.
2

The determinations

'

of

MM.

(335)
^

Deville and Troost are satisfactorily

represented by the equation

(3.178

2>)2 ,

3118.6

,^

which gives
i>=:3.l78
log^^

where
In the

umns

first

(->

W= 9.4/056

\/<'^

(3.178+0)

3118.6

- fTr^~^^Si oPa,-

part of the following table are given in successive col-

the temperature and pressure of the gas in the several experi-

MM.

Deville and Troost, the relative densities calculated

numbers by equation (336), the relative densities as
observed, and the difierence of the observed and calculated relative

ments of

from these

240

J.

densities.
in

W. Gibhs
It will

Equilibrium

of Heterogeneous Substances.

be observed that these differences are quite small,

.03, and on the average scarcely exceeding .01.

no case reaching

The signific.^ance of such correspondence in favor of the hypothesis by

means of which equation (336) has been established is of course
diminished by the fact that two constants in the equation have been
determined from these experiments. If the same equation can be
shown to give correctly the relative densities at other pressui'es than
that for which the constants have been determined, such correspon-

dence will be much more decisive.

t,.

J.

W. Gibhs

Equilihrinm of Heterogeneous Substances.

peroxide of nitrogen by

(3;^3), (334),

and (336)

241

be attected

will not

by the presence of free nitrogen, if the pressure expressed by p or

/> and contained implicitly in the symbol IJ (see equation (326) by
which D is defined) is understood to denote the total pressure diminished by the pressure due to the free nitrogen. The determinations

Wanklyn

of Playfair and

above

The

table.

given

are

the

in

latter

part

of the

pressures given are those obtained by subtracting

We

the pressure due to the free nitrogen from the total pressure.

may

suppose such reduced pressures to have been used

in the

reduction

by which the numbers in the column of observed

were obtained.
Besides the relative densities
calculated by equation (336) for the temperatures and (reduced)
of the observations

relative

densities

pressures of the observations, the table contains the relative densities

calculated for the

same temperatures and the pressure of one atmos-

phere.

The reader

second and third experiments

will observe that in the

of Playfair and

Wanklyn

the

and

calculated

there

a very close accordance

is

observed values of

Z>,

between

while in the second

and fourth experiments there is a considerable difference. Now the

weight to be attributed to the several determinations is very different.
The quantities of peroxide of nitrogen which were used in the
several experiments were respectively .2410, .5893, .3166, and .2016
grammes.
For a rough approximation, we may assume that the
probable errors of the relative densities are inversely proportional to

This would make the probable error of the

these numbers.

fourth observations

two or three times

and considerably greater than that of the

observe that

in the first of these

density 1.783

is

first

and

as great as that of the second

third.

We

must

also

experiments, the observed relative

greater than 1.687, the relative density calculated

by

equation (336) for the temperature of the experiment and the pressure of one atmosphere.
established

For

directly

in seven

Now

by the

the

number

1.687

we may regard

experiments of Deville

successive experiments in this part of the series the

by
by experiment,

calculated relative densities differ from the observed

If then

as

and Troost.

we accept

the numbers given

diluting the gas with nitrogen

is

less

than

.01.

the effect of

to increase its relative density.

As

this result is entirely at variance with the facts observed in the case

of other gases, and in the case of this gas at lower temperatures,

as appears

Wanklyn,

fi'om
it

the three

other determinations

of Playfair

and

cannot possibly be admitted on the strength of a single

Trans. Conn. Acad., Vol.

III.

?,\

May,

187(5.

242

J.

W. Glbbs

The

observation.

Equilibrium of Heterogeneous Substances.

experiment of this

first

apply with somewhat

ing the

less force to the last

cannot thei'efore

series

properly be used as a test of our equations.

Similar considerations

experiment.

temperatures and pressures of the three

with the observed relative densities, the reader

himself that

if

two

tions in the

we admit
first

last

may

By

compar-

experiments

easily convince

the substantial accuracy of the determina-

of these experiments (the second and third of

the series, which have the greatest weight), the last determination of
relative density 2.588

must be too

In

small.

fact, it

should evidently

be greater than the number in the preceding experiment 2.645.

If

we

confine our attention to the second and third experiments of

the series, the agreement

is

as

good

as could

be desired.

Nor

will

the admission of errors of .152 and .120 (certainly not large in deter-

minations of this kind) in the

first and fourth experiments involve

any serious doubt of the substantial accuracy of the second and third,
when the diflerence of weight of the determinations is considered.
Yet it is much to be desired that the relation expressed by (336), or
with more generality by (334), should be tested by more numerous

experiments.
It

not

should be stated that the numbers in the column of pi'essures are

quite

accurate.

In

the experiments

of Deville

and Troost

the gas was subject to the actual atmospheric pressure at the time of
the experiment.

The

This varied from 747 to 764 millimeters of mercury.

precise pressure for each experiment

periments of Playfair and

Wauklyn

not given.

is

In the ex-

the mixture of nitrogen and

peroxide of nitrogen was subject to the actual atmospheric pressure

at the

time of the experiment.

The numbers

in the

column of

pres-

sures express the fraction of the whole pressure which remains after

substracting the part due to the free nitrogen.

given

in the

Now

height of the barometer.

tion of

y'g^^

But no indication

is

published account of the experiments in regard to the

in the value of

it

may

easily

be shown that a

vai'ia-

can in no case cause a variation of more

In any
as calculated by equation (336).
than .005 in the value of
Wanklyn
variation
of
more
of
Playfair
and
a
experiments
the
of

than 30""" in the height of the barometer would be necessary to

produce a variation of .01 in the value of D. The errors due to this
source cannot thei'efore be very serious. They might have been
avoided altogether in the discussion of the experiments of Deville

and Troost by using instead of (336) a formula expressing the

relation between the relative density, the temperature, and the actual
densitv, as the reciprocal of the latter quantity

is

given for each ex-

J.

W. Gibhs

periment of this
sacrifice of

Eqidlihrium. of Heterogeyieous Substances.

series.

It

seemed

best, however, to

make

243

a trifling

accuracy for the sake of simplicity.

It might be thouglit that the experiments under discussion would

be better represented by a formula in which the term containing log t
But an examination of the figures
(see equation (333)) w^as retained.

show that nothing important can be gained

in the table will

respect,

and there

Any

to the formula of calculation.

values of ^, B'

this

in

hardly sufficient motive for adding another term

is

and

attempt to determine the real

equation (333), (assuming the absolute

validity of such an equation for peroxide of nitrogen,) from the ex,

in

periments under discussion would be entirely misleading, as the

may easily convince himself.

From equation (336), however, the
deduced. By comparison with (334) we
reader

obtain

B'
C
,^
A+
logjo - 7 = 9-4V056
^

3118.6

may

following conclusions

which must hold true approximately between the temperatures 11*^

and 90*^'. (At higher temperatures the relative densities vary too
slowly with the temperatures to afford a critical test of the accuracy

By

of this relation.)

dift'erentiation

we

obtain

J/:S'C_ 3118.6
where Jf denotes the modulus of the common system of logarithms.
Now by comparing equations (333) and (334) we see that

^=
C
Hence
B'
which

may

t-\-

MC =.43429
C

G 7181 2 = 3590

rtj,

be regarded as a close approximation at

40*^^

or

50*^,

and

a tolerable approximation between the limits of temperature above

mentioned.

Now

B'

version of a unit of

t -\-

NO2

represents the heat evolved

into

NgO^

by the con-

under constant pressure.

Such

conversion cannot take place at constant pressure without change of

temperature, which renders the experimental verification of the last

equation less simple.

B'

we

shall

But

since

B-\-a^

by equations

have for the temperature of

= ^ + ii,

40^^^

Bt-{- 6'= 3434

Now

t -\-

(322)

a,.

represents the decrease of energy

transformed into

NgO^

when

a unit of

without change of temperature.

NOg

is

It therefore

244

J.

W. Glbbs

Eqidlihrinm of Ileterogeneoxis Huhstmices.

work done by
compressed at constant

represents the excess of the heat evolved over the

when

external forces

a mass of the gas

NOg

temperature until a unit of

This quantity will be constant

constant volume of

would be more

NO^

if

has been converted into NgO^.

J5zii 0,

^2^4

and

is

i.

e., if

^^

^^'^

the specific heats at

same.

This assumption

simple from a theoretical stand-point and perhaps

safer than the assumption that

B' :=

If JB

0.

0,

H'

= u^.

wish to embody this assumption in the equation between

we may

Z>,

If

we

p, and

t,

substitute

6.5228

2977 4

log,

(C

+ 2V3) ^ j^^^Tf:^'

member of equation (336). The relative densities

by the equation thus modified from the temperatures and

for the second

calculated

pressures of the experiments under discussion will not differ from

those calculated from the unmodified equation by more than .002 in

any

case, or

It is to

by more than

relation expressed

.001 in the first series of experiments.

we
by equation

be noticed that

if

adniit the validity of the volumetrical

(333),

which

is

evidently equivalent

to an equation between p, t, v, an<l ni (this letter denoting the quantity of the gas without reference to its molecular condition), or if we

admit the validity of the equation only between certain limits of

temperature and for densities less than a certain limit of density, and
also admit that between the given limits of temperature the specific
heat of the gas at constant volume

quantity when the gas

sisting

wholly of

is

may be regarded

sufliciently rarefied to

NOg, or,
when

lar state of the gas,

as a constant

be regarded as con-

to speak without reference to the molecuit

is

rarefied until its relative density J)

we must also admit the

same limits of temperature and density) of all the
calorimetrical relations which belong to ideal gas-mixtures with
The premises are evidently equivalent to
convertible components.
that we may imagine an ideal gas with convertible components
this,
such that between certain limits of temperature and above a certain
limit of density the relation between p, t, and v shall be the same for
a unit of this ideal gas as for a unit of peroxide of nitrogen, and for
approximates to

its

limiting value 2>,,

validity (within the

a very ^reat value of v (within the given limits of temperature) the

thermal capacity at constant volume of the ideal and actual gases
Let us regard t and v as independent variables
shall be the same.

we may let these letters and p

we must distinguish the

but

entropy

/;

of the real gas.

refer alike to the ideal

entropy

Now

by

//'

(88)

and

real gases,

of the ideal gas from the

./

W. Gihbs

EqullibriuiH of Heterogeneous Substatu-es.

= *,

^^

245

(387)

therefore

dij

do

7lt

_ d
~ lit

_
~

dr]

dv

drp

dt

~dt^'

Since a similar relation will hold true for

dj}^_d_

d_

dv

?/',

we

'

ns8^
^

obtain

dr[

dv

dt

_
~di ~

d dp

dt''

which must hold true within the given limits of temperature and
density.

Now

it is

granted that

^-'#'

(3^0)
^

dt

dt

any temperature within the given

for very great values of v at

'

limits,

two members of the equation represent the thermal capacities

at constant volume of the real and ideal gases divided by t,) hence,
in virtue of (339), this equation must hold true in general within the
given limits of temperature and density. Again, as an equation like
(for the

(337) will hold true of

From

and

and entropy of the

have

w^e shall
dt}

dt}'

dv

dv'

the two last equations

relations the ideal

may

?/',

is

it

evident that in

real gases are identical.

calorimetrical

Moreover the energy

ideal gas are evidently so far arbitrary that

suppose them to have the same values as

given values of

all

and

v.

in the real

we

gas for any

Hence the entropies of the two gases are

and on account of the necessary

the same within the given limits

relation

de-=.

the energies of the

dr]

two gases are

p dv,
in like

manner

identical.

Hence

the fundamental equation between the energy, entropy, volume, and

quantity of matter must be the same for the ideal gas as for the
actual.

We may

easily form a fundamental equation for an ideal gas-mix-

ture with convertible components, which shall relate only to

the
use the equations
of the form (312) to eliminate from the equation of the form (273)

phases of equilibrium.

For

this purpose,

we may

which expresses the relation between the pressure, the terapei-ature

and the potentials for the proximate components, as many of the
potentials as there are equations of the former kind, leaving the

246

W. Gihhs

'/

Equilibrium of Heterogeneous Substances.

components which

potentials for those

convenient to regard as

is

it

the ultimate comj^onents of the gas-mixture.

In the case of a binary gas-mixture with convertible components,

may be denoted

the components will have the same potential, which

by

and the fundamental equation

//,

Ci+a,

//

p:=za^L^t

will

be

',

C2-\-a.2

-\-a.^Lt

E-i

fi

(342)

where

L,

From

by

this equation,

X.^e

""'

"^

(343)

and comparison with

differentiation

(98),

we

obtain

n-E,

c,

+2-f"

^2(^2
Ci

fi

E,

-=L^t'e
From

(244)

IIE^
^

(345)

the general equation (93) with the jDreceding equations the

following

is

easily obtained,
II Ey

Cj_

- = Z^{c,t+E^)t'''
We

L^t

',

^5

Ci
-\-

may

obtain the relation between p,

t,

p-a,t'^={a,-a,)L^t

(i -

a^)

^2

(346)

by eliminating

may proceed

"'

C2
,

and

v,

from (342) and (345). For this purpose we

From (342) and (345) we obtain

a^t

""'*

+L^{e2t+E.^)t'''

//

rtl

ii-Ej

Cj_

"'^

as follows-

"'^

+ a-z

(347)
li^E-i

rt,

a,.,t

"

(=^48)

'>

and from these equations we obtain

1 log [P

^) "

2 log

^^

'^*

" ^^
)

= (^1 ~

^^s)

jp
4-

a^

logZi-aglog L^ +(^2 -''2 +^,

~''2)log

^^S (^ 1

2)

-pi

~T^

'

^^^^^

Gihhs

J. IV.

Equilihrhim of Heterogeneous Substances.

(In the particular case

By

lent to (833)).

when a,

(347)

=2 Wg

247

this equation will be equiva-

and (348) we may

easily eliminate

fx

from

(346).

The reader

will

observe that the relations thus deduced from the

fundamental equation (34 2) without any reference to the different

components of the gaseous mass are equivalent to those which relate
to the phases of dissipated energy of a binary gas-mixture

ponents which are equivalent

in

with com-

substance but not convertible, except

that the equations derived from (342) do not give the quantities of

the proximate components, but relate solely to those properties which

are capable of direct experimental verification without the aid of

any

theory of the constitution of the gaseous mass.

The practical application of these equations is rendei'ed more simple

by the fact that the ratio , -.a^ will always bear a simple I'elation to
unity.
When a^ and f/g are equal, if we write a for their common
value, we shall have by (342) and (345)
j)V=zamt.^

(350)

and by (345) and (346)

_ L,{c^t+E^)^Lo{c^
-J-

-I-

t-\-

E^)t

""

""^

(351)

CjCi El Eft
at
a

this equation we may calculate dii-ectly the amount of heat

required to raise a given quantity of the gas from one given tempera-

By

The equation shows that the

be independent of the volume of the gas. The
heat necessary to produce a given change of temperature in the gas
at constant pressure, may be found by taking the difference of the

ture to another at constant volume.

amount of heat

will

values of J, as defined by equation (89), for the initial and final states
of the gas. From (89), (350), and (351) we obtain

E1E2

C2C;

L,{c^t^ at^E^)^L^(c^t-^at^E^)t

L^^^LJ,

By

differentiation of the

two

last

"

''^

._^.

equations

we may

obtain directly

the specific heats of the gas at constant volume and at constant pres.
sure.

The fundamental equation

of an ideal ternary gas-mixture with a

single relation of convertibility

between

its

components

is

248

J.

W. Gihhs Equilibrium of Heterogeneous

p = a^

di

+
where A^ and

X.^

Iiave the

a.t

a,

Substances.

0.2

cb.,

'

'

a.,t

same meaning as on page

230.

{To be co7itinued.)

ERRATA.
Page
"

Page

1G7, formula (168), for

formula (169), for

m, read
to,,

239. formula (333), for.^ read

t

^,.

to_j read//,,

-^.
a,t

//_!.

(35.3)

IX. On the Equilibrium of Heterogeneous Substances.

By J. WlTXARD GiBBS.
{Continued from page 248).

THE conditions OF INTERNAL AND EXTERNAL EQUILIBRIUM FOR

SOLIDS IN CONTACT WITH FLUIDS WITH REGARD TO ALL POSSIBLE
STATES OF STRAIN OF THE SOLIDS.
In treating of the physical properties of a
consider

state

its

of

strain.

relative position of its parts

A
is

body

is

solid, it is

necessary to

said to be strained

altered,

and

\i^ \%% state

when the

of strain

\^

meant its state in respect to the relative position of its parts. We

have hitherto considered the equilibrium of solids only in the case in
which their state of strain is determined by pressures having the
same values in all directions about any point. Let us now consider
the subject without this limitation.
If

cc', 2/', s'

body

are the rectangular co-ordinates of a point of a solid

any completely determined state of strain, which we shall

call the state of reference^ and cc, y, z, the rectangular co-ordinates of
the same point of the body in the state in which its properties are the
in

subject of discussion,

we may regard

;, _y,

z as functions of

a;',

y\

z'

the form of the functions determining the second state of strain.

For brevity, we may sometimes distinguish the variable state, to

which X, y, z relate, and the constant state (state of reference), to
which x\ y\ z' i-elate, as the strained and the unstrained states but
it must be remembered that these terms have reference merely to the
change of form or strain determined by the functions which express
the relations of ic, y, z and x', y\ z', and do not imply any particular
physical properties in either of the two states, nor prevent their
;

possible coincidence.
x'^

y\

z'

The axes

to which the co-ordinates

relate will be distinguished as the

AT', Y', Z'.

It is

a*,

y,

2,

and

axes of A', Y, Z, and

not necessary, nor always convenient, to regard

these systems of axes as identical, but they should be similar,

i.

e.,

capable of superposition.

The

state of strain of

any element of the body is determined by the

x, y, and z with respect to

values of the differential eotfficients of

x\

;y',

and

z'\

coefficients

for changes in the values of

.v,

y,

2,

when the

differential

remain the same, only cause motions of translation of the

Trans. Conn. Acad., Vol.

III.

44

May,

187T,

344

./.

IV.

Gibhs

Equilibrhim. of Heterogeneous Substances.

When the diiFereutial coefficients of the first order do not

vary sensibly except for distances greater than the radins of sensible

body.

molecular

we

actioji,

regard them as completely determining the

niaj^

any element.

state of strain of

There are nine of these

differential

coefficients, viz.,

dx

dx

dx

dx'^

dz'"'

^2/

dif
dy

^"

dy'^

dz'^

dz

W
It will

dy

dz

dz

%"

Ih''

^^^^^

be observed that these quantities determine the orientation of

the element as well as

strain,

its

and both these particulars must be

given in order to determine the nine differential coefficients.

fore, since the orientation

which do not

capable of

is

affect the strain, the strain of the element,

without regard to directions

must be capable of

in space,

There-

independent variations,

tliree

considered

six indepen-

dent variations.

The

physical state of any given element of a solid in any unvary-

ing state of strain

capable of one variation, which

is

addition or subtraction of

heat.

If

we

write

energy and entropy of the element divided by

state of reference,

But

if

we

shall

the strain varies,

have

we may

consider

may

the nine quantities in (354), and

8e^,=.t

6,/y,

any constant

for

+A\. S^. +

A-v,

A'x,,

Zy,

dz

witli respect to

-y^,

The

-j-,-

quantities will be apparent,

if

in

the

state of strain

(^^

7/v,

and

+ A',, rJ^

dz

(Jjt<j

^,

.^

dz
dz

denote the differential coefficients of

d'T^

for the

volume

as a function of

dy

dx
where

its

tv(j

dz

produced by

write

CCOC

_-

6v

is

fy/ find ;/v,

physical

we apply

signiffeation

fv

taken

of these

the formula to an element

which in the state of reference is a right parallelopiped having the

edges dx, dy', dz', and suppose that in the strained state the face in
which x' has the smaller constant value remains fixed, while the
opposite face

is

moved

parallel

to the axis of A".

If Ave also suppose.

J. TF.

Gibbs

Eqidlibrium

of Heterogeneous

345

Suhstanceti.

no heat to be imparted to the element, we shall have, on multiplying

by

dx' dy' dz\

Ssy, dx' dy' dz

Now

the

first

member

= A'x,

(^-77,

dx' dy'

dz'.

of this equation evidently represents the

done upon the element by the surrounding elements

member must

therefore have the

same value.

work

the second

we must regard

Since

the forces acting on opposite faces of the elementary parallelepiped as

equal and opposite, the whole work done will be zero except for the
face

which moves

distance

})arallel to

moved by

And

X.

this face, A"x <iy'

<^'^'

dx

represents

the

niust be eqiial to the

com-

since 3-^,

ponent parallel to A" of the force acting upon this face.

In general,

by the positive side of a surface for which x! is constant

we understand the side on which x has the greater value, we may say
that A"x, denotes the component parallel to A^ of the force exerted by
therefore, if

the matter on the positive side of a surface for which

a;'

is

constant

upon the matter on the negative side of that surface per unit of the
surface measured in the state of reference.
The same may be said,
mutatis mutandis, of the other symbols of the same type.
It will

be convenient to use

and 2' to denote summation with

respect to quantities relating to the axes ^T, Y, Z,

X',

V,

Z', respectively.

Sey.

This

is

With

t tf;/v<

:^

this

understanding

and to the axes

we may

2' (a:,, d^ij.

the complete \'alue of the variation of

write
(356)

y, for

a given element

we multiply by dx' dy' dz', and take the integral for

the whole body, we shall obtain the value of the variation of the total
energy of the body, when this is supposed invariable in substance.
But if we suppose the body to be inci-eased or diminished in substance
of the solid.

If

at its surface (the increment being

continuous

with the part of the body to which

it

is

in

nature and state

joined), to obtain the com-

plete value of the variation of the energy of the body,

we must add

the integral

fey,

SX' Ds'

which Ds' denotes an element of the surface measured in the state

of reference, and (^X' the change in position of this surface (due to
the substance added or taken away) measured normally and outin

ward

in the state of reference.

of the intrinsic

The complete value of the

energy of the solid

is

therefore

variation

346

W. Oibhs

J.

EquUihriuni of Heterogeneous

Suhstances.

y;

This

entirely independent

is

homogeneity of the

any supposition

of

regard to the

in

solid.

To obtain the conditions

we shonld make

in contact,

of equilibrinni for solid and fluid masses

the variation of the enei'gy of the whole

equal to or greater than zero.

But

since

the conditions of equilibrium for fluids,

we have already examined

we need here only seek the

conditions of equilibrium for the interior of a solid mass and for the
surfaces

where

comes in contact with

it

For

fluids.

necessary to consider the variations of the energy

this it will

be

only

of the fluids

so far as they are immediately connected with the changes in the

solid.

We may suppose

close proximity to

the solid with so

much

of the fluid as

to be enclosed in a fixed envelop,

it

is

in

which

is

impermeable to matter and to heat, and to which the solid is firmly

attached wherever they meet.
We may also suppose that in the
narrow space or spaces between the solid and the envelop, which are
filled with fluid, there is no motion of matter or transmission of heat
across any sui'faces which can be generated

by moving normals

to the

surface of the solid, since the terms in the condition of equilibrium

relating to such processes

equilibrium of the

fluids.

may be

cancelled on account of the internal

be observed

It will

tliat this

perfectly applicable to the case in which a fluid mass

enclosed in a solid.

method
is

is

entirely

detached portion of the envelo}) will then be

necessary to separate the great mass of the fluid from the small

Now

portion adjacent to the solid, which alone Ave have to consider.

energy of the

the variation of the

(13),

- f^^p

f^t SDt]

dIJv

fluid

mass

2^,r

/-' ,

will be,

by equation
(358)

^>'^'>*i

where f^ denotes an integration extending over all the elements of

the fluid (within the envelop), and ^\ denotes a summation with
regard to those independently variable components of the fluid of
which the

solid

is

composed.

Where

the solid does not consist of

substances which are components, actual or possible (see page 11 V),

of the
If

fluid, this

we wish

term

is

of course to be cancelled.

to take account of gravity,

in the negative direction of the axis

we may suppose
of Z.

It is

that

it

acts

evident that the

variation of the energy due to gravity for the whole mass considered
is

simply

fjfg n 6z dx' dy' dz\

(359)

where g denotes the force of gravity, and F' the density of the

W. G/M/s

J.

of

E<p',)UI)rliiiii

element in the state of reference, and the

extends throughout the

We have,

347

TIeterorjeneous Suhstdncei^.

triple integration, as before,

solid.

then, for the general condition of equilibrium,

ffft

6if dx' d.J dz! +/./:/--^^ ^' (a^x,

+ fffg r' 6z dx' dy' dz' +./"fv, 6N'

+fH dBtj

^p'p 6Dv

The equations of condition

H- :S , f'li-^

^^,) cW dy' dx!

Ds'

Dm

^ 0.

(:H)())

which these variations are subject are:

to

total entropy,
(1) that which expresses the constancy of the

fff Srjy, dx' dy' dz'

that Avhich expresses

(2)

the fluid

a,

how

^N' Ds'

= {a

/i,

surface of the

(h-

/i

+ J'^dDrj =
SDv

the value of

determined by changes in the

is

dDv
where

-{-fVs,

6y

for

any element of

solid,

v^, SJV' Ds',

Ds

(^z)

y
body

and

volume

its

(3)

in the state to

which

;,

y, z relate,

Ds

in the state of reference

any element of the

how

fluid are

dDni^, dDtn.^,

determined by the changes

by

etc.

for

in the solid,

r^'dJV'Ds',
]

r^'

dN' Ds',

(363)

\
J

etc.,
,

state of

the values of

dDm, = SDm^ = /',

the element

tlie

Vx, the volume of an element of the solid divided

those which express

where

(362)

denote the direction cosines of the normal to the

of the surfjice in this state corresponding to Ds' in

reference,

(3H 1

F^', etc. denote the separate densities of the several

com-

ponents in the solid in the state of reference.

Now,

since the variations of entropy are independent of all the

other variations, the condition of equilibrium (360), considered witli

regard to the equation of condition (361), evidently requires that

throughout the whole system

We may
from

= const.

(364)

therefore use (361) to eliminate the first and fifth integrals

(360).

If

we

multiply (362) by

/>,

and take the integrals

the whole surface of the solid and for the fluid in contact with

it,

for

we

obtain the equation

y*> SDv

= - fij {a dx ^ fddy ^ydz) Ds

by means of

Avhich

we may

- fp v^, 6N' Ds',

we add equations (363) multiplied respectively by

and take the integrals, we obtain the equation

If

(365)

eliminate the sixth integral from (360).

//^, /<2, etc.,

848

J.

TT'T

(xlhhs

EquiUbriidn of Heterb'/e neons

2,rM,<Wm,

/Svf/stances.

-/^\(//,r/) SA^'Bs',

by means of wliicli we may eliminate the last integral from

The condition of equilibrium is thus reduced to the form

(866)
(360).

///^ 2' ( JTx, S ^,) d.c' dy' dz' +ff/g F' Sz dxf dy' dz
+ y fv, dN' Ds' ft SN' Us ^f2y {a8x^ /i 6y \ y 6z) Ds
^fpi\.,SN'Bs' -/^\ (/',^V) QN' Bs'^^, (867)
//v,

in whicli

and

the variations are independent of the equations of condition,

which the only quantities relating to the

in

fluids are

and

//j,

//o, etc.

Now

by the ordinary method of the calculus of

wa'ite ix\ ff , y' for tlie direction-cosines of

of the solid in the state of reference,

variations,

if

we

the normal to the surface

we have

yyy'A'x, ^^^A dx' dy' dz'

=fa'

X^, dx Ds

- ff/~~ Sx dx' dy' dz'

(868)

with similar expressions for the other parts into which the first
may be divided. The condition of equilibrium is

integral in (367)

thus reduced to the form

-fff:^ 2' (-^ Sx\

+/:^' ^'

{a'

dx' dy' dz'

+fff;/

F' dz dx! dy' dz

2 {a dx) Bs

X^, 6x) Bs -^fp

+f[ey.-tt/y,+pv - ^, {i.iJ\')]6X'Bs'^
It

must be observed that if the

in nature and state, the

throughout

therefore the

first

solid

mass

is

(369)

0.

not continuous

surface-integral in (868),

surface-integral in (369),

must be taken

and

to apply

not only to the external surface of the solid, but also to every surface
of discontinuity within it, and that with reference to each of the

two masses separated by the

surface.

equilibrium, as thus understood,

it

is

To

satisfy the condition of

necessary and sufficient that

throughout the solid mass

2 2' (-ff Sx\ ~-yrSz=0

(370)

that throughout the surfaces where the solid meets the fluid

Bs'

2 2' {a

X^, dx) -f

Bsp ^^ {a dj-) =0,

(37

1)

and

[8^,^trfy,+pv-^,{/UJ\')]dX'^0;
and that throughout the internal surfaces of discontinuity

(872)

J.

W. Gihhs

Eqailihrhmi of Heterogeneous Svbstmices.

2 2' {a'Xy,,

2 2' {a> X^, 8x)^ =. 0,

,+

(Jic)

349
(373)

where the suffixed numerals distinguish the expressions relating to

the masses on opposite sides of a surface of discontinuity.
Equation (370) expresses the mechanical conditions of internal
If
equilibriitin for a continuous solid under the influence of gravity.
we expand the first term, and set the coefficients of 6x^ dy, and 6z
separately equal to zero,

^I^^
dx'

dY^
dx'

The

first

"^

we
dy'

dY^
(l^\i

"dAf

X, Y, Z
by the

As
it

dz'

'

UjAj'j,

+ ~c' ~

sum of

which

,,
'

neighlioring elements.

we have called

x, y, z relate,

the state of reference

dsy,

which

difi^er

and X', Y',

Z',

//,

d-^,

only by a rotation,

and

x', y', z'

d~

and

coincide,

represent

and the axes

displacements

we must have
Y^,

(375)

for similar i-easons,

Yy,=
The

i^ince

4^
dx

X^ =
and

arbitrarj^,

dy,

dy

Z,

^z-

d^,
states x,

is

coincide with the

this particular sup|)Osition

^^

when the

it

and the axes X', Y', Z' with the axes

.

X, Y,

dx' dy'

of the forces exerted on the six faces of the element

Z.

since,

by

the components parallel to one of

The values of X^,,

Zy, on
may be represented by the symbols A%;,

and

''

be convenient for some purposes to make

state to

X, Y,

'

of any one of these equations multiplied

the state which

may

dY^

dy'

d'^XI

dx' dy' dz'

'

dz'

1^ +
member

^^' n
^
"^
~

^"l'

dz' evidently represents the

the axes

obtain

six quantities

^x,

Z^

Zy,

^^y, ^z,

^y

= X,.

(376)

or Yx, Y^ or Zy, and Z^

ovX^

are

components of stress, the three first being the

longitudinal stresses and the three last the shearing stresses. The
mechanical conditions of internal equilibrium for a solid under the
called the rectangidar

infiiience of

gravity

may

therefore be expressed

by the equations

350

J.

W. Gihhs

Equilihrmm of Heterogeneoiis Snbfttances.

dx

dy

dY^

dl\

where

F denotes

dT,

dZy

dZx

'

dz

dZy^

the density of the element to which the other sym-

Equations (375), (376) are rather to be regarded as

expressing necessary relations (when X^^
Z^ are regarded as
bols relate.

internal forces determined

by the

They

expressing conditions of equilibrium.

which

not in equilibrium,

is

vibrations are propagated,

of

which

state of strain of the solid) than as

will

hold true of a solid

one, for example, through which

is

not the case

witli

equations (377).

Equation (373) expresses the mechanical conditions of equilibrium

for a surface of discontinuity within the solid.

cients of

fJir,

6y^ 6z, separately equal to zero

we

If

we

set the coeffi-

obtain

+ {a' T^.-^fi' Y+/ r,,),:=0,

{a'

rx,+/i'

{a'

z^,+ii' Zy,-{-r' z)^-^{a' z^,-\-fi z,,+r' z,,)=o.

Now

when

J\.,-\-y' Ty,,)

the a\

ft' ,

normal

on the positive side of any surface within the

an expression of the form

a'X^,
represents the component

the surface in the

evident from

the

+ ft'X^y'X,,,

]iarallel to

strained

side per unit of area

by

state

measured

in

^Y

(379)

of the force exerted

upon

matter on the positive

the

the state of reference.

This

is

consideration that in estimating the force upon

any surface we may substitute

for the given

of which

consisting

of elements for each

constant.

Applied to a surface bounding a

solid

(378)

}
J

y' re])resent the dii-ection-cosincs of the

in the state of reference

solid,

surface a broken one

either x' or y' or

z' is

any portion of a
when the normal is

solid, or

which may not be continuous with the

rest,

drawn outward as usual, the same expression taken negatively repreof the force exerted upon the
sents the component parallel to
surface (per unit of surface measured in the state of reference) by the

interior of the solid, or of the portion considered.

therefore express the

condition that the

surface of discontinuity

by the matter on one

its state

force
side

Equations (378)
exerted

ujion

of strain shall be equal and opposite to that exerted

matter on the other

side.

Since

the

and determined by

by

the

Wi Gihbs

J.

{a'),

we may

JEqulllbriuni of Heterogeneous Substances.

= - {a'),,

iff),

=-

(/i')

(/),

=-

351

(k%,

also write

etc.,

where the signs of

may

(x\ ft\ y'

be determined by the normal on

either side of tlie surface of discontinuity.

Equation (371) expresses the mechanical condition of equilibrium

where the solid meets a fluid. It involves the separate

for a surface

equations

a X,,-^

ft'

X +

cx'Y^.^ft' y,.

X=

y'

- ap^^,

+ y'Y^,= -ftp^,

(381)

JDs

the fraction -= denoting the ratio of the areas of the same element

Us

the strained and unstrained states of the solid.

These equations evidently express that the force exerted by the
of the surface in

interior of the solid

by the

upon an element of its

must be normal

strain of the solid,

surface,

and determined

to the surface and equal

by the
upon the same element of surface.
If we wish to replace a and Ds by a\ ft', y\ and the quantities
which express the strain of the element, we may make use of the
(but acting in the opposite direction) to the pressure exerted

fluid

The product a Ds

following considerations.

element

Ds

on the 3 -Z plane.

Now

dent of the form of the element,

convenient form.
=. const.,

y'

z'

Let

it

= const.,

is

the projection of the

since the ratio

we may suppose

JJs
-
Ds

-,

is

that

it

be bounded by the three surfaces

x'

and

indepen-

has any

const.,

the parts of each of these surfaces

let

included by the two others with the surface of the body be denoted

by i, M, and X, or by

i',

M' and N',

according as

to the strained or unstrained state of the body.

and

X'

are evidently a' Ds',

projections of

of

Ds upon

figure.

Z^,

ft'

and

Ds',

Jf and iV upon any

that j^lane, since L,

y' Ds'

plane

M, and

is

we have

reference

The areas of Z', J/',

and the sum of the

equal to the projection

X with

Ds

include a solid

(In propositions of this kind the sides of surfaces

distinguished.
solid figure, the

If the

normal to Ds

normals to X,

Trans. Conn. Ac.\d., Vol.

III.

M, and

must be
outward from the small
must fall inward, and vice

falls

X
45

May,- 1877,

352

Gihhs

J. 'W.

Noav L'

versa).

may

sides

is

Equillhrium

of H'eterhgeneous Substances.

a I'ight-aiigled triangle of which

be called dy' and

The

dz'.

perpendicular

tlie

projection of

on the Y-Z

plane will be a triangle, the angular points of which are determined

by the co-ordinates
dy

-,

dz

the area of such a triangle

^

dy

-,

( dy

dz

dz

dy

the area of

fdy_ dz __<h_

-,

dy\

(That this expression has the proper sign will aj^pear

and

and

y', z'

a' in

same plane

this expression

The sum of the

y'.

The

that the strain vanishes.)

jections of TUT and A^ upon the

ing

L\

dy' dz' )'' ^

\ dy' dz'

moment

is

or, since h dy' dz' re[resents

for the

dz

into

will

z', ',

if w^e

suppose

areas of the pro-

be obtained by chang-

and

(i' ,

three expressions

may

'2'

sum of

and into

x' , y',

be substituted for

I)s in (3S1).

We

shall hereafter use

to denote the

the three terms

obtained by rotary substitutions of quantities relating to the axes

Y\

JT',

Z',

(i. e.,

by changing x

y', z'

into y', z,

;',

and into

z', x',

y',

with similar changes in regard to a', ft', y', and other quantities
to denote the sum of the three terms
relating to these axes,) and

obtained by similar rotary changes of quantities relating to the axes

Jl,

This

Y, Z.

is

only an extension of our previous use of these

symbols.

With

this understanding, equations (381)

may

be reduced to the

form

etc.

The formula (372) expresses the additional condition of equilibrium

whicli relates to the dissolving of the solid, or its growth without
discontinuity.

If the solid consists entirely of substances

which are

actual components of the fluid, and there are no passive resistances

which impede the formation or dissolving of the solid, 6N' may have
either positive or negative values, and we must have
fv,

But

if

some

vv,

+V

Vy,

= 2,

{/I

/
,

',

').

(383)

of the components of the solid are only ]ossible com-

W. Gibbs

J.

Equilibrmra of Heterof/eveous tSnbstances.

ponents (see page 117) of the

diY'

fluid,

is

353

incapable of positive

values, as the quantity of the solid cainiot be increased,

and

it

is

sufficient for equilibrium that

iy,-tVy,+Py,^:>\{ft^I\').

To express condition
we may use

(384)

(383) in a form independent of the state of

reference,

r^,

ijy,

y,

etc.,

to denote the densities of

and of the several component substances in the

variable state of the solid.
We shall obtain, on dividing the equation by Vy
enei'gy, of entropy,

be remembered that the summation relates to the several

It will

components of the
throughout, or

and the

substance in the

we

fluid,

we

we may

use

F to

and

yu^

treat the solid as

composed of

to denote the potential for this

denote the density of the solid in the

(/", as before denoting its density in the state of

variable state,
reference,)

If

composition

care to consider the contact of the solid

fluid at a single point,

a single substance.

solid is of uniform

If the

solid.

we only

if

shall

have
fv,

tl/y,

+J)Vy,=

H^ r',

(3SG)

and
y ~tl/y-\-J>=:Z l.(J\

To

fix

our ideas in discussing this condition,

body which
we denote by s,

case of a solid
If

strain.

(387)

is
//,

let

us apply

it

to the

homogeneous in nature and in state of

v, and m, its energy, entropy, volume,

and mass, we have

Now the

1 1/ -\-

l-i

m.

(388)

mechanical conditions of equilibrium for the surface where

a solid meets a fluid require that the traction upon the surface deter-

mined by the

state of strain of the solid shall be normal to the sur-

This condition

face.

is

always

at right angles to one another.

we

tion,

shall

reference,

lose

which

is

satisfied

with respect to three surfaces

known
we make the

In proving this well

nothing in generality,

if

proposistate

of

arbitrary, coincident with the state under discus-

which these states are referred being also coincident.

normal component of the traction per unit
of surface across any surface for which the direction-cosines of the
normal are , /i, ;/, [compare (379), and for the notation JT^, etc.,
sion, the axes to

We

shall then have, for the

page

349,]

354

W. Gibhs

J.

Equilibrium of Heterdgeneoiis Substances.

+ y {a Zx +

or,

by

/i

Zv

^z),

(375), (376),

S=a^X^-\-f5^Y^J^y^Z^
a f3Xy~\-2/3y Yj_

-\-2

We

may

+ 2 y a Z^.

any convenient directions

also choose

for the co-ordinate

Let us suppose that the direction of the axis of

axes.

that the valne of

for the

(389)

so chosen

is

surface perpendicular to this axis

is

as

great as for any other surface, and that the direction of the axis of

X)

(supposed at right angles to

surface perpendicular to

passing

,1
through the
,

1^

<

mi
1 hen,

A.

axis oi

great as for any other surface

as

is

it

such that the value of S for the

is

.>

we write

it

-7

CtOt

the differential coefficients derived from the last (equation

a,

and y

fi,

(tfj

by

^-

,,

lor

CCJ^

treating

as independent variables,

dS

-j-

a=l,

and
is,

^77,

dp

A^y

Hence,

-,

,,

a r=

when

^ -

dy

=
y

0,

and

0,

-yr,

'

and

P=

dS
/^
dp

Moreover,

p dp -\- y dy = 0,
;/ = 0.
p = 0,

0,

nrrl,

when

dS

dS

a da

when

That

diS

diS

(iS

-=

Z^ ==

0,

0.

(390)

0.

dS

=
+ ^dy "K
,

^',

'

da =:

0,

0,

pdp-Vydy^(\
and

/:^=1,

Hence

i'z

Therefore,

when

0.

(391)

0.

the co-ordinate axes have the supposed directions,

which are called the principal axes of stress, the rectangular components of the traction across any surface {a,

aXx,

PY^,

/i,

yZ^.

y) are

by

(379)
(392)

Hence, the traction across any surface will be normal to that

surface,
(1),

when the

surface

is

perpendicular to a principal axis of stress;

W. Gihhs

J.

two of the principal tractions

(2), if

surface

is

ing axes,

(3), if

(in tliis case

Y^, Z, are equal, when the

the traction across any such surface

value of the two

constant for

all

is

equal to

principal tractions)

the principal tractions are

all

equal, the traction

is

normal and

surfaces.

be observed that

It will

A'x,

355

perpendicular to the plane containing the two correspond-

common

the

Equilibrium of Heterogeneous Substances.

in

the second and third cases the position of

the principal axes of stress are partially or wholly indeterminate, (so

may

that these cases

be regarded as included

in

the

first,)

but the

values of the principal tractions are always determinate, although not

always
If,

different.

therefore, a solid

bounded by

strain is

which

homogeneous

is

and

in nature

in state

of

six surfaces perpendicular to the principal axes

of strain, the mechanical conditions of equilibrium for these surfaces

may be

satisfied

[see (381),]

by the contact of

which

will in general

opposite sides, and

may

fluids

having the proper pressures,

be different for the different pairs of

be denoted by

/)',

p'\ p'"

(These pressures

are equal to the principal tractions of the solid taken negatively.)

It will

then be necessary for equilibrium with respect to the tendency

of the solid to dissolve that the potential for the substance of the
solid in the fluids shall

have values

//,', yu/',

fx^" determined

by the

equations
E

t}-i-\-p' n:=i }.i^

These values,

it

will

m^

(393)

i]-\-p" V =L lA^" m.,

tt/ -\-p"' v

{'iM)

= fA^"m.

(395)

be observed, are entirely determined by the

nature and state of the solid, and their differences are equal to the
differences of the corresponding pressures divided

by

the density of

the solid.
It

may

be interesting to compare one of these potentials, as ///,

(for the same substance) in a fluid of the same
and pressure />' which would be in equilibriiim with the
subjected on all sides to the uniform pressure p'. If we

with the potential

temperature

same

solid

write [\,, [f/]j.>, ["]/'? ^"*^ [^'i]/.' for the values which
//, would receive on this supposition, we shall have

[4'

f ['/].'

+P'

L"l'

= bu]r'

?;,

'"

v,

and

(=^96)

Subtracting this from (393), we obtain

f

Now

it

[f];,-

//-!-

[n],,

+;V

p' [vl.,

=n

;//

[//

follows immediately from the definitions of energy

J^ m.

(397)

and entropy

356

J.

that the

upon the

W. Gihhs

Equilibrium of Heterogeneous Substances.

four terms of this equation represent the

first

solid in bringing

it

from the state of hydrostatic

other state without change of temperature, and

/>'

work spent

stress to the

^:>'

[]^ evi-

dently denotes the work done in displacing a fluid of pressure p

surrounding the solid during the operation.
Therefore, the first
numlier of the equation represents the total work done in bringing
the solid when surrounded by a flxdd of pressure p> from the state of
hydrostatic stress p' to the state of stress jt>', p'\ p'".
This quantity is
necessarily positive,
p' =i 2^" ^=^p"'-

except of course in the limiting case

If the quantity of

when

matter of the solid body be unity,

the increase of the potential in the fluid on the side of the solid on

which the pressure remains constant, which

maintain equilibrium,

Hence, ///

greater than

is

will

be necessary to

equal to the work done as above described.

is

[yuj^,,

,and

for similar reasons, yw/'is

greater than the value of the potential which would be necessary for

equilibrium
yWj'"

if

the solid were subjected to the uniform pressure p", and

greater than that which would be necessary for equilibrium

if

That is, (if we

adapt our language to what we may regard as the most general case,
viz., that in which the fluids contain the substance of the solid but
are not Avholly composed of that substance,) the fluids in equilibrium
the solid were subjected to the uniform pr-essure

with the solid are

all

of the solid, except

when

that

if

/>"'.

supersaturated witli respect to the substance

the solid

is

in a state of hydrostatic stress

so

there were present in any one of these fluids any small frag-

ment of the same kind of

solid subject to the hydrostatic pressure of

the fluid, such a fragment

such fragment

would tend to increase. Even when no

must be perfect equilibrium

present, although there

is

so far as concerns the tendency of the solid to dissolve or to increase

by the accretion of similarly strained

solid

which

facilitate the

is

subject

to

commencement

the

mattei", yet the presence of the

distorting

stresses,

upon its surface, to the same extent, perhaps,

body, as if it were itself subject only
amorphous
an

stress

stress.

This

may

will

doubtless

of the formation of a solid of hydrostatic

sometimes, or perhaps generally,

make

in the case of

to hydrostatic
it

a necessary

condition of eqiiilibrium in cases of contact between a fluid and an

amorphous solid which can be formed out of it that the solid at the
surface where it meets the fluid shall be sensibly in a state of hydrostatic stress.

But in the case of a crystalline solid, subjected to distorting stresses

and in contact with solutions satisfying the conditions deduced above,
although crystals of hydrostatic stress would doubtless commence to

J.

t'oi-ni

W. Gihhs

upon

Equilibrhcm of Heterogeneoics Sicbstances.

surface

its

(if

distorting

the

be

should

supersaturation of the fluid

and consequent

stresses

carried

357

too

commence

before

far),

on
to be formed within the
most other bodies, yet within certain limits the
relations expressed by equations (39:3)-(395) must admit of realization, especially when the solutions are such as can be easily super-

would

they

the

or

fluid

of

surface

saturated.*
It

may

be interestino; to compare the variations of ^j, the pressure

the fluid which

in

determines

in

part the stresses and the state of

strain of the solid, with other variations of the stresses or strains in

the solid, with respect to the relation expi'essed

To examine

this point with

by equation

may

complete generality, we

(388).

proceed

in

the following manner.

Let us consider so much of the solid as has

in the state

of reference

the form of a cube, the edges of which are equal to unity, and

We may

parallel to tlie co-ordinate axes.

homogeneous
reference and

in

generality, since

suppose this body to be

nature and in state of strain both in

in

variable

its

we may make

its state

no

(This involves

of

loss

of

the unit of length as small as

we

state.

Let the fluid meet the solid on one or both of the surfaces
for which Z' is constant.
may suppose these surfaces to remain
choose.)

We

perpendicular to the axis of Z

edges in which
axis of JT.

and

y'

remain

]iarallel to

be observed that these suppositions only

It will

position of the strained

body

fix

relatively to the co-ordinate axes,

the

the

and

any way limit its state of strain.

follows from the suppositions which we have made that

do not
It

the variable state of the solid, and the

in

z are both constant to

in

_=
dz

clz

-^r= const.

==0,

const,

=0,

dy

-^ = const. =

(398)

and
.V

Yy,,

0,

Zy_,

Q,

= 2y~^-,.

(399)

Hence, by (355),

^- 7
1^-7
7
ch...^,.J...+X.4^,
+-\..d^,
^^^

f^''

(iy
dz
<^y
I ,4^-p^ JL, a _.
+ T^
.

(^^

-,

(400)

Again, by (388),
*

The

effect of distorting stresses in

liquefaction, as well as the effect of

solid

and

liquid,

Edin., vol. xvi,

xxiv, p. 395.

was
-p.

first

57.5

a solid on the phenomena of crystallization and

change of hydrostatic pressure common

described by Professor James Thomson.

and Proc. Roy. Soc.

vol. xi, p. 41?>, or

to the

See Trans. R. S.

PMl.

Mufj., S. 4, vol.

358

W. Gibhs

tT.

de

Now

Equilihrium. of Heterogeneous Snhstances.

t

(hi

p dv

dt

-|- '/

dp

4- in dyi^.

made

the suppositions which have been

dx du

(^01)

require that

dz

and
dii

dv

= -f-,
di/

dz
dx
-r d-^,
dz
dx

dx

dz

-,

dx du
dz
-/-, d
dx dy
dz

dy

.,

+ -yr
"T- d-f-, +
dz dx
dy

^-1

403)

Combining equations (400), (401), and (403), and ohservino- that

fy, and //v, are equivalent to f and /;, Ave obtain
;;

dt

V dp

-f-

'^

Tn

df.i^

dy dz\ ^dx

-.dx

,^

/^^

dx\ ^dy

dz

:^^'+fW IS y^' ^^^"w +( ^ ^+" lyTlie reader will observe that

when

the solid

is

T.rw ("^'

subjected on

all

sides

to the uniform normal pressure p, the coefficients of the difterentials

For the expresin the second member of this equation will vanish.

^,

sion

-^ri

dy

represents the projection on the J^-Z plane of a side of

dz

the parallelopiped for Avhich

will

The

case

is

i.

it

parallel to the axis of A" of the total

be equal to the component

pressui-e across this side,

by p

constant, and multiplied

x' is

be equal to

will

e., it

JTx,

taken negatively.

similar with respect to the coefficient of

d^,

and

A\.,

evidently denotes a force tangential to the surface on which it acts.

It will also be observed, that if we regard the forces acting upon the
sides of the solid parallelopiped as

sure

^>

composed of the hydrostatic

variation of the state of strain of the solid

will

be represented by the second

We

member

by these additional

mass of the

which the fluid is identical in

have then, by equation (97). for a

We

solid.

fluid equal to that of the solid,

dt

7/f

Vpdp

-\-

m djA^ = 0,

denoting the entropy and volume of the

/^F and Wf
obtain
tion we
{Vv

V) dt

/^
Now

(vf

-y)

the quantities -^,,

for the relation

is

(405)
fluid.

By

subtrac-

dp
dx

dy dz\ jdx
rTr

if

whicli

forces

of the equation.

will first consider the case in

substance with the

pres-

together with addition forces, the work done in any infinitesimal

UjQt

^
Uj%I

dz

dx\ dy

remain constant, we shall have

between the variations of temperature and pressure

necessary for the preservation of equililiiuni

W. Gibhs

J.

Kquilihrlnm of Heterogeneous S^ihstances.

359

dt^v,-^v^^^^,-^v^
where
should

(407)

VvV

dp

denotes the heat which would he absorbed

This equation

pressure.

the solid

if

body

change of temperature or
similar to (131), which applies to bodies

into the fluid state without

2J<'iss

is

But the value of

subject to hydrostatic pressure.

will not gener-

-j

ally be the same as if the solid were subject on all sides to the uniform normal pressure p for the quantities v and ?; (and therefore
Q) will in general have different values. But when the pressures on
;

normal and equal, the value of

sides are

all

will

dp

whether we consider the pressure when varied as

QjO^

equal on

all sides,

But

if

we wish

(A/tJ

or consider the quantities -^ -^

to

know how

(XiJ

the temperature

is

normal and

still

cloC

(AjtL'

be the same,

-j-,

as constant,

Ct'iJ

affected if the pres-

sure between the solid and fluid remains constant, but the strain of

the solid

is

varied in any

differential coefiicients of

way

press the strain are indicated

coefficients all vanish,

when

consistent with this supposition, the

with respect to the quantities which ex-

by equation

all sides

fit

equal, biat the differential coefficient

when

-y-,

These

(406).

the pressures on

differential

are normal and

ffni*

ftnc

fi^i

-=

-^

-j-,

are con-

when the pressures on all sides are normal and equal, vanwhen the density of the fluid is equal to that of the solid.
The case is nearly the same when the fluid is not identical in substance with the solid, if we suppose the composition of the fluid to

stant, or

ishes only

remain unchanged.

where the index

it is

We have necessarily

(f) is

used to indicate that the expression to which

affixed relates to the fluid.

/^f =_(^r

But by equation
and

Substituting these values in the

terms, and multiplying

*
etc.,

suflBxed

with respect to the fluid

feV" ={4^T
preceding

may

(409)

equation, transposing

by m, we obtain

stands here, as elsewhere in this paper, for

except such as

(92)

occur in the differential

Trans. Conn. Acad., Vol.

III.

all

the symbols m,, m.^.

coefficient.

46

May,

1877.

360

J. TFI

Gihbs

Equilibrium of Ileterorjeneous Substances.

\dni J /

By

dt

p,

1,

dv

- m /-

/ dti Y^'^

m.i^-

\am

Y"^^
I

/ 1,

'p,

+ in

and

//f

v^

df-i.

we may

subtracting this eqiitition from (404)

similar to (406), except that in place of

dp

(410)

0.

obtain an equation

we

shall

have the

expressions
/ di]

w(^-- Y^
\dm / p, m
J

The

\am i/t,

i,

discussion of equation (406)

Y^

dv

m(I -

^
and

p,

m'

therefore apply mutatis mutan-

Avill

dis to this case.

We may
which

fluid

also wish to tind the variations in the composition of the

will

~,

the quantities

sented by

'C,

-j-, ~^,

we know

If

constant.

be necessary for equilibrium when the pressure

the value for the fluid of the quantity repre-

m ^^

m^, m^,

substance of which the solid

of

yw, in

and the quantities of the

the first of which relates to the

on page 142 in terms of

several components

etc.,

in the composition of the solid,

it

Now

dp
TO

We

may

also constant,

M
+ r,
\dm/t,

in

considering variations

we make

will be sufficient if

one of the components variable.

constant value, and making

^,^>,

formed, we can easily find the value

is

terms of the same variables.

dfi,={~i^)
^
\dp /t,

temperature remaining

the

are varied,

2^ oi*

dm^

we

p, TO

all

therefore give to
shall

but

have

-^1
Xdm^/t,

p,

dm^

+ etc.

Substituting this value in equation (404), and cancelling the term

containing

dt,

we

obtain

\dph,7n

\dm/t,p.m

/du-,\^^

+ '" (*i)<,
^^

*"=

''"

,, .

^dx

+Av,<?^,+

/ ^^

(lv,

dy dz\ ^dx

/ ^^

= (-^- +
dz

dx\

'"

<^'

<) "ii^'

-.dy

.^^

+ /'^,;^,)"!^,.
,

(411)

This equation shows the variation in the quantity of any one of the
components of the fluid (other than the substance which forms the
solid)

which

will balance a variation of

/;,

or of

spect to the tendency of the solid to dissolve.

^)%i

(I'X/

(%Q^>

-j-,,

-v- -i

with

re-

^Y.

'T.

EqaUlhrium of Heterogeneous ^Substances.

Gihhs

Fundamental Equations for

The

361

Solids.

show that the

principles developed in the preceding jjages

solution of problems relating to the equilihrium of a solid, or at least

may

their reduction to purely analytical processes,

he made to de-

pend upon our knowledge of the composition and density of the solid
at every point in some particular state, which we have called the
state of reference, and of the lelation existing between the quantities
which have been represented by

and

When

z.

the solid

fy,,

among

fluids

nature and in
of reference,

'''^
'

>

^''

also requisite, but only such as is

is

the equilibi-ium of

))r())lems relating to

themselves.

any state of which a

If in

'

contact with fluids, a certain knowledge

is in

of the properties of the fluids

necessary for the solution of

^" ^"

Vy<->

its

sofid is capable,

and the

between

relation

it is

we may choose

state of strain,

fy/,

homogeneous

in its

this state as the state

dx
t-/
dx

'/.

dz
?

"i
dz'

will

be

But it is not always possible, even in the

homogeneous in nature, to bring all the
elements simultaneously into the same state of strain. It would not

independent of

cc',

y\

z'.

case of bodies Avhich are

be possible, for example,

If,

for

however, we

know

in the case of a

the relation between

any kind of homogeneous

reference,

we may

Prince Riipert's

For

co-ordinates of points of the solid in the

if x',

the co-ordinates of the same points

reference,

we

dx dx"

if

we

write

divided by

its

-7-0

y\

z'

denote the

in

and

the second state of

have necessarily

^ = d^'W-^
and

j,

state of reference,

first

x'\ y'\ z"

dx

'/v

a similar relation with respect to

it

any other state as a state of reference.

shall

with respect to any given state of

solid,

derive from

fy*

droj).

dx dy"
dy" tc'

dx

R for the volume

volume

dz"

+ d^' dx'

^*^- (""'^ ^^q"^^tions),

of an element in the state

in the state {x\

R=z

,
'

y\

iM

dx"^

dx'

dy'

dz'

dy^

(i/

dy"

dx'

dy'

dz'

<M

d2![

dz!^

dx'

dy'

dz'

z'),

we

shall

(,",

(412)
y", z")

have

dx"

(413)

362

Gihhs

J. Tf^

Equilibrium of Heterogeneous Substances.

8y,= Jiy,

we

If, tlien,

liave ascertained

dz

dm'

of

--^,

7/v,,

we

(414),

,,

shall

(414)

,/,,..

by experiment the value of

terms

Sy, in

-^,,

and the quantities which express the composi-

by

the substitution of the vahies given in (412)-

tion of the body,

,

,;,,= i?

obtam

e^,,

dx

terms of

in

?/v,

dx"

dz

-^,

^o

^,,

dz"

and the quantities which express the composition of the body.

We may apply this to the elements of a body which may be varia-

and state of strain in a given

body is fully described in
that state of reference, both in respect to its composition and to the
displacement which it would be necessary to give to a homogeneous
ble from point to point in composition
state of reference {x",

solid of the

dx
,

bring

it

s"),

same composition,

dz

-y

y\

^,

and

if

the

for wliich fy,

is

known

and the quantities which express

from the state of reference

(;c',

in

terms of

composition, to

its

into a similar

y', z')

//y,,

and

similarly situated state of strain with that of the element of the non-

dx"

homogeneous body, we may evidently regard -^,

element of the body, that

for each

We

shall then

have

fy"

ii^i

terms of

since the composition of the

the density,
of the

if

?/v,

is

known

in

-^,

known

in

-=^,

as

known

terms of x\ y",
-p,

terms of

z^\

and

x", y", z",

and

x",y",z"

of reference

in its state

{x', y',

.-;'),

this is

determining the equilibrium of any given state of the

non-homogeneous

An

body

as

not given directly, can be determined from the density

homogeneous body

sufficient for

is,

dz"
.

solid

equation, therefore, which expresses for any kind of solid, and

with reference to any determined state of reference, the relation

between the quantities denoted by

also the qviantities

that

is

fy,,

i/y,,

-^,

...

-^,

involving

which express the composition of the body, when

capable of continuous variation, or any other equation from

which the same relations may be deduced, may be called a pmdamentcd equation for that kind of solid. It will be observed that the
sense in which this term is here used, is entirely analogous to that in
which we have already applied the term to fluids and solids which
are subject only, to hydrostatic pressure.

When

the fundamental equation between

fv,

'/v5

7^/

'

^t

^^

W. Gihhs

J.

Equilih'iiim of Heterogeneous Substances.

known, we may obtain by

diiFerentiation the values of

terms of the former quantities,

in

vvliicli

will

A'x,,

t,

363

^z.

give eleven independent

between the twenty-one quantities

relations

^"' ^^^"

which are

dx"

'

'

^"

^'

di'

'

^^^^^

'"

that exist, since ten of these quantities are independent.

all

All these equations

may

also involve variables

composition of the body, when that

is

which express the

capable of continuous varia-

tion.

If we use the symbol ?/>, to denote the value of

(as defined on
pages 144, 145) for any element of a solid divided by the volume of
the element in the state of reference, we shall have
//

^V,=
The equation

(356)

may

6t

we know

Thei'cfore, if
-y-,

-y,

the body,
.

(416)

^7/v,.

be reduced to the form

;a, St

+ ^ ^' (^A\, (J^,).

the value of

if-y,

(417)

terms of the variables

in

t,

together with those which express the composition of

we may

by differentiation the values of 7/v J^xt

same variables. This will make eleven indebetween the same quantities as before, except that
instead of Sy,.
Or if we eliminate if-y, by means
obtain

Zy, in terms of tlie

pendent relations

we

fv,

shall

have

if\,

of equation (416),

we

tween the quantities

tion of the body.

value of

i/'v,

shall obtain eleven

in (415)

An

independent equations be-

and those which express the composi-

equation, therefore, which

as a function of the quantities

t,

-y^,

determines the
.

,
,

and the

which express the composition of the body when it is capable of continu.ous variation, is a fundamental equation for the kind of
solid to which it relates.
quantities

we

In the discussion of the conditions of equilibrium of a solid,

might have started with the principle that

it is

necessary and sufficient

be uniform throughout the

and that the variation of the force-function

for equilibrium that the temperature shall

whole mass
(-//")

of the

in question,

same mass

shall

be null or negative for any variation

the state of the mass not affecting

assumed that the value of

//

for

its

temperature.

We

in

might have

any same element of the

solid

is

364

Gibhs

J. TT\

JEquilihrhmi of Heterogeneous Substances.

function of the tem]>eratnre and the state of strain, so that for con-

we

stant temperature

miglit write

"""
the quantities A'x,

= ^^'(-^-4)'

would be only a formal change

Avoiild
.

This

equation.

this

in the definition of A'x,

^z

and

not aifect their values, for this equation holds true of A'x.
as defined

Zy_,

by

Zy, being defined

by equation

{'355).

With such

data,

by

transfor-

mations similar to those which we have employed, we might obtain

similar

results.'''

It is

would be that

tions

evident that the only difterence in the equa-

//-y,

would take the place of

terms relating to entropy would

be wanting.

and that the

e^,,

Such a method

is

evidently preferable with respect to the directness with which the

The method

results are obtained.

of this paper shows

more

distinctly

the role of energy and entropy in the theory of equilibrium, and can

be extended more naturally to those dynamical problems in which

motions take place under the condition of constancy of entropy of
the elements of a solid (as when vibrations are propagated through a
solid), just as the other

dynamical problems

in

method can be more naturally extended to

which the temperature is constant. (See

note on page 145.)

We have

already had occasion to remark that the state of strain

of any element considered without reference to directions in space

Hence,

capable of only six independent variations.

ble to express the state of strain of an element

dx

;,

-^-,

by

it

must be

is

possi-

six functions of

which are independent of the position of the element.

dz

For these

quantities

we may choose

the squares of the ratios of

elongation of lines parallel to the three co-ordinate axes in the state

of reference, and the jjroducts of the ratios of elongation for each
pair of these lines multiplied

by the

cosine of the angle which they

include in the variable state of the solid.

ties

by A, B,

C, a,

b, c,

we

shall

* For an example of this method, see

p.

705.

Memoir

With regard
"

On

If

we denote

these quanti-

have

Thomson and

Tait's Natural Philosophy, vol.

to the general theory of elastic solids,

compare

also

i,

Thomson's

the Thermo-elastic and Thermo-magnetic Properties of Matter" in the

Quarterly Journal of Mathematics, vol.

i,

propagation, reflection, and refraction of

Philosophical Society, vol.

vii.

p.

57 (1855), and Green's memoirs on the

ligiit

in the

J'ransactions of the

Cambridge

 Equilibrimn of Heterogeneous Suhatauces.

J. TF. (jrlhbs

365

^=^(1)^ ^=^($^- -=^(y^/dx dx\

^=^W^'>

^ fdx dx\
'-=^\d^'dy'}

^-,/dxdx\

^=^\d^'dx'}

b, c,

^'''^

of the fnndamental equation for a solid

The determination

reduced to the determination of the relation between

C, a,

<-)

or of the relation between

i/.\,,

t,

A,

f y,

C, a,

i>,

7/v,

thus

is

A,

7i,

b, c.

In the case of isotropic solids, the state of strain of an element, so

far as it

can

aftect the relation of Sy,

and

t/y,,

ble of only three independent variations.

or of

i/\,

and

capa-

is

t,

This appears most

dis-

tinctly as a consequence of the pi'oposition that for

any given strain

of an element there are three lines in the element which are at right
angles to one another both in its inistrained and in its strained
If the unstrained element

state.

tion

for these three lines

with

determine

tlie

To demonstrate

is

isotropic,

must with

value of

//y,

the ratios of elonga-

determine the value

fy*,

or

i/\,.

the existence of such lines, which arc (tailed the

principal axes of strain, and to find the relations of the elongations

of such lines to the quantities -^,

The

lows.

,...,, we may

ratio of elongation r of

any

line of

the direction-cosines in the state of reference

is

proceed as

which

<t',

/i',

fol-

y' are

evidently given

by

the equation

/dx

Now

(dz

dx

dz

^,

the proposition to be established

that

is

dx

A2

dz

A2

evidently equivalent to this

always possible to give such directions to the two systems of rectangular axes JT', Y\ Z', and X, Y, Z, that
it

is

dx
(421)

We may

choose a line in the element for which the value of r

least as great as for

allel

to this line in

is

at

any other, and make the axes of -.Tand A"' parthe strained and unstrained states respectively.

J.

.366

W. Glhbs Equilifyrium of Heterbgeneous

Moreover,

if

we

cients obtained

f/fr^)

write -A^-r

da

d{r^\

(:?(r-)

d/y
V-r V-r
dy

/Substances.

from (420) by treating

for

the

rv',

/J',

difFerential

y'

as

coefii-

itidependent

variables,

'

when

<?^v'

' z=

and

That

r7/f -f

/J'

A.y^O,

IS,

'

when

/i'

1,

^-,=

y'

0,

dx

^.

0,

;=

AJ

dx
Hence,

dy' =z
;/'

0,

and
/i'

1,

;/'

0,

0.

== 0,

0.

Therefore a line of the element which in the unstrained state

X' is perpendicular to JY" in the strained state.

we may choose one for whicli the value of r is at
any

gi'eat as for

this line in

other,

is

per-

Of

pendicular to

such lines

(423)

0.

all

least as

and make the axes of Y' and I" parallel to

the unstrained and in the strained state respectively.

Then

= 0.

|,-,

and

it

may

just been

easily

(424)

be shown by reasoning similar to that which has

employed that

1=

Lines parallel to the axes of A"',

will therefore

be parallel to

,42.)

0.

Y\

JT, Y,

and Z'

and

the unstrained

in the strained

body

body, and

the ratios of elongation for such lines will be

dx
dx'

dy
'

dy'

dz
'

dz'

have the common property of a stationary value of

the ratio of elongation for varying directions of the line. This
appears from the form to which the general value of r^ is reduced by
These

lines

the positions of the co-ordinate axes,

viz..

J.

W. Gibbs

Equilibrium of Heterogeneous Substances.

Having thus proved the existence of

particiUar strain,

lines,

367

with reference to any

let us pro-

which have the properties mentioned,

ceed to find the relations between the ratios of elongation for these
dz
dx
-rj
lines (the Jor^?tc^/:>/ axes of strain) and the quantities y^, ,
.

under the most general supposition with respect to the position of

the co-ordinate axes.

For any principal axis of

when

a' da'

strain

+ // dfV + y' dy' =

the diflferential coefficients in the

mined from

1 c?(r2)

From

(420)

we obtain

a' 2

two

the
ft'2

_^ y'2

last

i^

_
~

d{r^-)

'ft'

"dj^

dft'

we

d{r^)
(426)

'

(427)

dy'

necessary relation

dft'

^^

'

'

^ dy'

r-'

(428)

substitute the values of the ditterential coefficients taken

from (420),

If

l_

y' dy'

we obtain
^

we

_
~

equations, in virtue of the

^d{r-^)

or, if

of these equations being deter-

first

directly

da

From

1i^

0,

Therefore,

(420) as before.

a'

we have

368

W. Gibbs

J.

We may

Equilibriurn of Heterogeneous Substances.

write

+ Er^ Fr^ +(9 =

/-e

(431)

0.

Then
(432)

Also

(dx dx

\dxi)

2'^

/dx

/dx

/dx\^ /dy \^_|A^^

dxc

z=i2'2

/cfe

~^W/

\dx') \dy')

\2

\dy')

/dx

6fe

may

also

<^y

dx dz dz^\

(^'^

t?.K

f?a;

dx' dy'j

be written

^'

dx

dx

dx'

dy'

dy

dy

dx'

dy'

(434)

it

will

be convenient to use the

to denote the sum of the six terms formed by changing

+3

X, y, z, into y,

symbol

In the reduction of the value of G,

dx\\_

dy dy
Y_
~
dx'dy'dx'dy')
\%7
Wv
W'/
dxy
^/dxdy^_dy^
_ ^^

F=i

symbol

~dx'dy'd^'dy'~dx'dy'd^dy']

\dx' dy'

This

c?c

dx\)

\dx' dy'j

(dy y/dx

YY^^y \^

^')
dx'

dx dx

/dx

"
\dx'
c' dy' J

\dy'J

z,

in the

x-, z, x, y; x, z, y; y, x, z; and z, y, x; and the

same sense except that the last three terms are to

3-3

be taken negatively
to

x', y,' z'

and

2' in a similar sense with respect

3-3
as equivalent to x', y', z', except that

also to use

to use x', y',

z'

they are not to be affected by the sign of summation.

understanding we may write

G= 3-3

/dx dx\

:^'

* The values of

deduced

at length,

and

may be

\dl' d^'J

/dx dx \

\dy' dy'j

\d^' dz')

/dx dx

given in equations (434) and (438),

With

this

(435)

which are here

derived from inspection of equation (430) by means of the

usual theorems relating to the multiplication of determinants. See Salmon's Lessona

to the Modern Higher Algebra^ 2d Ed., Lesson III; or Baltzer's Theorie und

Introductory

Anwendung

der Determi'aanten^

5,

J.

W. Gihhs

Eqxdlihrixim of Heterogeneous Substances.

In expanding

369

the product of the three sums, we may cancel on

account of the sign ^' the terms which do not contain all the three
3-3
expressions dx, dy, and dz.

Hence we may write

/dx dx dy dy dz dz

3-3 3+3 \dx' dx' dj' dy' d?! dz'/

^
3+3

^
(

dx dy dz

/dx dy dz

dx' dy' dz' z^^\dx' dy' dz'J

(dx dy dz

870

W. Gibhs

J.

Equilihrium of Heterogeneous Substances.

single-valued function of

//y,

E^ E, and H.

The determination of

the fundamental equation for isotropic bodies

therefore reduced to

is

the determination of this function, or (as appears from similar considerations) the determination of

//\

as a function of

t,

E^ E, and H.

appears from equations (489) that

represents the sum of the
squares of the ratios of elongation for the principal axes of strain,
It

sum of the squares of the ratios of enlargement

by these axes, and that G repre-

that ^represents the

for the three surfaces determined

sents the square of the ratio of enlargement of volume.

E represents

shows that

tion (432)

Again, equa-

the sum of the squares of the

X', 1", and Z';

shows that J^ represents the sum of the squares of the

ratios of elongation for lines parallel to

eqiiation

(434)

ratios of

enlargement for surfaces parallel to the planes X'-

and equation

(438), like (439),

of the ratio of enlargement of volume.

co-ordinate axes

arbitrary,

is

it

shows that

Y\

Y'-Z\ Z'-X'

represents the square

Since the position of the

sum

follows that the

of the squares of

the ratios of elongation or enlargement of three lines or surfaces

which

in the unstrained state are at right angles to

otherwise independent of the direction

Hence,

^^and ^F

mean squares

are the

There

is

one another,

lines

all

possible directions in

solid.

not only a practical advantage in regarding the strain as

determined by E, E, and H, instead of E^ F, and G^ l^ecause

more simply expressed

terms of -^,

in

^,

certain theoretical advantage on the side of

l)ut

there

E^ F^ H.

X\ Y\

tems of co-ordinate axes X^ Y, Z, and

tical or

is

or surfaces.

of the ratios of linear elon-

gation and of superficial enlargement, for

the unstrained

the

of

is

is

also a

If the sys-

Z', are either iden-

such as are capable of super}>o8ition, which

it

will

always be

convenient to suppose, the determinant TI will always have a posi-

which a l>ody can be capable. But it

x\ y\ z' that
have a negative value. For example, we may make

tive value for

any

possible to give to
shall

This

will give

strain of
a*,

I[t=

y, z such values as functions of

1,

x',

11=

1.

= y\

--

(440)

s'.

while

X :=
will give

is

a-.',

y r= y\

=z

(441

z'

Both (440) and (441) give

\.

Now

although

such a change in the position of the jjarticles of a body as is represented by (440) cannot take place wliil(> the body remains solid, yet

W. Gihhs

J.

a method

Equilihrium of Heterogeneous Substances.

of representing

may be

strains

371

considered incomplete,

by (440) and (441).

such confusion by using E, 1\ and II to repreconsider an element of the body strained which in

which confuses the cases represented

We may

avoid

the state

X\ Y\
which

all

Let us

sent a strain.

y\
Z\ and

a cube with

z') is

(a?',

call

the edges

tliey are parallel,

dy\ dz according to the axes to

cc',

y\ or

~,

to the
shall

-^

it

fZ^c',

dy\

and

dz'

in the state
is

form of a cube and to a position

and

which

edges

ffe',

dy'

the positive ends of the

1",

edges toward the positive directions of the axes, and this

without giving the volume of the

2)

continuous changes

in whicli the

(,t, ?/,

determined by the quanti-

may always be brought by

be parallel to the axes of

as posi-

Whatever

are the greater.

2'

be the nature of the parallelopiped

corresponds to the cube

ties

edges parallel to the axes of

and consider the ends of the edges

tive for whicli the values of

may

c^a?',

its

parallelopiped

may be done

the value zero,

and therefore without changing the sign of H. Now tw^o cases are
possible
the positive end of the edge ffe' may be turned toward the
positive or toward the negative direction of the axis of Z.
In the
;

first

case,

evidently positive;

is

in

the second, negative.

The

we may say,
or negative, according

determinant // will therefore be positive or negative,

if

we

choose, that the volume will be ])Ositive

as the element can or cannot be brought from the state

state

(a;',

y\

z')

by continuous changes without giving

(a*,

y, z) to the

volume the

its

value zero.
If

we now

recur to the consideration of the principal axes of strain

and the principal

f/2, ZTg and T^,
',

ratios of elongation r^, ^2,

U2',

U^

/"g,

and denote by

C/j,

the principal axes of strain in the strained

and unstrained element respectively, it is evident that the sign of r.,

depends upon tlie direction in U-^^ which Ave regard as

for example,

corresponding to a given direction in JJ^.

If

we choose

directions in these axes so that r,, rg, r^ shall

positive or negative value of

axes

t^j,

tem

?7j',

coincide.

U^,

f/3

is

or

is

will determine

all

to associate

be positive, the

whether the system of

not capable of superposition upon the sys-

ZT21 C^a' so that corresponding directions in the axes shall

Or,

if

we

prefer to associate dii-ections in the

two systems

of axes, so that they shall be capable of superposition, correspondinodirections coinciding, the positive or negative value of

will deter-

mine whether an even or an odd number of the quantities r^^r^^^r

arc negative.

In this case

we may

write

372

tT.

Wi Gibhs

Equillhrium of Heterogeneous Substances.

dx
dx'

= H=

W.

J.

values to

G-ibbs

//v/,

when the stresses in the solid vanish. If we

common value of rj, r2, r^ which will make the

denote by r^ the

rpy,

and

373

etc.,

any given temperature, and imagine the true value

stresses vanish at

of

Equilibrium of Heterogeneous Substances.

also the vahie given

by equation

(444) to be expressed in

terms of the ascending powers of

^2^0.

''i-^o,
it is

(446)

''a-'^o.

evident that the expressions will coincide as far as the terms of

That

the second degree inclusive.

is,

the errors of the values of

if.\,

given by equation (444) are of the same order of magnitude as the

cubes of the above diiferences.

will

errors of the values of

dipy,

dlj:y,

dr^

The

'

dr^

dipy,
'

dr^

be of the same order of magnitude as the squares of the same

differences.

Therefore, since
dipy,
<dx

d-^.

_ dipy, dr^
dr.
^

ax

dipy.dr^
dr..

<dx
dr^j-i

jIx

dr^

Ax

dr..

^'

ci^n

<^-^r->

dx

dx

dipy,

dx

whether we regard the true value of ipy, or the value given by equaand since the error in (444) does Jiot affect the values of

tion (444),

dr.

dr^

dr..

-AJjvU

-J.tJC'

~.\A/iMj

dx'

dx'

dx'

which we may regard as determined by equations (431), (432), (434),

(437) and (438), the errors in the values of A'x, derived from (444)
will be of the same order of magnitude as the squares of the differences in (446). The same will be true with respect to A\,, X^,, Yy^,
,

etc., etc.

be interesting to see

It will

how

the quantities

e,

/*

and h are

related to those which most simply represent the elastic properties of

If we denote by
isotropic solids.
and
the elasticity of volume

and the

determined under the condition of constant

temperature and for states of vanishing stress), we shall liave as
rigidity'^ (both

definitions

^'^~''\)t'
* See

Thomson and

^^^"^

= r,^v',

Tait's Natural Philosophy, vol.

i,

(448)

p. 711.

3*74

where
V

W. Gibhs

j^

denotes a uniform pressure to which the solid

volume, and

its

]quUibrmni of Heterbgeneous ISubstances.

J.

volume

v' its

in

the state of reference

dx

subjected,

and

f&y

^_^_^_,.

when

is

(449)
\

dx ^^dx

dy

di/

dz

dz

dy'

dz'

dx'

dx'

dy'

Now
we

when

the solid

consider so

reference,

dz'

we

subject to uniform pressure on

is

much

'

of

it

as has the

volume unity

all

sides, if

in the state of

have

shall

=r

r,

and by (444) and

=:

r-g

=: y^,

(450)

(430),
if\;

Hence, by equation

~^'

= +3

+ 3/ 0^ + h V.

e /'^

(88), since //v, is equivalent to

= (M)t == 2

e ^'-^

(451)

//,

+ ifvi + ^

-^,(^)^=-t6^)-* +

(452)

i/.i;

(453)

and by (448);

Frr-t-^ +

1/V,,

(454)

'

To obtain the value of Ji in accordance with the definition

given by equations
we may suppose the values of E, F^ and

(434),

and (437) to be substituted

for the value of

^ must

From

2e

r^, like

differential coefficient

sion of the solid

4/r^,2.

when

(455)

= r^^, we have

+ 4/r2+A,.^:^0.

the three last equations

terms of r^, F, and

The quantity

vanish in (452)

2e

A, in

(432),

This will give

R
i^zz:

Moreover, since

in equation (444),

(449),

R\

may

e, /',

viz.,

and V,

be obtained the values of

(45G)

^'*

when without

is

a function of the temperature, the

representing the rate of linear expanstress.

Gihhs

J. TF.

It will

case

Equilibrium, of Heterogeneous Substances.

3V5

not be necessary to discuss equation (443) at length, as the

which has just been treated. [It

entirely analogous to that

is

must be remembered that

i]xi

the discussion of (443) will take the

bi

place everywhere of the temperature in the discussion of (444).]

If

the elasticity of volume and the rigidity,

both determined under the condition of constant entropy, (i. e., of no

we denote by Y' and R'

transmission of heat,) and for states of vanishing

have the equations
1e'

+ I/'^o,

F'=~;t--

(458)

= 2e' + 4/'r(,2,
+ 4/' r2 j^ h' r =

7^'

e'

shall

sti-ess, Ave

(459)
(460)

0.

Whence

^,_R'+^r,V'

P^'-^r,V'

^ _ I^
^^'=-^j^,

f'=~~V-l-^'--^
In these equations

the quantity
If

R', and

are to be regarded as functions of

i/y,.

we wish

to change from one state of reference to another (also

changes required

isotropic), the

easily

r,,,

made.

If

in

the fundamental

a denotes the length

we change from

second the values of the symbols

E by

a"^

and that of

state of reference,

we must

i/\,,

In

a*.

are

first, it is evi-

state of reference to the

first

y,, ?/v,

equation

line of the solid in the

length in the

its

the

E by

any

of

second state of reference divided by

dent that when

that of

(461)

are divided

making the change

by

a^,

of the

therefore sul)stitute in the fundamental

r<3//v,, ci^E, a^F, a^H for //,,, E, F,

and H, respectively. In the fundamental equation of the form (443),
we must make the analogous substitutions, and also substitute a^7]x,

equation of the form (444)

for

7/v,.

tions of

[It will
i]y,,

sul)stitiited,

be remembered that

and that

it is

i',

e',f',

and

represent func-

Jt

only when their values in terms of

ijy,

are

that equation (443) becomes a fundamental equation.]

Concernrng Solids uihich absorb Fluids.

There are certain bodies which are solid with respect to some of
have other components which are fluid.

their components, while they

In the following discussion,

we

shall suppose

both the solidity and

the fluidity to be perfect, so far as any properties are concerned

which can

aflect the conditions of equilibrium,

pose that the solid matter of the body

is

i.

e.,

we

shall sup-

entirely free from plasticity,

and that there are no passive resistances to the motion of the

Trans. Conn. Acad., Vol.

III.

48

fluid

June, 1877.

J.W.

376

Gibhs

Equilibrium of Heterogeneovs Substances.

components except such as vanisli with the velocity of the motion,

leaving it to be determined by experiment how far and in what cases
these suppositions are realized.
It is

evident that equation (356) must hold true with regard to

when the

such a body,
in a

quantities of the fluid components contained

given element of the solid remain constant.

Let 7',,', IV, etc.,

denote the quantities of the several fluid components contained in an
element of the body divided by the volume of the element in the
state of reference, or, in

other words, let these symbols denote the

which the several fluid components would have, if the body
should be brought to the state of reference while the matter contained in each element remained unchanged.
We may then say that
densities

equation (356) will hold true,

when

/"',

complete value of the differential of

fyi

are constant.

/"/, etc.,

will therefoie

The

be given by an

equation of the form

fZfv,

Now when
this

-\-:2 2'

t di],.,

denoting,

(^Y

divided by

is

its

^\ + X cir: + L,, cir,! +

volume

etc.

(462)

in a state of hydrostatic stress, the tei'm in

containing the signs of summation will

equation

joc^Uvi

body

the

Ix^.

as

in the state

reduce to

volume of the element

For in this case
of reference).

elsewhere,

the

:2:e

dx

j> d

=
We have, therefore,
dsy,

dx'

dy'

dy

dy

dy

dx

dy'

dz'

dz

dz

dz

dx'

dy'

dz'

dz'

2^ dvy,.

(464)

for a state of hydrostatic stress,

d)]y,

2^ <Jvy,

L,,

drj

Z^ dl]! -f

and multiplying by the volume of the element

which we may regard as constant,

in

etc.,

(465)

the state of refer-

ence,

de

di]

J) dv

-\-

L dm^,

+ Z,, dm,. + etc.,

(466)

J. TF.

where

f,

//,

Gibbs

Equilihriuin of Heterogeneous Substances.

v, w<, ni^, etc.,

denote

energy, entropy, :vnd volume of

tlie

the element, and the quantities of

several fluid components.

its

evident that the equation will also hold true,

if

only limitation with respect to the variations

to

which

symbols relate

tlie

The varied

matter.

state

It is

these symbols are

understood as relating to a homogeneous body of

body

377

The

finite size.

that the element or

is

always contain the same solid

shall

may be

one of hydrostatic stress or

otherwise.

But when the body

matter

is

de =^

ih]

and the

in a state of hydrostatic stress,

considered invariable,

is

jo dv

we have by equation

-\-

yi/

dm,,

//,,

dmi,

-f-

solid

(12)

etc.

(467)

should be remembered that the equation cited occurs in a discus-

It

which relates only to bodies of hydrostatic stress, so that the

is there regarded as one of hydrostatic stress.
But a comparison of the two last equations shows that
the last will hold true without any such limitation, and moreover,
that the quantities i, X^, etc., when determined for a state of hydrosion

varied state as well as the initial

static stress, are equal to the potentials

Since

we have

ence to bodies of hydrostatic stress,

state of the

stress or not, since this use of the

former definition.

symbol

may

etc.

we may apply

the potentials for the several

body considered, whether the

its

//,,,

It will also

this

term as we

We may therefore call the quanti-

choose with regard to other bodies.

ties X, Z,,, etc.,

//,

hitherto used the term potential solely with refer-

fliiid

body

is

components

in the

one of hydrostatic

term involves only an extension of

be convenient to use our ordinary

Equation (462)

for a potential to represent these quantities.

then be written

f?fv

dih,

+ '^ 2' (x^, d^-^\ +

pi

drj +

/x,,

dl\'

etc.

(468)

This equation holds true of solids having fluid components without

any limitation with respect to the initial state or to the vaiiations,

except that the solid matter to which the symbols relate shall remain
the same.

In regard to the conditions of equilibrium for a body of this kind,

it is

we

evident in the

shall obtain

ditions

first

place that

from the general

which wo have obtained

if

we make FJ, /V,

etc.,

constant,

criterion of equilibrium all the con-

for ordinary solids,

and which are

expressed by the formulae (364), (374), (380), (382)-(384).

The
quantities /',', F^, ^tc, in the last two formulae include of course

378

TK Gibbs

J.

JEquilibriuta of Heterogeneous Substances.

by /"', jTj', etc., and which

components of the body, as well as the correspond-

those which have just been represented

relate to the fluid

ing quantities relating to

Again,

solid components.

its

if

we

sup-

pose the solid matter of the body to remain without variation in

quantity or position,

it

will easily

appear that the potentials for the

substances which form the fluid components of the solid body must
satisfy the

tact with

same conditions

it,

in the solid

body and

The above conditions must however be

to make them sufticient for equilibrium.

may

in like

It is evident that if

the

components which are

set

be absorbed by the solid as well as by the

manner

the quantity of the solid

if

ponents of the ncAV portion

ing solid mass.

body

See eqs. (22).

slightly modified in order

solid is dissolved at its surface, the fluid

free

the fluids in con-

in

as in the case of entirely fluid masses.

may

is

fluid mass,

increased, the fluid

and
com-

be taken from the previously exist-

Hence, whenever the solid components of the solid

are actual components of the fluid mass, (whether the case

body or

the same with the ftdd components of the solid

not,)

is

an

equation of the form (383) must be satisfied, in which the potentials

/7, /^; etc., contained implicitly in the second member of the equation are determined from the solid l)ody.

body

ents of the solid

Also

if

the solid compon-

are all jjossible but not all actual

of the fluid mass, a condition of the form (384)

must be

components

satisfied,

member being determined

values of the potentials in the second

the

as in

the preceding case.

The

quantities
t,

X^,,

being difierential coeflacients of

^^-'

Z^,,
^y.

/<,

/<,

(409)

etc.,

with respect to the variables

"!" ^-

^^^''

^'''

('^'^

will of course satisfy the necessary relations

= -^

etc.

(-471)

dx'

This

i-esult

member

may

be generalized as follows.

Not

only

of equation (468) a couiplete differential in

its

is

the second

present form,

but it will remain such if we transfer the sign of differentiation {d)

from one factor to the other of any term (the sum indicated by the
symbol '2 '2' is here supposed to be expanded into nine terms), and
For to
to
at the same time change the sign of the term from

W. Gibbs

J.

substitute

iug

Equilibrkon of Heterogeneous Substances.

for tdtfy,, for

^]^i,(Jt

complete cUfFereutial d{t

tlie

example,

is

equiA'alent to subtract-

Therefore,

>/y,).

379

if

we

consider the

and (470) which occur in any same term in equation (468) as forming a pair, we may choose as independent variables
either quantity of each pair, and the differential coefficient of the
<puintities in (409)

remaining quantity of any pair with respect to the independent

variable of another pair will be equal to the differential coefficient of

the remaining quantity of the second pair with respect to the inde-

pendent variable of the

first,

taken positively,

the independent

if

by the

variables of these pairs are both affected

sign

equation

in

(468), or are neither thus affected, but otherwise taken negatively.

Thus

dx'

^\lx'

WJx - [dxj,,:
where

\di

;;|rx,

-~

\dx;Jr.:

addition to the quantities indicated by the suffixes, the

in

following are to be considered as constant: either

\-

(^*'

Ay, or -

It will

ditions

^^'^'

'

either

dz

ry

Zj,,

or y-;, eitiier

or /

//^

= const.,

//,,

= const,

or

//y,

either

etc.

,/,

be observed that when the tempei-ature

//.,

^,,

is

constant the con-

represent the physical condition of a

body in contact with a fluid of which the phase does not vary, and
which contains the components to which the potentials relate. Also
that
in

when FJ,

any

Ff,',

infinitesimal

are constant, the heat absorbed by the body

change of condition per unit of volume measured

etc.,

in the state of reference

represented by

is

by dQy,, and use the suffix

transmission of heat, we may write
quantity

/^og_A
\

_((IX^\

d^ )q~ UQv.)':^.'

/^oi_\
\ dX^, }q

\dxJt-vi\ogt)x.:

tdi]^,-,.

If

we denote

this

q to denote the condition of

_
-

('1^\

\dQjxJ

\/lt-

\d\o^t)%,^

no

^^^^^

^^^'')

^'dx'

where ZV, F/,

etc.,

must be regarded

and either X^, or -^,,

as constant in all the equations,

either Z^, or

-
,

in

each equation.

380

W. Gihhs

J.

E<iallihrlaui of Heterogeneous Substances.

Influence of sukfaces of discontinuity upon the equilibrium

OF heterogeneous masses. Theory of capillauity.

We

have hitherto supposed,

in treatiiig

of lieterogeneous masses in

might be considered as separated by mathematical

surfaces, each mass being uuaifected by the vicinity of the others, so
that it might be homogeneous quite up to tlie separating surfaces
contact, that tliey

both with respect to the density of each of

and

also with resjject to the densities of

such

is

not rigorously the case

is

its

various components

evident from the consideration that

were so with respect to the densities of the components

if it

That

energy and entropy.

it

could

not be so in general Avith respect to the density of energy, as the

sphere of molecular action

observation that
face that

it is

any mass

is

But we know from

not infinitely small.

only within very small distances of such a suris

sensibly affected

by

its

vicinity,

natural

consequence of the exceedingly small sphere of sensible molecular

action,

and

this fact renders

account of the variations

and of energy and entropy, which occur

discontinuity.

We may

method of taking
component substances

possible a simple

in the densities of the

in the vicinity of surfaces of

use this term, for the sake of brevity, with-

out implying that the discontinuitj'

is

absolute, or that the

distinguishes any surface with mathematical precision.

It

term

may be

taken to denote the non-homogeneous film which separates homo-

geneous or nearly homogeneous masses.

Let us consider such a surface of discontinuity

in a fluid mass
and uninfluenced by gravity. For the premeasurement of the quantities with which we have to do, it will

which
crise

is

in equilibrium

be convenient to be able to refer to a geometrical surface, which

shall

be sensibly coincident with the physical surface of discontinuity,

but shall have a precisely determined position.

For

this end, let us

take some point in or very near to the physical surface of discontinuity,

and

all

and imagine a geometrical surface to pass through this point

other points which are similarly situated with respect to the

condition

Let this geometrical surface be

and designated by the symbol S. It

of the adjacent matter.

called the dividing surface,

will be observed that the position of this surface is as yet to a certain

extent arbitrary, but that the directions of

everywhere determined, since

all

its

normals are already

the surfaces which can be formed in

the maimer described are evidently parallel to one another.

also

Let us
imagine a closed surface cutting the surface S and including a

part of the homogeneous mass on each side.

We will

so far limit the

J.

form of

W. Gihbs
tliis

Equilihriam of Heterogeneotis ^nhstances.

381

closed surface as to suppose that on each side of S, as far

any want of perfect homogeneity in the fluid masses, the

closed surface is such as may be generated by a moving normal to S.
as there

is

included by the closed surface be

Let the portion of

is

denoted by

this portion

vS
which
and the area of

by s. Moreover, let the

s,
mass contained within the closed surface be divided into three parts
by two surfaces, one on each side of S, and very near to that surface,
although at such distance as to

lie

the discontinuity in

Let us

its vicinity.

entirely

beyond the

call the j)art

infliience

of

which contains

the surface s (with the physical surface of discontinuity) M, and the

homogeneous parts M' and M", and distinguish by f, i', t\ if, //', 7/',
m,, m^\ *'*/, *'*2? ^25 ^"2'? ^^c--, the energies and entropies of these
masses, and the quantities which they contain of their various components.
It

is

necessary, however, to define

more

precisely

what

is

to be

understood in cases like the present by the energy of masses which

are only se])arated from other masses by imaginary surfaces.
A part
of the total energy which belongs to the matter in the vicinity of the

separating surface, relates to pairs of particles which are on different

sides of the surfjice,

referable to either

and such energy is not in the nature of things

mass by itself. Yet, to avoid the necessity of

taking separate account of such energy,

it

will often

be convenient to

which we refer to the separate masses.

When there is no break in the homogeneity at the surface, it is
natural to treat the energy as distributed with a imiform density.
This is essentially the case with the initial state of the system which
we are considering, for it has been divided by surfaces passing in
include

in the energies

it

general tlu'ough homogeneous masses.

The only exception

that

of

the surface which cuts at right angles the non-homogeneous film

(apart from the consideration that without any important loss of
generality

we may regard

the part of this surf^ice within the film as

very small compared with the other surfaces)

real, as there is

no change

in the state of the

perpendicular to this surface.

But

is

rather apparent than

matter in the direction

be considered
be convenient to limit ourselves

in the variations to

in the state of the system, it will not

do not create any discontinuity at the surfaces bounding

M, M', M" we must therefore determine how we will
estimate the energies of the masses in case of such infinitesimal
discontinuities as may be supposed to arise.
Now the energy of
each mass will be most easily estimated by neglecting the disconto such as

the masses

tinuity,

i.

e.,

if

we

estimate the energy on

the supposition that

382

Wl Gibhs

(T.

Equilihrium of Heterogeneous Substances.

beyond the bounding surface the phase

is

identical with that within

This will evidently be allowable,

the surface.

the total

amount of energy.

(juantity,

we have

To show

only to observe that,

one side of a surface where there

that

if

it

if it

does not affect

does not atfect this

the energy of the mass on

an infinitesimal discontinuity of

is

is greater as determined by this rule tlian if determined by

any other (suitable) rule, the energy of the mass on the other side
must be less by the same amount when determiued by the first rule
than when determined by the second, since the discontinuity relative
to the second mass is equal but opposite in character to the discon-

phase

tinuity relative to the

first.

entropy of the mass which occupies any one of the spaces

If the

considered

is

not in the nature of things determined without refer-

ence to the surrounding masses,

we may suppose

a similar

method to

be applied to the estimation of entropy.

With

this understanding, let us retxirn to the consideration of the

equilibrium of the three masses

M, M', and

We

JNI".

shall

suppose

that there are no limitations to the possible variations of the system

due to any want of perfect mobility of the components by means of

which we express the composition of the masses, and that these components are independent, i. e., that no one of them can be formed out
of the others.

With regard
tinuity,

is

it

to the

mass M, Avhich includes the

boundaries are considered constant,

reversible

sui"fixce

variations

(i.

that

those of which the opposite

e.,

possible), the variation of its

are

also

energy should vanish with the varia-

and of the quantities of

tions of its entropy

of discon-

when its
when
consider
only
and
we

necessary for its internal equilibrium

its

various components.

mass will not affect the energy or the entropy

of the surrounding masses (when these quantities are estimated on
the princi]>le which we have adopted), and it may therefore be
treated as an isolated system. For fixed boundaries of the mass ]\r,

For changes within

and

this

we may therefore write

6m^ + A^ dm^ + etc.,
A^
6= A^dii+

for reversible variations,

where

^If,,

A^, A2,

etc.,

are quantities determined

(unvaried) condition of the system.

It

is

(470)

by the

evident that

A^

initial
is

the

temperature of the lamelliform mass to which the equation relates,

or the temperature at the surface of discontinuity.
of this equation with (12)
^4 2, etc., is entirely

it

will

IJy com])arison

be seen that the definition of

analogous to that of the potentials

in

yl

,,

homo-

W. Gibhs

J.

Equilibrmm, of Heterogeneoxis Substances.

383

geneous masses, although the mass to which the former quantities

relate

not homogeneous, while

is

we may

tension of the term potential.,

etc.,

By

the value of these quantities

lamina (M) to which they

which

fact,
is

i-elate.

we

If

true of

This designation

substitue

for

jii^

we may

dm

-f- ;/.

write

(Jw,

energy could have a value

less

(477)

etc.

the formula will hold

in this equation,

variations whether reversible or not

all

appear hereafter, that

will

independent of the thickness of the

If we employ our ordinary sym-

bols for temperature and potentials,

de =zt6f^-\-

a natural ex-

the quantities .Ij, .ig,

call

potentials at the surface of discontinuity.

x.\\Q

be farther justified by the

will

our ])revious definition of poten-

in

only homogeneous masses were considered.

tials,

;*

for if the variation of

than that of the second

energy

its

diminished without change of

is

quantities of

its

its

member

the equation, there niAst be variation in the condition of

in

of

which

entropy or of the

various components.

important, however, to observe that for any given values of

6m ^, 6m2, etc., while there )naij be possible variations of the

It is
rf//,

nature and state of

of the second

for

member

which the value of Se

is

greater than that

of (477), there niust always be possible varia-

tions for Avhich the value of 6e

is

equal to that of the second member.

* To illustrate the difference between variations which are reversible, and those

which are
rium

at a

them

as

not,

we may

conceive of two entirely different substances meeting in equilib-

mathematical surface without being at

of mixture

is

mixed.

We may also

conceive of

in a thin film about the surface

amount

are absolutely unmixed, the

diminution, and

member

which the substances commence

of (477).

cases actually occur

of mixture can be increased, but is incapable of

then consistent with equilibrium that the value of Se

it is

tion of the system in

the second

all

where they meet, and then the amount

capable of variation both by increase and by diminution. But when they

mixed

but

it

to mix) should

(for a varia-

be greater than

not necessary to determine whether precisely such

It is

would not be legitimate to overlook the possible occur-

may be

rence of cases in which variations

possible while the opposite variations are

not.
It will

tirely

be observed that the sense in which the term reversible

different

from that

in

which

it

is

namics, where a process by which a system

called reversible, to signify that the system

the state

is

here used

is

en-

frequently used in treatises on thermodyis

brought from a state

may

also be brought

to a state

from the

state

B is
B to

through the same series of intermediate states taken in the reverse order

by means of external agencies of the opposite character. The variation of a system

from a state A to a state B (supposed to differ infinitely little from the first) is here
called reversible

when

relation to the state

the system
that

is

capable of another state B' which bears the same

bears to B.

Te.\ns. Conn. Acad., Vol. III.

49

June, 1877.

384

J.

It will

TT'T

Gihhs

EqxdUhrlum

of Heterogeneous

be convenient to have a notation which

press this

by an

will enable us to ex-

Let be denote the smallest value

equation.

value nearest to

of de consistent with

oo)

ISuhstances.

(i.

e.,

the

given values of the

other variations, then

bf

Sj]

-\- lA^

diti^ -\-

/.(^

+ etc.

Sm.^

(478)

For the internal equilibrium of the whole mass which

the parts M, M', M", it is necessary that
6e-\- St'

which do not

for all variations

consists of

+ Se"^0

(479)

affect the enclosing surface or the

total entropy or the total quantity of

any of the various components.

we also regard the surfaces separating M, M', and M" as invariable, we may derive from this condition, by equations (478) and (12),
If

the following as a necessary condition of equilibrium

+ ^tc.
+ 61/ //j' Sin^' + /'o'
+ etc.
dill/'
/i/
^"i/
+ etc.^0,
+ (h/" + /</'
+
-\- /fj

6?/

d7)i^ -\-

J.I2

Sni^

<Si>i2'

-\-

t'

t"

(480)

the variations being subject to the equations of conditions

dm^

-f

dm/ + dm/ =

61^2

-\-

6111/

0,

6)112" ^^ ^5

-J-

etc.

It

may

also be the case that

(5^2 ', 6m2",

etc.,

the value zero.

some of the quantities 6ni^\ 6m/',

are incapable of negative values or can only have

This will be the case when the substances to which

these quantities relate are not actual or possible components of M'

(Seepage 117.) To satisfy the above condition it is necesor M".

sary and sufficient that

t

jji/'

It will

6m/^).i^6m/,

be observed

that,

if

= t'

1.1/'

(482)

t",

67n

/'^

f.12

^^^2%

the substance to which

^tc.
/(,, for

(484)
instance,

an actual component of each of the homogeneous masses,

relates
If it is an actual component of the
yu/
///'.
we shall have //,
is

first

possible

have

If it is also a
//,'.
we shall have yu,
component of the second homogeneous mass, we shall also

only of these masses,

/A^=}.i/'.

If this substance occurs only at the surface of dis-

W. Gihhs

J.

Equilibrium of Heterogeneous Substances.

continuity, the value of the potential

will not be

/<,

385

determined by

any equation, but cannot be greater than the potential for the same
substance in either of the homogeneous masses in which it may be a
possible component.

conditions of equilibrium

It appears, therefore, that the particular

relatiiig

and

tem2)erature

to

which we have

the potentials

befoi-e

obtained by neglecting the influence of the surfaces of discontinuity

(pp. 119, 120, 128) are not invalidated

by

M' and M" by imaginary

bounded

like

limits of

homogeneity,

the influence of such dis-

homogeneous parts of the system

continuity in their application to

surfaces lying within the

may be

condition which

faces very near to the surfaces of discontinuity.

It

fulfilled

by

sur-

appears also that

similar conditions will apply to the non-homogeneoiis films like M',

which separate such homogeneous masses. The properties of such

which are of course different from those of homogeneous

films,

masses, require our farther attention.

The volume occu|)ied by the mass M is divided by the surface

two parts, which we will call '" and v"'\ v'" lying next to M',
and v"" to M". Let us imagine these volumes filled by masses hav-

into

ing throughout the same temperature, pressure and potentials, and

the same densities of energy and entropy, and of the various com-

ponents, as the masses

by equation

(12), if

=
de"" =
Se'"

t'

M' and M"

we regard

ch/"

6i/"'

t"

whence, by (482)-(484),
Si:"'

(U""

From

//,

Or,

if

rf(w,

we

t'"

(hn^'"

///' (h,i^""

we have

j.i^

//,

6"")

m,'"

t rf(//

m,"")

dm^"'

Srn.J'"

f.1^"

Sm.J"

iA

-\- /.i^

then have,

shall

etc.,

(485)

+ etc.

(48G)

for reversible variations

= dif" + dm,'" -f
= t6j/""-{- M,6m^""

these equations and (4V7),

S{e

//,'

We

respectively.

the volumes as constant,

we have

//'"

-f /t2

6m2'"'

etc.,

(48V)

+ etc.

(488)

for reversible variations

//'")

S{m^ -m"' - m.J'")

+ etc, (489)

set*

= - m\ =mj Wj'" w,"",

6'"

f "",

* It will be understood that the

= 7/

//'"

;/"",

m\=zm^ rn^" ^

here used

only intended as a distinguishing mark.

denote any quantity.

if

is

m^"",

(490)
etc.,

(491)

not an algebraic exponent, but

The Roman

letter

is

S has not been used to

386

J.

we may

W. Gibhs

of Heterof/eneoiis Substances.

write
St^

This

JEquilihrimn

(h/^

ih/f^

//

//2 c^?"|

etc.

(492)

true of reversible variations in which the surfaces whicli have

is

been considered are

fixed.

be observed that

It will

a^

denotes the

excess of the energy of the actual mass which occupies the total

volume which we have considered over that energy which

have,

if

it

would

on each side of the surface S the density of energy had the

same uniform value quite up to that surface which it has at a sensiand that tf, m^, m|, etc., have analogous significations.
It will be convenient, and need not be a source of any
misconception, to call 6* and ?f the energy and entropy of the surface

ble distance from it;

in
sities

and entropy),

(or the siijierficial energy

of energy and entrojiy,

and

the superficial den-

171^

-,

~, etc.,

the stqyerficinl densities of

the several components.

Now

these quantities

[e^,

if,

m\,

by the various imaginary

ties

have been defined.

surfaces

The

determined partly by

etc.) are

the state of the physical system which

we

are considering, and partly

by means

of which these quanti-

position of these surfaces,

will be

it

remembered, has been regarded as fixed in the variation of the system. It is evident, however, that the form of that portion of these
surfaces,

which

lies in

the region of homogeneity on either side of the

surface of discontinuity cannot affect the values of these quantities.

To

we have

obtain the complete value of 6t^ for reversible variations,

therefore only to regard variations in the ]josition and form of the

limited surface s, as this determines

all

of the surfaces in question

lying within the region of non-homogeneity.

the form of s to remain unvaried and only

vary, either

necessary to

Let us
its

suppose

fii'st

position in space to

by translation or rotation. No change in (492)

make it valid in this case. For the equation is

S I'emains fixed and the material system

is

varied in position

will

valid

be
if

also, if

the material system and s are both varied in position, while their
relative position

remains unchanged.

the surface alone varies

But

if

Therefore,

it

will be valid if

its position.

the form of s be varied,

we must add

to the second

member

(492) terms which shall represent the value of

Sa^

due to such variation

dtp" ~~ jA

in

Srn^^

the form of

~
s.

f^

Sm% ~
If

we

^^^c.

su]pose s to be

suffi-

W. Gibbs

J.

Equilibnum of Heterogeneous Substances,

887

ciently small to be considered uinfoi-m throughout in its curvatures

and

surrounding matter, the value of the

in respect to the state of the

above expression will be determined hy the variation of its area 6s

and the variations of its principal curvatures (Jc^ and (Jcg, and we

may

write
St^ =.

Sif -f

/<, 8tiii\

-\-

a 8s

dm\

//g

6\ 8c

+ etc.
+ C'g

(Jc2,

(493)

or

=
+

8t^

<j,

6ff

4-/^2 ^^"%

yUi Stn^^

^^^-

Ss -\-^{C, -^ C,) S{c, -^ c,)

ff

C,, and

initial state

6*2

+ i{C\

- C,)8{c,-c,),{494)

denoting quantities which are determined by the

of the system and position and form of

the complete value of the variation of

But

the system.

surface s that 6\

To show

s.

Tlie

above

is

for reversible variations of

always possible to give such a position to the

is

it

f**

vanish.

C.^ shall

this, it will l)e

convenient to write the equation

in

tlie

longer form [see (490), (491)]

de

8e"'

=
i.

e.,

8e

/J

8m^

o-8s^i

{C\

C,) 8{c,

by (482)-(484) and

87}

81/"

_ Se"" +

etc.
//g 8711
^"'
^" + etc.
/z,
8711
8m
+
+ //,
^""
8?/"" + //, 8m
+ /1 2 8m.^ "" + etc.

8?/

^x^

8m

this equation

i{C\ -

(J,)

8{c^~c,), (495)

(12),

|<2

^^2

= ff8s + ^{C\ + C,) 8{c, +

From

c,)

it

appears

r-^)

^^c.

+^>' 8v"' +^>" 8v""

+H

(^\

- O2)

^(c,

c,).

(496)

in the first place that the j^ressure is

the same in the two homogeneous masses separated by a plane surFor let us imagine the material system to
face of discontinuity.

remain unchanged, while the plane surface s without change of area

or of form moves in the direction of its normal.
As this does not
affect the

boundaries of the mass M,

8m,^
8 87/
8m2
=:
= (J(e,+C2) = 8{c,^C2) = and 8v"' =
= p'\ when the surface of discontinuity plane.
t

Also

8s

Hence j)'

0,

etc.

//g

//j

0,

0.

0,

8v"".

is

Let us now examine the effect of different positions of the surface !^

same material system upon the value of 6', -|- (', supposing at
first that in the initial state of the system the surface of discontinuity

in the

is

plane.

Let us give the surface ^ some particular position.

Tn the

388

W. Gibhs

J.

Equilibrium

the system

initial state of

tliis

of Heterogeneous

Siihstances.

surface will of course be plane like the

physical surface of discontinuity, to which

In the

parallel.

is

it

become a portion of a spherical

surface having positive curvature
and at sensible distances from
this surface let the matter be homogeneous and with the same phases
as in the initial state of the system; also at and about the surface let
the state of the matter so far as possible be the same as at and about
varied state of the system, let

it

(Such a variation

the plane surface in the initial state of the system.

may

the system

in

the

as

tively,

whether such
librium

is

evidently take place negatively as well as posi-

surface

may

be curved toward either

But

side.

with the maintenance of equi-

a variation is consistent

of no consequence, since in the preceding equations only

the initial state

Let the

supposed to be one of equilibrium.)

is

surface s, placed as supposed, whether in the initial or the varied

state of the surface, be distinguished

changing either the

make another

us

let

initial

but removed from

tion

it

same distance

It will

A.

it

be parallel to

its

former posilie

the

In the varied state of the system, let

be spherical and concenti'ic with

s',

of course

Let the surface

unvaried system.

Without

a distance A on the side on which

centers of positive curvature.

it

s'.

supposition with respect to the imaginary sur-

In the imvaried system let

face s.

by the symbol

or the varied state of the material system,

lie

s,

and sepai-ated from it by the

on the same side of s' as in the

placed in accordance with this

second supposition, be distinguished by the symbol

initial

and the varied

state, let the

Now

by a common normal.

in

equation (496)

is

+ v""), ^'"'+ v""

member

Now
we

the vahie of

the same

is

and

'

if

",

being the volume of M.

Moreover, ^(Cj

we may

we make

shall

s,

being deter-

true p' 6v"' -^ p" 6v"" or

Cg) =

Therefore the second

both for

distinguish the quantities determined for

marks

Both in the
s".
and s" be traced

of (496) will have the same value whether the expressions

relate to s' or s".

we

'

not aifected by the position of

mined simply by the body

j)'6{v"'

perimeters of

therefore write

Ss"

z=z 0,

have by geometrical necessity

s'

and

s'

and

for s"

s".

If

by

the

W. Gihbs

J.

EquU'ibrmm of Heterogeneous Sxhstances.

389

Hence

But

tf(e,'+c'./)r=dXc/+C2").
6*/ +

Therefore,

This equation shows

to

G ^" +
it

tliat

'

+2

tf'.s

must

= 6\

we may give

G2" by placing s" a

other side of
plane,

^'3

"

distance on one or on the

when

s'.

Since this

also

be true when the surface

this piirpose a surface

true

C\ ".

a positive or negative value

sufficient

is

may be regarded

the (unvaried) surface

is

And

nearly plane.

as nearly plane,

is

for

when

the

radii of curvature are very large in proportion to the thickness of the

when the

non-homogeneous

film.

This

have any sensible

size.

Tn general, therefoi'e, whether the surface of

discontinuity
so that Cj

plane or curved

is

Now we may
is

the case

is

it

radii of curvature

possible to place the surface s

is

in equation (494) shall vanish.

easily convince ourselves

by equation

placed within the non-homogeneous film, and s=z

(498) that

1,

if

the quantity

same order of magnitude as the values of 6^, 7f, ni\, //<|, etc.,
while the values of C, and G2 ai"e of the same order of magnitude

is

of the

as the changes in

by

must

Hence, on account of the

unity.

thinness of the non-homogeneous film,

by such a change of curvature

affected

since

can be very

it

in s, the values of

be very small relatively to

in general

by

the values of the former quantities caused

increasing the curvature of s

o'.

And

little

C, and G^

hence,

if s'

placed within the non-homogeneous film, the value of A which

be

Avill

make Cj"

-f C\" vanish must be very small (of the same order of

magnitude as the thickness of the non-homogeneous film). The position of s, therefore, which will make G 4- G2 in (494) vanish, will
^

in

general

be

sensibly

coincident

with the

physical

surface

of

discontiniiity.

We

shall hereafter suppose,

when the contrary

is

not distinctly

indicated that the surface s, in the unvaried state of the system, has

such a position as to make C,

the surface s

cUvidmg

is

surface,

of discontinuity.

Cg 1=

0,

It will

be remembered that

and which

We may

is

we have

called the

coextensive with the physical surface

suppose that the position of the dividing

everywhere determined by similar considerations. This

evidently consistent with the suppositions made on page 380 with

surface
is

a part of a larger surface S, which

is

reacard to this surface.

390

TK Gibbs

J.

We

may

l^quilibriwa of Heterogeneous Sxibstances.

therefore cancel the term

In regard to the following term,

in (494).

Cj must necessarily be equal to t\^ when

when

the surface of discontinuity

is

it

Cj

Now

plane.

thinness of the non-homogeneous film,

will

be observed that

= Cg, which

is

the case

on account of the

we may always regard

as

it

composed of parts which are a})proximately plane. Therefore, without danger of sensible error, we may also cancel the term

Equation (494)
6t^

We may

is

thus reduced to the form

S)f

+ o- 6s+ //

dm^^

+ //g 6m\ -f etc.

regard this as the complete value of

(497)

6t^, for all reversible

variations in the state of the system supposed initially in equilibrium,

when the dividing surface has its initial position determined in the
manner described.
The above equation is of fundamental importance in the theory
It expresses a relation

of capillarity.

with regard to surfaces of

dis-

continuity analogous to that expressed by equation (12) with regard

homogeneous masses. From the two equations may be directly

deduced the conditions of equilibrium of heterogeneous masses in con-

to

tact, subject or not to the action of gravity,

influence of the surfaces of discontinuity.

cluding the action of gravity,

we

we

shall take

without disregard of the

The general problem,

up hereafter:

in-

at present

shall only consider, as hitherto, a small part of a surface of dis-

continuity with a part of the homogeneous mass on either side, in

order to deduce the additional condition which

we take account

may be found when

of the motion of the dividing surface.

We sup})Ose as before that the mass especially considered is

bounded by a surface of which all that lies in the region of nonhomogeneity is such as may be traced by a moving normal to the
But instead of dividing the mass as before into
dividing surface.
four parts, it will be suflicient to regard it as divided into two parts
by the dividing sui-face. The energy, entropy, etc., of these parts,
estimated on the supposition that
energy,

etc.)

is

its

nature (including density of

uniform quite up to the dividing surface, will be

Then the total energy

rf, etc., ", ?/', etc.
and the general condition of internal equilibrium

denoted by e\
^

+ '-f f",

will

be

will

be

that

d^iH(^i'+(5f"^0,

(498)

W. Gibhs

J.

when

Equilibrium of Heterogeneous Substances.

is fixed, and the total entropy and total

components are constant. We may sup]ose

the bounding surface

quantities of the various

V^

391

'"n

V'> V"->

by (497) and

'^^''2

'*^^2'i

set =: for

-p

6s

o-

(We may

"4'

"*]'? '"i">

to be all constant,

Tlien

(499)

^t'C-,

(12) the condition reduces to

Sv'

- p"

dv"

0.

since changes in the position of the dividing

^,

surface can evidently take place in either of

two opposite

This equation has evidently the same form as

if

directions.)

membrane without

and having a tension ff, uniform in all directions, existed

Hence, the ])articular position which we

rigidity

at the dividing surface.

have chosen
ff

for this surface

a uniform normal distance

Ss z=

(c

+ C2

may

SN, we

s dJV,

whence

{c^

-\-

This

relates.

jo'

is

of equality of pressure

masses

6v'

= SK

c^)

^p' Jo",

Sv"

=-

.s

6JV;
(500)

their centers lie on

the side to

the condition which takes the place of that

(see p).

119,

128) for heterogeneous

we take accoimt of the

in contact, vvlien

We

faces of discontimiity.

move

have

shall

when

the curvatures being positive

which

be called the surface of tension, and

If all parts of the dividing surface

the superficial tension.

flixid

influence of the sur-

have already seen that the conditions

relating to tem])erature and the potentials are not affected

by these

surfaces.

Fundamental

JEq nations for /Surfaces

of Discontinuity.

In equation (497) the initial state of the system

one of equilibrium.
state

is

The only

that the variation shall be reversible,

variation shall be i)ossible.

variations in

dt^

Both the

we may

dif' -f

i.

e.,

that an o])po8ite

in equilibrium.

use the character

(T ffe

sup[)osed to be

Let us now confine our attention to

which the system remains

guish this case,

is

limitation with respect to the vaiied

-f

/^

d7n\

To

distin-

instead 6, and write

Mz ^''4

^'t<^'-

(501)

states considered being states of equilibrium, the limitation

with respect to the reversibility of the variations

may

be neglected,

since the variations will always be reversible in at least one of the

states considered.
If

we

integrate this equation, supposing the area s to increase

any finite value s, while the material system to a part

equation relates remains without change, we obtain
the
which
of

from

zei'o to

f^

f if^

-\- (7 s

Trans. Conn. Acad., Vol. HI.

+ n

m^,

-J-

//g

50

n%\ -f etc.,

(502)
July, 1877.

:592

whicli
(in

W.

J.

(irU>hs

may be

Eiuillhrhim

variable,

o",

^,

same nature throughout, or through^tc are constant.

//,, f^^i

diiFerentiate this equation, regarding all

and compare the

if

If

of the

is

out which the values of

we

(It -\-

we denote

sdG

m\

-\-

the quantities as

result with (501), avc obtain

+ m\

f?//j

diA^

etc.

by

fg? Vs?

l\i

^2->

we have
f^

jf

,s

r,

==

-1,

i ,

= -^,

etc.,

= td?^^ + dl\ + Mo ^^^2 +

= t?/^+ G + Ml I\ + M2 ^2 +
da = dt r^
^hh ~
de^

(506)
"

t^tc,

8^

f?yu,

7/s

Now

^^tc,

//,

7^2

(505)

and the preceding equations may be reduced to the form

any

(503)

0.

the superficial densities of energy, of entropy, and

of the several component substances (see page 380)

etc.,

ISiihstanees.

applied to any portion of any surface of discontinuity

equilibrium) which

If

of Heterogeneous

^tc.

(507)

(508)

the contact of the two homogeneous masses does not impose

upon the variations of phase of

restriction

either, excej^t that

the temperatx;re and the potentials for actual components shall have

the same value in both.

For however

[See (482)-(4S4) and (500).]

the values of the pressures in the homogeneous masses

may vary

(on

account of arbitrary variations of the temperature and potentials),

and however the superficial tension may vary, equation (500) may

always be

satisfied

by giving the proper curvature

to the surface of

tension, so long, at least, as the difference of pressures

is

not great.

any of the potentials /.i^, /.i.^, etc. relate to substances

which are found only at the surface of discontinuity, their values
may be varied by varying the superficial densities of those subMoreover,

if

stances.

The values of

variable,

and

it

these quantities.

derive from

number

it

t,

f.i\->

/*3'

^^^- ^^'^

therefore independently

appears from equation (508) that c

by

If the

form of

this function

is

is

a function of

known, we may

differentiation w-ff equations {n denoting the total

of component substances) giving the values of

7/s,

/'j,

I\,

This will give us,

etc. in terms of the variables just mentioned.
2n \- A quantities
the
between
ecpxations
independent
(507),n-|-3
with

which occur

in

that ecpiation.

These

.are

all

that exist, since

';/-f 1

W.

./

<rlJ>hs

Equilibrium of Heterogeiieous ISxhstances.

of these quantities are independently variable.

we have

that
tities

y/

+3

Or,

we may

independent equations between the

occurring in equation

of which n-\-2 are

(5ti2),

2^/,

393

consider

+5

quan-

independently

variable.

An

equation, therefore, between

(T,

may be

An

(509)

called a fundamental equation for the surface of discontinuity.

between

may
it is

//,

fs,

also be called a

'h->

-{-

^H

fundamental e([uation

for the

n.

and one

the variables

may

(-510)

^^.c,

^s?

evident from (501) that an equation

2 of

etc.,

))i\^

)ii\

ft',

ing between the variables (510), and

etc.,

//g,

equation between
f^

or

yUj,

^,

if this

For

the same sense.

in

may

('51 1)

be regarded as subsist-

equation be known, since

be regarded as independent

(viz.,

ii

-|-

variations in the nature of the surface of discontinuity,

-f- 1

for the area of the surface considered),

differentiation

and comparison with (501), m

-}-

we may

2 additional

obtain

by

equations

between the 2;^ -}- 5 quantities occurring in (502). Equation (50(3)

shows that equivalent relations can be deduced from an equation

between the variables (511). It is moreover quite evident that an

equation between the variables (510) must be reducible to the form
of an equation between the ratios of these variables, and therefore to
an equation between the variables (511).
The same designation may be applied to any equation from which,
by differentiation and the aid only of general principles and relations,

-\-

may
If

we

independent relations between the same 2n

we

set

quantities

ij)^

^,

t rf,

(512)

obtain by differentiation and comparison with (501)

dtp^

An

-|-

be obtained.

=.

if'

dt

ds-\-

jx^

d)n\

-\-

pi^ dni,2

+ etc.

(513)

t, s, m\, ni\, etc., is a fundamental

be regarded as entirely equivalent to either of the

equation, therefore, between ^^,

equation, and

is

to

other fundamental equations which have been mentioned.

The reader

will not fail to notice the

analogy between these funda-

mental equations, which relate to surfaces of discontinuity, and those

relating to homogeneous masses, which have been described on pages
140-144.

3 94

Gibbs

J. TF.

On

the

Eqallibrluiu of Heterogeneous Substances.

Experimental Determination of Fundamental Equations for

Surfaces of Discontinuity.

When

all

tinuity are

the substances which are found at a surface of disconcomponents of one or the other of the homogeneous

masses, the potentials Wj,

//g,

ttc, as well as the temperature,

may

The tension o' may

But our measure-

be determined from these homogeneous masses,*

be determined by means of the relation (500).

ments are practically confined to cases in which the difference of the
pressures in the

homogeneous masses

small

is

for
is

become too small

Therefore, although the equation

measurement.

equivalent to an equation between

cases in which
is

it is

may

jt>'

=: ji>" (which

since

2^'

and

p>"

not be exactly satisfied in

convenient to measure the tension, yet this equa-

measurements of tension which

such measurements as simply

so nearly satisfied in all the

we can make,

//j, //g, etc.,

t,

are both functions of these variables)

tion

with increasing

for

differences of pressure the radii of curvature soon

we must regard

that

establishing the values of

for values of

o"

etc.,

/.i^, /.(2,

t,

which

satisfy

the equation // =z p", but not as sufficient to establish the rate of

change

in the value of

for variations of

inconsistent with the equation

To show

this

more

/>'

t^

//,, /z,, etc.,

which are

=:^>".

distinctly, let

t,

m^,

//g,

etc.

remain constant,

then by (508) and (98)

= [\
dp = Yi' d^i^,
dp" = y,"diA

da

;// and ;//

denotmg the
f?y

r,

and
But by

ni'

densities

-dp"

r?(;y

d/^i^,

Wi,"

^
and

__

Hence,

(;/,'- y^")dp^,

~ p") =

(;//'_;/,') da.

(50()

(c, -f ('2)

da + a

d{c^

+ C2)

= (Hp'-

j>").

Therefore,

l\
or

{c,

Ir/'

C2) dff

r/

+
^1

r, a d{c,
(i

^2)1

C2)

= ir,"

^^=

^\ ^4^1

;/,') dff,

Cg).

* It is here supposed that the thermodynamic properties of the liomogcneous

masses liave already been investigated, and that the fundamental equations of these

masses may be regarded as known.

W. Gihbs

J.

Now
Y

i"

To

[\

(Cj

y i'.

Equilibrium of Heterogeneous Substances.

generally be

will

c^)

integrate this equation,

compared with

very small

Neglecting the former term,

395

we have

we may regard F^,

;/,',

^"

as constant.

This will give, as an approximate value,

a'

denoting the value of a when the surface

From

plane.

is

this

it

appears that when the radii of curvature have any sensible magnitude, the value of

will V)e sensibly the

o'

plane and the temperature and

all

same

as

when

the surface

is

the potentials excejjt one have

the same values, unless the component for which the potential has

not the same value has very nearly the same

densitj'^ in

the

two

homogeneous masses,

in

which case, the condition under which the

variations take place

is

nearly equivalent to the condition that the

pressures shall remain equal.

Accordingly,
cial density

we cannot

l\ from

its

in

general expect to determine the superfi-

value

(^

by measurements of super-

\dj.ii/t,fi
ficial

with

The

tensions.
//s,

The

case will be the

same with

I\,,

F^,

etc.,

and also

the superticial density of entropy.

quantities

fg,

to admit of direct

however,

is

%, T\, /'a, etc. are evidently too small in general

measurement. When one of the components,

found only at the

sui-face

of discontinuity,

it

may

be

more easy to measure its superticial density than its potential. But
except in this case, which is of secondary interest, it will generally
be easy to determine

ff

in

terms of

t,

//j,

/.i,

accuracy for plane surfaces, and extremely

etc.,

with considerable
impossible to

difficult or

determine the fundamental equation more completely.

Fundamental Equations for Plane Surfaces of Discontinuity.

An

equation giving a

in

terms of

<,

/<i, yWgi

^^c, which will hold

true only so long as the surface of discontinuity

is

plane,

may be

called a fundamental equation for a plane surface of discontinuity.

It will

be interesting to see precisely what results can be obtained from

such an equation, especially with respect to the energy and entropy

* The suffixed

ft

ia

used to denote that

all

the poteutials except that occurring in

the denominator of the differential coefficient are to be regarded as constant.

and

W. Gibhs

J.

39(3

of TIeterogentous Substances.

JEqidllbrititn

quantities of the conn)oneiit substances in the vicinity of the

tlie

siu'face of discontinuity.

These

in a more simple form, if we deviate

method which we have been following.

be exliibited

results can

to a certain extent from the

The

position

particular

ado])ted

for

term i

C'j-j-

Cg)

of the surface

ing surface
is

(^

(c^

(which

dividing surface

the

determines the superficial densities) was chosen in order to

make

the

But when the curvature

Cg) in (494) vanish.

not supposed to vary, such a position of the divid-

is

not necessary for the simjilification of the formula.

is

It

evident that equation (501) will hold true for plane surfaces (sup-

posed to remain such) without reference to the position of the dividing surfaces, except that

We

tinuity.

the dividing surface as

None

it

be parallel to the surface of discon-

shall

are therefore at liberty to choose such a position for

may

any purpose be convenient.

for

of the equations (502)-(513), which are either derived from

(501), or serve to define

new symbols,

will

be affected by such a

But the expressions

and y^^, will of course

change in the position of the dividing surface.

^, if,

have

m\, m\,

etc.,

as also

when

different values

The quantity

fg, ?/s,

F^, F^,

however, which we

o",

we

tions (501), or, if

etc.

the position of that surface

by

choose,

may

is

changed.

regard as defined by equa-

(502) or (507), will not be affected in

For if the dividing surface be moved a

distance A measured normally and toward the side to which v" relates,
value by such a change.

the quantities
Vsj

^s?

^15

will evidently receive the respective

A(fv"-fv'),
fv', fv", 'A'',

(//v"

//v'),

^25

etc.,

increments

A(ri"-ri'),

^{y/-y2),

denoting the densities of energy and entropy

i]\"

Hence, by equation (507),

two homogeneous masses.

o"

etc.,

in the

will receive

the increment

A(f/-fv')_a(//v" //v')-/'i^(/i" ri')-/^2'^(r3"-r2')-etc.

But by

(93)

p"

6v"

p'

Therefore, since

The value

of

ing surface,

o'

jt>'

is

when

ey

vv" -- /'i ri"

t //v'

/'i

ri'

=i^", the increment

- /'2 r-z" - etc.,

- /'s V-2 - etc.
in

the value of

o'

is

zero.

therefore independent of the position of the divid-

But when we call this quanwe must remember that it will not have

this surface is plane.

tity the superficial tension,

W. Gibhs

J.

its

Equilihrmrn of Hetefogeneous

properties as a tension with reference to any arbi-

chai'acteristic

trary surface.

C/Onsidered as a tension,

position

its

which we have called the surface of tension, and,

nowhere

we
to

The

else.

in the surface

is

strictly speaking,

positioire of the dividing surface,

however, wliich

vary from the surface of tension

shall consider, will not

make

397

S?d>sfa>ices.

sufficiently

any practical importance.

this distinction of

generally possible to place the dividing surface so that

It is

tlie

any desired component in the vicinity of the surface

of discontinuity shall be the same as if the density of that component
were uniform on each side quite xip to the dividing surface. In other
total quantity of

may

make any one of

The only exception is with
regard to a component which has the same density in the two homogeneous masses. With regard to a component which has very nearly
the same density in the two masses such a location of the dividingwords, Ave

place the dividing surface so as to

the quantities /\, 7^2

vanish.

etc.,

might be objectionable, as the dividing surface might

surface

coincide sensibly with the physical siu-face of discontinuity.

suppose that ;//

fail

to

Let us

not equal (nor very nearly equal) to y^'\ and that

is

the dividing surface

so placed as to

is

make F^

Then equation

0.

(508) reduces to
dff

where the symbols

//scd? ^"y(i)i etc.,

to denote the values of

second

etc.,

^o,

?/si

1\

face placed so that

tials in the

- Ad) <^M2 -

//s( I) (?

etc.,

(514)

are used for greater distinctness

as determined

Now we may

0.

member

Tsd) f^/<3

by

consider

a dividing surall

the differen-

of this equation as independent, without

violating the condition that the surface shall remain plane,

dp' =. dp".

given by equation

(98).

e.,

that

Moreover, as has already been observed,

when the fundamental equations

known, the equation
t,

i.

This appears at once from the values of dj/ and dp"

yUj, yWgi etc.

/)'

of the

two homogeneous masses are

Hence, when the value of

surfaces in terms of

^,

between the quantities

=ji>" affords a relation

//j,

/.I2,

etc.,

we can

ff

is

known

also

eliminate

yUj

for plane

from this ex-

by means of the relation derived from the equality of presand obtain the value of a for plane surfiices in terms of
From this, by differentiation, we may obtain directly
//3, etc.

pression
sures,
t,

yUg,

the values of

would

l)e

Acd? Ad)?

p\ p>" and
difficulties, we can

elimination oi
braic

?^s(i)

etc., in

terms of

t,

/n.^,

from the corres])onding

/^j

in

from the
all

finite

But,

if

the

equations jiresents alge-

dp\
and thus

cases easily eliminate

differential

This

//g, etc.

a convenient form of the fundamental equation.

e([uations

dp/',

d^.

ol)tain

398

W. Gibhs

J.

Equilibrium of Heterogeneous Substances.

from whicli the values of

differential equation
etc. in

terms of

may

/^o, etc.,

t, f4
^,

^'2(1)5

?/s(i)>

^3(1)5

be at once obtained by comparison

with (514).*
* If liquid mercury meets the mixed vapors of water and mercury in a plane surface,

and we use

tively,

//,

and

/i.^

to denote the potentials of

and place the dividing surface so that F, =0,

i.

mercury and water respec-

so that the total quantity of

e.,

mercury is the same as if the liquid mercury reached this surface on one side and the
mercury vapor on the other without change of density on either side, then r2(i) will
represent the amount of water in the vicinity of this surface, per unit of surface,
above that which there would be, if the water-vapor just reached the surface without
change of density, and this quantity (which we may call the quantity of water condensed upon the surface of the mercury) will be determined by the equation

da

^2(1)=-^(In this differential coefficient as well as the following, the temperature is

remain constant and the surface of discontinuity plane.

to

dition

may

be regarded as

If the pressure in the

we

shall

fulfilled in

the case of any ordinary curvatures.)

mixed vapors conforms

to the

law of Daiton

(see pp. 215, 218),

have for constant temperature

dp-2

where

supposed

Practically, the latter con-

2^-2

= 72

df^'i,

denotes the part of the pressure in the vapor due to the water-vapor, and

yj the density of the water-vapor.

Hence we obtain
da

For temperatures below 100 centigrade, this will certainly be accurate, since the presmay be neglected.

sure due to the vapor of mercury

The value of a forp-^^O and the temperature of 20 centigrade must be nearly the
same as the superficial tension of mercury in contact with air, or 55. CS grammes per
The value of a at the
linear metre according to Quincke (Pogg. Ann., Bd. 139, p. 27).
same temperature, when the condensed water begins
in

mass, will be equal to the

sum

with water and of water in contact with

the same authority, 42.58

+ 8.25,

to

have the properties of water

of the superficial tensions of

or 50.8.{

its

own

vapor.

grammes per

mercury

in contact

This will be, according to

metre,

if

we

neglect the differ-

As p.^, therefore,
grammes per square metre (when water begins to be
a diminishes from about 55.03 to about 50.83 grammes per linear

ence of the tensions of water with

its

vapor and water with

air.

increases from zero to 236400

condensed in mass),
metre.

If the general course of the values of a for intermediate values of 2^2

were

determined by experiment, we could easily form an approximate estimate of the

values of the superficial density Fgd) for different pressures less than that of saturated vapor.

It

will be observed that the determination of the superficial density

does not by any means depend upon inappreciable differences of superficial tension.
The greatest difficulty in the determination would doubtless be that of distinguishing

between the diminution of superficial tension due

substances which might accidentally be present.
sideraVile practical

to the

water and that due to other

Such determinations are of con-

importance on account of the use of mercury in measurements of

the specific gravity of vapors.

J.

Eqidlihrimn of Heterogeneous Substances.

W. Gibhs

The same physical

may

relations

;J99

of course be deduced Avithout

giving up the use of the surface of tension as a dividing surface, hut

them

the formulae which express

will be less simple.

If

we make

constant, we have by (98) and (508)

/<3, /<4, etc.

dp'

= y^'

df.1^

dp"

=y^"

di^t^

4- y^"

da

I\

=.

where we may suppose l\ and

{,'

/"g

Tlien,

to the surface of tension.

-yr")<h',

d/.t^

if

;/,' f^/'2?
di-t^,

1\

f^yUg?

to be determined with reference

dp =:dpj\

-r,")<^M2

{y2

^.

and

da
That

= r, -,

~,, du^

I\ du.

is,

vhh/
2/ i'J-i'
P'
The reader

,<,/;), /4, etc.

will observe that

7-Yi

j.

Yi

represents the

Yi

distance

be-

tween the surface of tension and that dividing surface whicli would
make T^j zz
the second number of the last equation is therefore
;

equivalent to

j'^^d)-

any component substance has the same density in the two homogeneous masses separated by a plane surface of discontinuity, the
value of the superficial density for that component is inde})endent
If

of

the position of the dividing surface.

derive the value of the

superficial

In this case alone

we may

density of a component with

reference to the surface of tension from the fundamental equation for

Thus

plane surfaces alone.

second

member

in tlie last equation,

will reduce to

/"g-

make jo' ji^", /^3, /<^, etc. constant

making t, /<j, /.<3, /.(^, etc. constant.
i(,

Substantially the same

is

is

when

y^' =z y^', the

will be observed that to

It

in this case

equivalent to

true of the superficial density of entro})y

or of energy, wlien either of these has the

same density

in the

two

homogeneous masses.*
* With respect to questions which concern only the form of surfaces of discontinuity,

such precision as
is

we have employed

evidently quite unnecessary.

in

regard to the position of the dividing surface

This precision has not been used for the sake of the

mechanical part of the problem, which does not require the surface to be defined

with greater nicety than

we

Trans. Conn. Acad., Vol.

can employ in our observations, but in order to give

III.

51

July, 1877.

400

W. Gibhs

J.

Concendng

We

Kqii'dibrlum of Heterogeneous

Suhstcmces.

of Surfaces of Discontinuity.

the Stability

shall first consider the stability of a film separating

neous masses with respect to changes

in its nature,

will be convenient

it

to

its

homogeposition

For this
suppose that the homogeneous

and the nature of the homogeneous masses are not

purpose,

while

altered.

masses are very large, and thoroughly stable with respect to the
possible formation of any different homogeneous masses out of their

components, and that the surface of discontinuity

plane and

is

uniform.

Let us distinguish the quantities which relate to the actual components of one or both of the homogeneous masses by the suffixes

and those which

components which are found only

suffixes ,,,;,, etc., and consider
the variation of the energy of the whole system in consequence of a
given change in the nature of a small part of the surface of discontinuity, while the entropy of the whole system and the total quantities of the several components remain constant, as well as the
volume of each of the homogeneous masses, as determined by the
, J, etc.,

relate to

by the

at the surface of discontinuity

This small part of the surface of discontinviity in

surface of tension.
its

as

changed

may

state

subsist

is

in

supposed to be

still

uniform

between the

equilibrium

and such
homogeneous

in nature,

given

masses, which will evidently not be sensibly altered in nature or ther-

modynamic

state.

The remainder

also supposed to remain uniform,

of the surface of discontinuity

and on accoxmt of

its infinitely

is

greater

be infinitely less altered in its nature than the first part. Let
As^ denote the increment of the superficial energy of this first part,

size to

Arf^

Ami,

^^iif

ftc, Ainfj,

Amf

etc.,

the increments of

its superficial

determinate values to the superficial densities of energy, entropy, and the component
substances,

which

quantities, as

has been seen, play an important part in the relations

between the tension of a surface of discontinuity, and the composition of the masses

which

it

separates.

The product

cr

of the superficial tension

and the area of the surface, may be

regarded as the available energy due to the surface in a system in which the temperature

and the potentials

//,, /i 2, etc.

or

gravitational potential (see page 208)

maintained sensibly constant.

pendent of the precise position

as this

is

the differences of these potentials and the

when

the system

is

subject to gravity

sensibly coincident witii the surface of discontinuity), but es

density of energy^ as the term

entropy and of

tlie

dividing surface.

is

are

The value of a, as well as that of s, is sensibly indewhich we may assign to the dividing surface (so long
used

in

this paper,

lilce

the suiwrficial

the superficial densities of

component substances, requires a more precise

localization of the

W. Gihbs

J.

Equilibrium of Heterogeneous

401

jSub.stances.

entropy and of the quantities of the components which we regard

The increments of entropy and of the
as beh)nging- to the surface.
various components which tlie rest of the system receive will be
expressed

by

^ /Itf,

-^nr:,

-Anvi,,

Jw.!;

etc.,

and the consequent increment of energy

tAif"

Hence the

//

Anil

//,,

Jnv),

total increment of

At^

Aif

energy

value of this ex])ression

changes as well as infinitesimal

which Aa^,

to

etc.

relate,* the

Ani\

Anv},

/<!,

its

and the film

ii/,Ani.l

De^,

JJif^,

Dntl,

Anif,

etc.

(516)

etc.

positive,

the nature of the

|iart

for

finite

of the film

increment of energy of the whole

will be stable, at least

nature, as distinguished from

f-i,,

etc.

system will be positive for any possible changes

film,

necessarily

is

in

etc.,

the whole system will be

in

Ami
// Anr; ^

//,,

^'*

be by (12) and (501)

will

etc.

ii

If the

its })ositi()n.

Bin^,,

in the

nature of the

with respect to changes in

i>m^

etc.,

we

write

Bn^,

etc.

For,
,

if

any element of the surface of discontinuity, we

have from the supposition just made
for the energy, etc. of

ABe^ -

ADif

-//

A Due: -

//,,

,j,

AJJnil

ADmf,

;/;,

etc.

ADmf

etc.

>

(51V)

and integrating for the whole surface, since

AflJm':,

0,

A/Dmt=0,

etc.,

we have
z//7>6^

- A/Bift

//

A/Ihn^,

/,,

A/Bml -

etc.

>

0.

(518)

Now AfDif is the inci-ement of the entropy of the whole siirface,

and A f Dff is therefore the increment of the entropy of the two
homogeneous masses. Tn like manner, AfDm\^ AfDrnl, etc.
are the increments of the quantities of the components in these masses.

The expression

- AfDif t

//

AfBml -

;/

AfBml -

* In the case of infinitesimal changes in the nature of the

film,

etc.

the sign

A must be

interpreted, as elsewhere in this paper, without neglect of infinitesimals of the higher

orders.
zero.

Otherwise, by equation (501), the above expression would have the value

402

Gihhs

J. TT^

Equilibrium of Heterogeneous Snhstances.

denotes tlierefore, according to equation (12), tlie increment of energy

tlie two homogeneous masses, and since A/De'^ denotes the

of

increment of energy of the surface, the above condition expresses

that the increment of the total energy of tlie system is positive.

That we have only considei-ed the possible formation of such tilms as

are caj^able of existing in equilibrium between the given homogeneous
masses can not invalidate the conclusion

in

regard to the stability of

the film, for in considering whether any state of the system will have
less

energy than the given

which

least energy,

state,

we need only

consider the state of

necessarily one of equilibrium.

is

If the expression (51G)

is

capable of a negative value for an

infini-

tesimal change in the nature of the part of the film to which the

symbols

the film

relate,

obviously unstable.

is

If the expression is capable of a negative value,

and not

for infinitesimal changes in

the film

film,

made

in

is

finite

practically unstable*

e.,

i,

if

such a change were

small part of the film, the disturbance would tend to

But

increase.

but only for

the nature of this part of the

might be necessary that the initial disturbance

finite magnitude in respect to the extent of

it

should also have a

surface in wliich

dynamic

it

occurs

for

we cannot

siippose that the thermo-

relations of an infinitesimal part of a surface of discontinuity

are independent of the adjacent

On

parts.

the other hand, the

changes which we have been considering are such that every part
remains

of the film

on each side

and

if

in

equilibrium with the homogeneous masses

a finite change satisfying this condition,

of diminution

same

by an

in

may

perhaps be capable

change which does not satisfy the

must therefore leave it undetermined whether

the film, which in this case

unstable

it

infinitesimal

We

condition.

by

the energy of the system can be diminished

is

practically unstable,

is

or

is

not

the strict mathematical sense of the term.

Let us consider more particularly the condition of practical

stabil-

which we need not distinguish between finite and infinitesimal

changes. To determine whether the expression (516) is capable of a
ity, in

negative value,
capable.

we need only

Let us write

it

/.;

consider the least value of which

in the fuller

(mf - mf

it

is

form

,il

{mr - mT] -

etc.,

^^^^

where the single and double accents distinguish the quantities which
*

With respect

to the sense in wliich this

term

is

used,

compare page 133.

W. Gibhs

J.

EquilihrmTn of Heterogeneous Substances.

and second states of the

relate to the first

film,

403

the letters without

accents denoting those quantities which have the same value in both

The

states.

when

differential of this expression

the quantities distin

guished by double accents are alone considered variable, and the area
of the surface

constant, will reduce

is

(//;- ;<) <ln^"

To make

(//r

(501) to the form

dmr + etc.

i.i;)

this incapable of a negative value,

//''zr:yu',

unless

mf

=:

unless

wif"

/j"

//;' ,

In virtue of these relations and

(519),

i.

which

will

e.,

we must have
=1

0,

by equation

0.

(502), the expression

(516), will reduce to

(}"s-

ff's,

be positive or negative according as

a"

is

by

g'

(520)

positive or negative.

That is, if the tension of the film is less than that of any other film
which can exist between the same homogeneous masses (which has
therefore the same values of t, yu yu^ etc.), and which moreover has
etc., so far as it contains the
the same values of the potentials jj^
substances to which these relate, then tlie first film will be stable.
But the film will be practically unstable, if any other such film has a
[Comj^are the expression (141), by which the practical
less tension.
stability of homogeneous masses is tested.]
,

It is,

/j,, ,

however, evidently necessary for the stability of the surface

of discontinuity with respect to deformation, that the value of the

superficial tension should

be positive.

Moreover, since

we have by

(502) for the surface of discontinuity

and by

(93) for the

s'

e"

if

two homogeneous masses

+ pv' -^ mj
- if + p v" /A nij'

/J

7/'

//,,

/J

etc. = 0,

m/'
I,

m,"

etc.

=.

0,

we denote by
f,

?/,

V,

m,

m^,

etc.,

m,

m,,,

etc.,

etc. of a composite mass consisting of two such

homogeneous masses divided by such a surface of discontinuity we
shall have by addition of these equations

the total energy,

404
s

Now
this

W. Gihhs

J.

1 1/ -\-

pv

Equilihrmin of Heterogeneons Substances.

the value of

if

equation

//

is

/<,,

etc.

/j

>//,,

jj,,

etc.

mi

negative, the value of the

=:

<J s.

member

first

may

as s increases, and

decrease

will

7n,,

of

therefore be

decreased by making the mass to consist of thin alternate strata of

the

two kinds

There

will

homogeneous masses which we are considering.

of

be no limit to the decrease which

given value of

long as the equation

v, so

thus possible with a

is

applicable,

is

i.

e.,

so long

have the properties of similar bodies in mass. But it

may easily be shown (as in a similar case on pages 131, 132) that
as the strata

when the values

of

i,

Ma,

P,

/'/,,

etc.,

by the

are regarded as fixed, being determined

tinuity

ill

7/,

?',

the

first

r/i/,,

1)1^,,

may

are variable and

volume

surface of discon-

and the values of

question,
f,

etc.

//,,

//,

etc.,

?^,

?/,

etc.

be determined by any body having the given

member

of this equation cannot have an infinite

negative value, and must therefore have a least possible value, which
will

be negative,

if

any value

The body determining

f,

is

?/,

negative, that
etc.

which

if o" is

is,

negative.

will give this

least value

With

to this expression will evidently be sensibly homogeneous.

respect to the formation of such a body, the system consisting of the

two homogeneous masses and the surface of discontinuity with the

negative tension is by (53) (see also page 133) at least practically
unstable,

if

the surface of discontinuity

very large, so that

is

it

can

afford the requisite material without sensible alteration of the values

of the potentials.

(This limitation disappears,

if all

substances are found in the homogeneous masses.)

system satisfying the conditions of practical

the possible formation of

all

the component
Therefore, in a

stability with respect to

kinds of homogeneous masses, negative

tensions of the surfaces of discontinuity are necessarily exchided.

Let us now consider the condition which we obtain by applying

(516) to infinitesimal changes.

The expression may be expanded as

by equation (502) to the

before to the form (519), and then reduced

form
s{G"

a')

That the value of

ties are

+ if {m/ - ///) + if-h" -

/'//)

this expression shall be positive

determined by two films which

differ

etc.

when the

quanti-

infinitely little

is

necessary condition of the stability of the film to which the single

W. Gihbs

J.

Eqidlihrmrn of Heteroyaneous Substances.

405

But if one film is stable, the other will in general be

and the distinction between the films with respect to stability
If all films for all
of importance only at the limits of stability.

accents relate.
so too,
is

values of

ja^^

jj,,,

etc. are stable, or all

within certain limits,

that the value of the expression must be positive

are determined

same

limits.

condition

may

when

it is

evident

the quantities

by any two infinitesimally difierent films within the

For such collective determinations of stability the

be written

sJff-^mfj

Aj.iy

nt^,zij.i,^

etc.

etc.

0,

or
z/ (7

On

< r; J
j.i,j

r,,

jj,,

(521)

comparison of this formula with (508), it apj)ears that witliin the

and higher difierential coeflicients of the

limits of stability the second

tension considered as a function of the potentials for the substances

which are found only at the surface of discontinuity (the potentials

for the substances found in the homogeneous masses and the temperature being regarded as constant) satisfy the conditions which would

make
the

is

the tension a

maximum

if

first difierential coefiicients

the necessary conditions relative to

were

fulfilled.

In the foregoing discussion of stability, the surface of discontinuity

supposed plane. In this case, as the tension is supposed })Ositive,

there can be no tendency to a change of form of the surface.

We

now

pass to the consideration of changes consisting in or connected

with motion and change of form of the surface of tension, which we
shall

at first suppose

to be

and to remain

sj)herica]

and uniform

throughout.
In order that the equilibrium of a spherical mass entirely surrounded by an indefinitely large mass of different nature shall be
neutral with respect to changes in the value of r, the radius of the
sphere,

may

it

is

evidently necessary that equation (500), which in this

be written

2G=r{2^'.-p"\

(522)

as well as the other conditions of equilibrium, shall continue to hold

true for varying values of r.
Hence, for a state of equilibrium which
is

on the limit between stability and

instability,

it is

necessary that

the equation

2do-={p' -p")dr
be

when

rdp'

the relations between da., dp\ and dr are

determined from the fundamental equations on the sup])osition that

shall

satisfied,

406

J.

TK Glbbs

Equilibrlmn of Heterdgeneoiis Siihstances.

the conditions of equililnium relating to temperature and the potentials

remain

satistied.

(The

ditferential coefficients in the equations

which follow are to be determined on this supposition.)

i.

e.,

if

Moreover,

if

the pressure of the interior mass increases less rapidly (or

decreases more rapidly) with increasing radius than

preserve neutral equilibrium, the equilibrium

'%>'%
the equilibrium

ijs

is

dp

necessary to

But

if

-"'^^'^

In the i-emaining case,

unstable.

is

stable.

do'

<^^*)

when
,

farther conditions are of course necessary to determine absolutely

whether the equilibrium

stable or unstable, but in general the

is

equilibrium will be stable in respect to change in one direction and

unstable in respect to change in the opposite direction, and
fore to be considered unstable.

In general, therefore,

is

there-

we may

call

(523) the condition of stability.

When the interior mass and the surface of discontinuity are formed
entirely of substances

which are components of the external mass, p'

and a cannot vary and condition (524) being satisfied the equilibrium is unstable.
But if either the interior homogeneous mass or the surface of discontinuity contains substances which are not components of the
enveloping mass, the equilibrium may be stable. If there is but one
such substance, and we denote its densities and potential by y\^ 7",,

and

or,

yUj,

by

the condition of stability (523) will reduce to the form

(98)

and

(508),

(r;//

r,)'^-'

</'-/.

(526)

In these equations and in all which follow in the discussion of this

case, the temperature and the potentials //g, /'s, etc. are to be

regarded as constant.

But

W. Glhhs

J.

Equilihrium of Heterogeneous Substances.

which represents the total quantity of the component

suffix, must be constant.
It is evidently equal to
I nr^

Dividing by

4;r

and

y ^'

we obtain

dr-\-i

(.,V

By means

dy ^

r^

y^' and P^ are functions of

or, since

by the

4 7tr~ r^.

diiFerentiating,

(r2 y^' -f 2 r /',)

specified

407

r^

dl\

0,

//,,

dl\
V2r?;//
+ 2r,,*+(^|^ + ,.|-.).,.=o.

of this equation, the condition of stability

is

(627)

brought to

the form

If

we

eliminate r

by equation

we have

(522),

\P'-P"^ ^)

3 ( jo'

If

/:>'

and

member

ff

are

known

in

jt>") fZ//

terms of

"*"

t,

//j

>i

o- djJ.

yUg? ^^.c,

of this condition in terms of the

.529)

we may express

same variables and

the

p".

first

This

any given state of the external mass,

which will make the equilibrium stable or unstable.
the component to which y^' and F^ relate is found only at the

will enable us to determine, for

the values of
If

//,

surface of discontinuity, the condition of stability reduces to

y

'

-^
Smce

we may

(I If

dT,

>
5

(^^^)

2-

also write

r.

dff

d log

o"

'

Again,

if

("'')
Vdr<--2'
m-o^r<-2and - = 0, the condition of stability reduces to
r'j =
*

3 y,'^

y'

Since

du,

= ^,
djji^

we may

also write

_y,'_d

^gjy_y')

p'-p" dy"^^?,'
Trans. Conn. Acad., Vol.

III.

d\ogy^
52

^3

^^'^'^^

Nov., 1877.

408

W. Gibbs

J.

When

is

Equilihrmm, of Heterogeneous Substances.

large, this will be a close

approximation for any values of

The two

very small.

special conditions (531) and

might be derived from very elementary considerations.
Similar conditions of stability may be found when there are more
substances than one in the inner mass or the surface of discontinIn this case,
uity, which are not components of the enveloping mass.
we have instead of (526) a condition of the form

Fj, unless

;Ki' is

(533)

r/

(*

+ 2 I\

from which -

1^'

-y-^, etc.

',

r, '+27

(r

may

,) '^^

etc.

<y' - p\

(534)

be eliminated by means of equations

derived from the conditions that

;//?;'

must be

1\

Nearly the same method

Two

ra' ^'

s,

+ ^2

etc.

^S

constant.

different

ing a circular

may

homogeneous
orifice, their

be applied to the following problem.

by

fluids are separated

diaphragm hav-

volumes being invariable except by the

motion of the surface of discontinuity, which adheres to the edge of

the orifice

to

determine the stability or instability of this surface

when in equilibrium.
The condition of stability derived from
written

d(p'

;/)

da

,,.

where the quantities relating to the concave

sion are distinguished by a single accent.
If

both the masses are infinitely large, or

the components of the system

is

(522)

may

in this case

dr

be

/..\

side of the surface of ten-

if

one which contains

infinitely large, p'

jf

and a

all

will

be constant, and the condition reduces to

The

equilibi-ium will therefore be stable or unstable according as the

surface of tension

To

is less

or greater than a hemisphere.

return to the general problem:

if

we denote by x

the part of

the axis of the circular orifice intercepted between the center of the
orifice

by

and the surface of tension, by

the value of

v'

when

the radius of the

the surface of tension

is

have the geometrical relations

and

v'

= V' + i7rr- x iTt E^

zV+ r x^ \
71

{r

7t x"^.

x)

and

orifice,

plane,

we

shall

W. Gibbs

J.

By

Equilibrium of Heterogeneous Substances.

we

diiierentiation

obtain
(r

and

civ' z=. 71

whence

x)

x^ dr

(r

By means

409

clx
-\-

x) dv'

-\-

xdr

=.

0,

rX

{2 TT

n r x^

x~) dx

dr.

(536)

may be reduced

of this relation, the condition of stability

to the form

2da

dp"

dp'

-J-'-^i-r ZT'
dv <
dv
dv
now suppose

liet us

cept one,

(P

- P)

it

that the tempei'ature and

are to be regarded as constant.

//,,

when one of

the

homogeneous masses

i2-

all

'

the potentials ex-

This will be the case

very large and contains

is

^,

(537)
^

r^ x?

all

components of the system except one, or when both these

masses are very large and there is a single substance at the surface
the

of discontinuity which

not a component of either;

is

the whole system contains but a single component, and

to a constant temperature at its surface.

also
is

when

exposed

Condition (537) will

re-

duce by (98) and (508) to the form

But

y^'v'

(the total quantity of the

constant

y^" v"

I\s

z=z

dv\

and

ds

When

d}.i^

the substance specified by the sufiix

When

be neglected.
,

dy
-=

suffix)

must be

dy
-z

it is

may

brought to the form

d}x^

of the homogeneous masses, the terms

by the

= -2 dv',

this equation, the condition of stability is

dfx^

Ki

specified

therefore, since

dv"

By

component

is

and

component of
s

-j

'

may

either

generally

not a component of either, the terms ;//,

of course be cancelled, but

we must not

apply the formula to cases in which the substance spreads over the
diaphragm separating the homogeneous masses.

410

J.W. Gihhs Equilihrium of Heterogeneous

Substances.

In the cases just discussed, the problem of the stability of certain

surfaces of tension has been solved

equilibrium,

a condition

This method probably leads as directly

tion of the limit of stability.

as

any to the

result,

by considering the case of neutral

of neutral equilibrium aifoi'ding the equa-

when that

consists in the determination of the

value of a certain quantity at the limit of stability, or of the relation

which

require a

Let

between certain quantities specifying the

exists at that limit

But problems

state of the system.

it

system

of a

more general character may

more general treatment.

be required to ascertain the stability or instability of a fluid
given state of equilibrium with respect to motion of the

in a

surfaces of tension

and accompanying changes.

It is

supposed that

the conditions of internal stability for the separate homogeneous

masses are

satisfied, as well

surfaces of discontinuity

as those conditions of stability for the

which relate to small portions of these

surfaces with the adjacent masses.

(The conditions of stability
which are here supposed to be satisfied have been already discussed
in part and will be farther discussed hereafter.)
The fundamental

equations for

all the masses and surfaces occurring in the system are

supposed to be known. In applying the general criteria of stability

which are given on page 110, we encounter the following

The question

of the stability of the system

is

difficulty.

be determined by

to

the consideration of states of the system which are slightly varied

from that of which the stability

is in

question.

These varied states

of the system are not in general states of equilibrium, and the rela-

by the fundamental equations may not hold

More than this, if we attempt to describe a varied

tions expressed

them.

true of
state of

the system by varied values of the quantities which describe the

initial state, if

these varied values are such as are inconsistent with

equilibrium, they

masses are

may

to determine with precision

fail

any

state of

Thus, when the phases of two contiguous homogeneous

the system.

specified, if these phases are such as satisfy all the condi-

tions of equilibrium, the nature of the surface of discontinuity (if with-

out additional components)

do not

is

entirely determined

but

if

the phases

satisfy all the conditions of equilibrium, the nature of the sur-

face of discontinuity

is

not only undetermined, but incapable of deter-

mination by specified values of such quantities as

we have employed

to express the nature of surfaces of discontinuity in equilibrium.

if

different,

we cannot

tinuity

For

the temj)eratu]"es in contiguous homogeneous masses are

example,

by assigning

specify the thermal state of the surface of discon-

to

it

any particular temperature.

It

would be

J.

W. Gihhs

Equilibriuni of Heterogeneous Substances.

41

necessary to give the law by which the temperature passes over from

one value to the other.

use of

it

And

if this

were given, we could make no

in the determination of other quantities, unless

tlie

rate of

change of the temperature were so gradual, that at every point we

could regard the thermodynamic state as unaffected by the change
of temperature in

It is true that

its vicinity.

we

are also ignorant in

equilibrium of the law of

respect to surfaces of discontinuity

in

change of those quantities which are

different in the

two phases

in

contact, such as the densities of the components, but this, although

unknown

to us,

is

entirely determined

contact, so that no vagueness

the quantities which

by

the nature of the phases in

occasioned in the definition of any of

is

we have occasion

with reference to such

to use

surfaces of discontinuity.

may be

It

obsei'ved that

we have

e(piations, especially (497), in

sarily one of equilibrium.

established certain differential

which only

Such equations

initial

tlie

state

may be regarded

lishing certain properties of states bordering

as estab-

upon those of equilib-

JUit these are properties wdiich hold true only

rium.

neces-

is

when we

dis-

regard quantities })roportio)ial to the square of those which express

the degree of variation of the system from equilibrium.

Such equa-

tions are therefore sufficient for the determination of the conditions of

equilibrium, but not sufficient for the determination of the conditions

of stability

We

may, however, use the following method

to decide the question

of stability in such a case as has been described.

Beside the real system of which the stability

is

in question,

it

be convenient to conceive of another system, to which we shall

bute

in its initial state the

will

attri-

same homogeneous masses and surfaces of

discontinuity which belong to the real system.

We

shall also sup-

pose that the homogeneous masses and surfaces of discontinuity of

this system,

which we may

call the

imaginary system, have the same

fundamental equations as those of the

ary system

is

to differ

from the

real system.

But the imagin-

real in that the variations of its state

are limited to such as do not violate the conditions of equilibrium

relating to temperature and the potentials,

and that the fundamental

equations of the sui^faces of discontinuity hold true for these varied

states,

(500)

although the condition of equilibrium expressed by equation

may

not be satisfied.

we must decide whether we are to

examine the question of stability under the condition of a constant
Before proceeding farther,

external temperature, or under the condition of no transmission of

412

<J.

'tV.

Glhhs

Equllibriuni of Heterogeneous Stihstances.

heat to or from external bodies, and in general, to what external

we

are to regard the system as subject.

be conand that
neither matter nor heat can be transmitted through it.
Other cases
may easily be reduced to this, or treated in a manner entirely
inflnences

venient to suppose that the exterior of the system

It will

is

fixed,

analogous.

Now if the real system in the given state is unstable, there must be
some slightly varied state in which the energy is less, but the entropy
and the quantities of the components the same as in the given state,
and the exterior of the system unvaried. But it may easily be shown
that the given state of the system may be made stable by constraining the surfaces of discontinuity to pass through certain fixed lines
situated in the unvaried surfaces.

Hence,

if

the surfaces of discon-

tinuity are constrained to pass through corresponding fixed lines in

the surfaces of discontinuity belonging to the vai'ied state just mentioned, there

must be a

state

of stable equilibrium for the system

thus constrained which will differ infinitely

of the system, the stability of which

is in

little

from the given state

question, and will have the

same entropy, quantities of components and exterior, but less energy.

The imaginary system will have a similar state, since the real and
imaginary systems do not difter in respect to those states which
satisfy all the conditions of equilibrium for each surface of discontin-

That is, the imaginary system has a state, differing infinitely

from the given state, and with the same entropy, quantities of
components, and exterior, but with less energy.
Conversely, if the imaginary system has such a state as that just
This may be
described, the real system will also have such a state.
uity.

little

shown by

fixing certain lines in the surfaces of discontinuity of the

imaginary system

in its state of less

energy and then making the

energy a minimum under the conditions.

The

state thus determined

will satisfy all the conditions of equilibrium for each

surface of dis-

continuity, and the real system will therefore have a corresponding

which the entropy, quantities of components, and exterior

same as in the given state, but the energy less.
may therefore determine whether the given system is or is not

state, in

will be the

We

unstable,

by applying the general

criterion of instability (7)

to the

imaginary system.
If the
stable.

system

is

not unstable, the equilibrium

is

either neutral or

Of course we can determine which of these

refei'ence to the

imaginary system, since

upon states of equilibrium,

in

is

the case

this determination

by

depends

regard to which the real and imaginary

J.

W. Gihhs

systems do not

Equilibrhim. of Ileterogeneo^is Suhstances.

We

diifer.

may

equilibrium of the given system

applying the criteria

The

result Avhich

(3)-(7) to the

413

therefore determine wliether the

is

stable, neutral, or unstable,

by

imaginary system.

we have obtained may be expressed

In applying to a fluid system which

is

in

as follows:

equilibrium, and of which

the small parts taken separately are stable, the criteria of stable,

all

neutral,

and unstable equilibrium, we may regard the system as

under constraint to satisfy the conditions of equilibrium relating to

temperature and the potentials, and as satisfying the relations expressed by the fundamental equations for masses and surfaces, even

when the
(500)]
It

is

condition of equilibrium relating

to

pressui'e

[equation

not satisfied.

follows immediately from this principle, in connection with equa-

and (86), that in a stable system each surface of tension'

must be a surface of minimum area for constant values of the volumes
which it divides, when the other surfaces bounding these volumes

tions (501)

and the perimeter of the surface of tension are regarded as fixed

that in a system in neutral equilibrium each surface of tension will

have as small an area as it can receive by any slight variations under

the same limitations and that in seeking the remaining conditions of
;

when these are satisfied, it is only

necessary to consider such varied surfaces of tension as have similar
stable or neutral equilibrium,

properties with reference to the varied volumes and perimeters.

We may illustrate

the method which has been desci'ibed by applyproblem but slightly different from one already (pp. 408,
409) discussed by a different method. It is required to determine the
conditions of stability for a system in equilibrium, consisting of two
diiferent homogeneous masses meeting at a surface of discontinuity,
the perimeter of which is invariable, as well as the exterior of the
whole system, which is also impermeable to heat.

ing

it

to a

To determine what
minimum

condition of

is-

necessary for stability in addition to the

we need only
consider those varied surfaces of tension which satisfy the same condition.
may therefore regard the surface of tension as deterarea for the surface of tension,

We

mined by

the volume of one of the homogeneous masses.

But the
would evidently be completely determined by the
position of the surface of tension and the temperature and potentials,
if the entropy and the quantities of the components were variableand therefore, since the entropy and the quantities of the components
are constant, the state of the system must be completely determined
v',

state of the system

by

the position of the surface of tension.

We may

therefore reo-ard

414
all

J.

W. Gibhs

Equilibrium of Heterogeneous Substances.

the quantities relating to the system as functions of

may be

condition of stability

de

(Z2f

-j-,av 4- -

dv

where

TTo dv
dv^

and the

+ etc. -^
> 0,

'

Now the conditions

denotes the total energy of the system.

v' ,

written

of equilibrium require that

di

Hence, the general condition of stability

is

that
(541)

,,-^.>0.

Now

we

if

write

f", f^

f',

we have by

for the energies of the

two masses and of

and (501), since the total entropy and

the total quantities of the several components are constant,
the surface,

(86)

= de' + dE" + ds^ =

dv" = dv',

d^
or, since

jo'

dv'

ds,

ds
^_

de
_,=
_y+,/ +

p" dv"

(542)

Hence,
d'^e

dv^^

_ _ dp'

and the condition of

If

we now

da

dp"

d^s

ds

~~dv'^d^'^ dv' dv' + ^2'

^'

may

stability

'^)

be written

d^s

dj)'

dp"

da

dv'^

dv'

dv'

dv' dv''

simplify the problem

v-5

ds

by supposing,

as in the similar case

on page 409, that we may disregard the variations of the temperature and of all the potentials except one, the condition will reduce to
d^s ^

The

T^

ds \ du,

Making

this constant,

."

The condition

r.

^y."^"

by the sufRx

is

r\s.

we have

|,)*/+(.

of equilibrium

d^s

<"='

->-+'<??) sf-

total quantity of the substance indicated

y.'v'

(./

''<r.->('''

"^dv'^^

is

g + -|^ +

/^)...=o.,o)

thus reduced to the form

{y^'-^'^"
,dr,'

V -4^ClfX^

+
,

+ ^^%)'

dr/'
V -f-~ -+

dry

ClfX^

-^
(IfX^

^^^'^

W. Gihhs

J.

Eqidlihrivm of Heterogeneous Substances.

415

where ^= and ^ are to be detertnined fioni tlie form of the surface

civ
dv
of tension by purely geometrical considerations, and the other differential coefficients are to be determined from the fundamental equations of the homogeneous masses and the surface of discontinuity.
Condition (540) may be easily deduced from this as a particular case.
The condition of stability with reference to motion of surfaces of
,

discontinuity admits of a very simple expression

the temperature and potentials as constant.

when we can

treat

This will be the case

Avhen one or more of the homogeneous masses, containing together

the component substances,

all

may

be considered as indefinitely large,

the surfaces of discontinuity being

F'or if

finite.

we

write

2 As for

the sum of the variations of the energies of the several liomogeneous

sum

masses, and '2Ae^ for the

of the variations of the energies of the

several surfaces of discontinuity, the condition of stability

may

be

written

2/le

-f-

:^At^

>

(548)

0,

the total entropy and the total quantities of the several components

being constant.

The

but the character

z/ signifies,

pression

is

variations to be considei*ed are infinitesimal,

as elsewhere in this paper, that the ex-

to be interpreted without neglect of infinitesimals of the

Since the temperature and potentials are sensibly con-

higher orders.

stant, the same will be true of the pressures and surface-tensions, and

by

integration of

mass
/ie

and

for

(Sti)

and (501) we may

p -iv +

J/;

-\-

//g -^'i^i

any homogeneous

+ etc.,

any surface of discontinuity

At^

These equations

Ajf

will

(7

As

-{- //j

hold true of

A7n\ -f

//|

Am.^ -f

finite differences,

etc.

when

<,

^, a, //,,

and will therefore hold true of infinitesimal difunder the same limitations, without neglect of the infinitesi-

are constant,

/ig, etc.

ferences,

mals of the higher orders.

By

substitution of these values, the condi-

tion of stability will reduce to the

:^{pAv)
2{2jAv)

or

That

Am

Hi

ol)tain for

is,

the

sum

form

+ 2{(TAs) >
2{(tAs) <

0,
0.

(549)

of the products of the volumes of the masses

by
by the sum of the products of the areas of
of discontinuity by their tensions must be a maximum.

their pressures diminished

the surfaces

This

is

purely geometrical condition, since the pressures and ten-

Trans. Conn. Acad., Vol.

III.

53

Nov., 1877.

416

J.

sioiis

Wl Gihhs Equilibrium' of Heterogeneoiis

This condition

are constant.

sufficient for stability

tinuity.

is

iSubstances.

of interest, because

it is

always

with reference to motion of surfaces of discon-

For any system may be reduced

to the kind described

by

putting certain parts of the system in communication (by means of

line

tubes

if

necessary) with large masses of the proper temperatures

and potentials. This may be done without introducing any new

The condition (549) when
movable surfaces of discontinuity.
applied to the altered system is therefore the same as when applied
But it is sufficient for the stability of the
to the original system.
and therefore sufficient for its stability if we diminish
freedom by breaking the connection between the original system

altered system,
its

and the additional

parts,

and therefore

sufficient for the stability of

the original system.

On

the PosslhlUty

of

the

Formation of a Fluid of

different

Phase

within any Homogeneous Fluid.

The study of

surfaces of discontinuity throws considerable light

upon the subject of the stability of such

homogeneous

fluid

masses

as have a less pressure thau others formed of the same components

(or

some of them) and having the same temperature and the same

potentials for their actual components.*

In considering this subject,

method of treating

we must

first

of all inquire

surfaces of discontinuity

is

how

far

our

applicable to cases in

which the radii of curvature of the surfaces are of insensible magniThat it should not be applied to such cases without limitation
tude.
is evident from the consideration that we have neglected the term
i(Ci C^8{c C2) i" equation (494) on account of the magnitude
^

of the radii of curvature compaied with the thickness of the nonhomogeneous film. (See page 390). When, however, only spherical

masses are considered, this term will always disappear, since Cj and
C2 will necessarily be equal.
Ao^ain, the surfaces of discontinuity have been regarded as separat-

homogeneous masses. But we may easily conceive that a globumass (surrounded by a large homogeneous mass of diflerent
nature) may be so small that no part of it will be homogeneous, and
that even at its center the matter cannot be regarded as having any
ino-

lar

phase of matter in m-ass. This, however, will cause no difficulty, if

reoard the phase of the interior mass as determined by the same

vve

* See page 161, where the term stable

strict

is

used (as indicated on page 159)

sense than in the discussion whicli liere follows.

in a less

J.

W. Gihbs

Equilihriarn of Heterogeneous Substances.

417

mass as in other cases. Beside the pliase of

the exterior mass, there will always be another phase having the
same temj^eratui-e and potentials, but of the general nature of the
small globule which is surrounded by that mass and in equililjrium
relations to the exterior

with

This phase

it.

sidered,

and

completely determined by the system con-

is

and perfectly capable of realizamass could exist in

This is the phase which we are to

in general entirely stable

tion in mass, although not such that the exterior

contact with

it

at a plane surface.

attribute to the mass which

we

conceive as existing within the divid-

ing surface.*

With

this

understanding with regard to the phase of the

interior mass, there will be

no ambiguity

fictitious

the meaning of any of

in

we have employed, when applied to cases in

which the surface of discontinuity is spherical, however small the
radius may be.
Nor will the demonstration of the general theorems
the symbols which

The dividing surface, which

any material modification.
**,
if, in\, m|, etc., is as in other cases to be
placed so as to make the term ^(C^ 4- 6\)^(Cj -f-Cg) in equation (494)
It has been shown
vanish, i. e., so as to make equation (497) valid.
require

determines the value of

on pages 387-389 that when thus placed

it

will sensibly coincide

when this consists of a

separating homogeneous masses, and having

witl^ the physical sui-face of discontiiuiity,

non-homogeneous film
But
of curvature which are large compared with its thickness.
in regard to globular masses too small for this theorem to have any
application, it will be worth while to examine how far we may be
certain that the radius of the dividing surface will have a real and
I'adii

positive value, since

it

only then that our method will have any

is

natural application.

The value of the

of any
fluid

(500)

radius of the dividing surface, supposed spherical,

globule in

may
and

equilibrium with

(502),

surrounding

which have been derived from

the radius implicitly.

may

be most easily obtained by eliminating

If

we

homogeneous

G from equations
(497),

and contain

write r for this radius, equation (500)

be written
2

0'

{p'

-p")r,

(550)

the single and double accents referring respectively to the interior

and exterior masses.

If

we

write

[f],

[//],

[m.^],

[m^],

etc.

for the

* For example, in applying our formulae to a microscopic globule of water in

we should understand, not the

steam, by the density or pressure of the interior mass

actual density or pressure at the center of the globule, but the density of liquid water
(in kirge quantities)

which has

tlie

temperature and potential of the steam.

418

J.

W. Gibhs

Equilibrium of Heterogeneous Substances.

excess of the total energy, entropy, etc. in and about the globuhir

mass above what would be

same space

in the

if it

were uniformly

with matter of the phase of the exterior mass, we shall have

necessarily with reference to the whole dividing surface

filled

,s

^^1

where

^,]

[''^il

' (,^.'

^''

iVi

fy', fy", //y', 7/y",

^ _
"4 = D^s] ,^s

,/),
Yi")^

y y"

y^',

^,

[-,^j

etc.

(,^^/
^''

,^^,.)^

iVi

r/)^

etc.,

denote, in accordance with our

usage elsewhere, the volume-densities of energy, of entropy, and of

the various components, in the two homogeneous masses.

We may

thus obtain from equation (502)

= [e] -

aS

V' (fy'

6y")

t [/;]

V' (//y'

//y")

-^i,[m,'\-\-fi,v'{y,'-y,")-ti2[m^-]+^i.,v'{y.,--y.,")-^^tc.

But by

(551)

(93),

p'

6y'+n/v'+/^l ri'+/'2 7'2'+et<-'.,

p"

Let us also write

W=

^x"+t ;/y"+

//j

/V2

ri"+

^2" +

etc.

for brevity

[f]

t [;/]

[m,]

//,

1.1,

[m.^

etc.

(552)

is entirely determined by
be observed that the value of
and that the notion of
considered,
system
physical
the nature of the

(It will

the dividing surface does not in any

We

shall then

have

a
or, substituting for s

and eliminating

ff

by

and
r^

W+
v'

we

v' ip'

enter into

2)"),

a z=

W+

irrr^

(^V

its definition.)

(553)

their values in terms of

p"),

r,

(554)

(550),

^rrr^

If

way

eliminate r instead

ff,

{jy'

-p")

= W,

(555)

we have

Now, if we first suppose the difference of the pressures in the homogeneous masses to be very small, so that the surface of discontinuity is nearly plane, since without any important loss of generality

Gihhs

J. AV.

Equ'dibruim of Heterogeneous

we may regard a as ])ositive (for if

surface when phine would not be
it

certainly

fulfilled

is,

in

}>'

o',

p\

and r

be positive.

TF. that

when

p'-=.p",

the

regard to position, as

stable in

perimeter), we see by (550) that the presmust be the greater; i. e., we may regard

its

By

as all positive.

But

it is

the value of this quantity

and p'^zp".

(555), the value of

will

evident from equation (552), which defines

case of equilibrium, and can only

infinite

not positive

419

every actual case, when the proper conditions are

with respect to

sure in the interior mass

also

o' is

/Substances.

is

necessarily real, in

become

any possible

when r becomes
as p' p" increases

infinite

Hence, by (556) and (558),

from very small values, W, r, and o' have single, real, and positive
values imtil they simultaneously reach the value zero.
Within this
limit,

our method

such exist,
equaiions.

it

will

is

evidently

applicable

beyond

this

limit,

if

hardly be profitable to seek to interpi-et the

But it must be remembered that the vanishing of the

somewhat arbitrarily determined dioiding surface may

radius of the

not necessarily involve the vanishing of the physical heterogeneity.

however,

(see pp. 387-389,) that the globule must bemagnitude before r can vanish.
It may easily be shown that the quantity denoted by
is the
work which w^ould be required to form (by a reversible process) the
It is evident,

come

insensible in

heterogeneous globule

in

the interior of a very large mass having

uniform phase of the exterior mass.

For

work

is

equal to the increment of energy of the system wlien the globule

is

initially the

this

formed without change of the entropy or volume of the whole system

or of the quantities of the several components.
Now [//], [^/^,], [^ig],
etc.

denote the increments of entropy and of the components in the

is formed.
Hence these quantities witli the

space where the globule

negative sign will be equal to the increments of entropy and of the

components in the rest of the system. And hence, by equation (86),

will denote the increment of energy in

the globule

is

But

formed.

that part of the system.

increment of energy

in

[f]

all

the system except where

denotes the increment of energy in

Therefore, by

(55-2),

W denotes

the total

the circumstances supposed, or the work

re-

quired for the formation of the globule.

The conclusions which may be drawn from

these considerations

with respect to the stability of the homogeneous mass of the pressure p" (supposed less than ^>', the pressure belonging to a difi^erent
phase of the same temperature and

jiotentials)

are very obvious.

420

W.

J.

(iibbs

Within those

Eqxdlihrhmi of Heterogeneous Substances.

limits within

which the method used has been

justified,

the mass in question must be regarded as in strictness stable with

respect to the growth of a globule of the kind considered, since

work required

the

size (viz., that

which would be

equilibrium with the surrounding

in

Nor can

mass), will always be positive.

smaller globules be formed,

ioY they can neither be in equilibrium with the

being too small, nor grow to the

If,

W,

for the formation of such a globule of a certain

surrounding mass,

of that to which

size

relates.

however, by any external agency such a globular mass (of the

necessar)'^ for equililtrium)

size

were formed, the equilibrium has already

(page 406) been shown to be unstable, and with the least excess in
size,

the interior mass would tend to increase without limit except

that depending on the

magnitude of the exterior mass.

therefore regard the quantity

the stability of the phase to which

value of

is

given

in

We may

as affording a kind of measure of

j>"

In equation (557) the

relates.

terms of C and p' p".

If the three

funda-

mental equations which give o', ^j*', and jt>" in terms of the temperature and the potentials were known, we might regard the stability
(

known in terms of the same variables.

is infinite.
when p'=zp" the value of

TF) as

that

It will

If p'

be observed

p"

increases

without greater changes of the phases than are necessary for such
will vary at first very nearly inversely as the square of
increase,

p'

p\

p'^p" continues

\i

to increase,

may

it

perhaps occur that

TFreachcs the value zero; but until this occurs the phase is certainly
Another kind
stable with respect to the kind of change considered.
of change

be great

is

conceivable, which initially

is

small in degree but

may

Stability in this respect or stability

in its extent in space.

in respect to continuous changes of phase has already been discussed

These limits depend
(see page 162), and its limits determined.

homogeneous mass of
But with respect to the kind of

entirely upon the fundamental equation of the

stability is in question.

which the

chano-es here considered, which are initially small in extent but great
in

degree,

it

does not appear

how we

can

fix

the limits of stability

with the same precision. But it is safe to say that if there is such a
This
limit it must be at or beyond the limit at which o' vanishes.
equation
of
fundamental
the
by
the
entirely
determined
latter limit is
stability
the
is
of
which
phase
the
between
discontinuity
surface of
is
in
question.
formation
possible
which
the
of
that
in question and

We have

already seen that

ing surface

and the work

when

o'

vanishes, the radius of the divid-

W vanish

homogeneity of the mass vanishes

with

at the

it.

If the fault in

same time,

(it

the

evidently

 Eqidlihrmm, of Heterogeneous Substances.

421

cannot vanish sooner,) the phase becomes unstable at this

limit.

W. Gihbs

J.

But

if

the fault in the homogeneity of the physical mass does not

vanish with

r,

a and W,

and

no

sufficient reason

should not be considered as the general case,

work necessary

of

mal, this

to upset the equilibrium of the phase

this

amount

the

is infinitesi-

make the phase vmstable. It appears

somewhat one-sided measure of stability.

not enough to

is

therefore that TF
It

why

appears

although

is

must be remembered

in this connection that the

fundamental

equation of a surface of discontinuity can hardly be regarded as

capable of experimental determination, except for plane surfaces, (see

l^p.

394, 395,) although the relation for spherical surfaces

is

in the

nature of things entirely determined, at least so far as the phases are

Yet the foregoing discussion yields

It has been shown that the real
genei-al beyond that limit (discussed

separately capable of existence.

the following practical results.

stability of a

phase extends

in

on pages 160, 161), which may be called the limit of practical stability, at which the phase can exist in contact with another at a plane
surface,

and a formula has been deduced to express the degree of

measured by the amount of work necessary

stability in such cases as

to upset the equilibrium of the phase

nitely in space.

It

when supposed

to extend indefi-

has also been shown to be entirely consistent

with the principles established that this stability should have

and the manner

in wdiich the general equations

limits,

would accommodate

themselves to this case has been pointed out.

By

equation (553), which

may

Wz=z

we

see that the

and

positive,

is

work

ffs

be written

- (y - p")

W consists of

v',

(559)

tw^o parts, of

which one

is

always

expressed by the product of the superficial tension

and the area of the surface of tension, and the other is always negative, and is numerically equal to the product of the diiFerence of pres-

by the volume of the interior mass. We may regard the first

work spent in forming the surface of tension,
and the second part the work gained in forming the interior mass.*
sure

part as expressing the

* To make the

two processes

ph}'sical significance of the

to be

performed separately

above more

clear,

in the following

we may suppose the

We may sup-

manner.

pose a large mass of the same phase as that which has the volume
initially in

the interior of the other.

Of course,

it

must be surrounded by

envelop, on account of the difference of the pressures.

this envelop permeable to all the
ties that a

We

like

to exist

a resistino-

may, however, suppose

component substances, although not

mass can form on the exterior

v'

that within.

of such proper-

We may

allow the

422

J. VT. Glbhfi

Equilihrhim of Heterogeneous Substances.

Moreover, the second of these quantities,

always equal to two-thirds of the

and the geometrical relation

On

Formation

the Possible

geneous Fluids meet of

Let A, B, and

We

v'^r^^'s.

W ^as=h^

we

if

neglect

may

- p")

{p'

(560)

v'.

at the Surface ii^here tv}0 different

a.

Fluid of different Phase from

he three

difl:erent fliiid

by a very

when they meet

its

be the same or

and B to be separated

This sheet

principal curvatures

not necessarily

will

must be

We

zero.

treat such a system as consisting simply of masses of the phases

and

with a certain surface of discontinuitj^, for in our previous

discussion there lias been nothing to limit

of the film separating

The value of

of curvature.

be Cac+o'bc,

tlie

thickness or the nature

homogeneous masses, except that

has generally been supposed to be small

will

B may

comjionents except such as belong to

thin sheet of the phase C.

be plane, but the sum of

Homo-

either.

phases of matter, which

and

Let us su])pose masses of the phases

or B.

may

The components of

C must have no

but

diffei'cnt,

is

therefore write

satisfy all the conditions necessary for equilibrium

at plane surfaces.

its sign,

as appears from equation (550)

first,

if wt"

in

its

thickness

comparison with

its radii

the superficial tension for such a fihn

denote by these symbols

tlie

tensions of

tlie

and C, and B and C, respectively.

from
evident
mechanical considerations, but
appears
only
not
This
verified
by
equations
easily
be
also
(502) and (93), the first of
may
surfaces of contact of the phases

which

may

be regarded as defining the quantity

not be affected

envelop to yield to the internal pressure until

materially affecting

This value will

a.

by diminishing the thickness of the

its

the

contents are increased by v' without

its

If this

superficial area.

film, until

be done

sufficiently slowly, the

phase

mass within will remain constant. (See page 139.) A homogeneous mass of
the volume v' and of the desired phase has thus been produced, and the work gained
of the

evidently {l^ i>')v'.

is

Let us suppose that a small aperture

to let out exactly the

volume

//

of the

is

now opened and

in another place so as to diminish its contents

of the drop

and

closed in the envelop so as

mass within, the envelop being pressed inwards

by

this

amount.

During the extrusion

until the orifice is entirely closed, the surface of the

drop must adhere

to the edge of the orifice, but not elsewhere to the outside surface of the envelop.

The work done

Of

this

and the

in

forming the surface of the drop will evidently be as or

work, the amount {p'j)")v'

rest in

will be resisted

will

opening and closing the

by the

capillary tension.

^{'p' p")v'

be expended in pressing the envelop inward,

orifice.

Both the opening and the closing

If tlie orifice is circular, it

widest open, the radius determined by equation (550).

must have, when

W. Gibbs

J.

limit

is

Equilibrium of Heterogeneous Substances.

reached at which the interior of the

Now

properties of matter in muss.

if

fihii

ceases to have the

o'ac+ ^bc

the tension of the ordinary surface between

greater than Cab?

is

and B, such a

(See page 408.)

be at least practically unstable.

423

We

film will

cannot sup-

pose that 0'ab^<5'ac+ <^BCi for this would make the ordinary surface
A and B unstable and difficult to realize. If o'ab=o"'ac+ Cbc,

between

we may assume,

in general, that this

relation

that the ordinary surface of contact for

we have

and

is

not accidental, and

is

of the kind

which

described.

Let us

now

su|)pose the phases

and

to vary, so as

to

still

satisfy the conditions of equilibrium at plane contact, but so that the

C determined by

pressure of the phase

the temperature and poten-

and B. A
A and B will be entirely stable with
respect to the formation of any phase like C.
(The case is not quite
identical with that considered on page 161, since the system in question contains two different phases, but the principles involved are
tials

of

and

shall

become

less

than the pressure of

system consisting of the phases

entirely the same.)

With

respect to variations of the phases

direction

we must

consider

two

and

cases separately.

ient to denote the pressures of the three phases

in

the opposite

be conven-

It will

by /ja, Pk, Pc-, and

to

regard these quantities as functions of the temperature and potentials.

If o'ab=<5'ac+<5'bc for values of the

make jii9A=Jt)B=^:>c5

it

will not

temperature and potentials which

be possible to alter the temperature and

potentials at the surface of contact of the phases

jOa=/*b,

and Pc^pA,

foi"

and

so that

the relation of the temperature and potentials

necessary for the equality of the three pressui-es will be preserved

by

the increase of the mass of the phase C.

Such variations of the phases

A and B might be brought about in separate masses, but if these
were brought into contact, there would be an immediate formation
of a mass of the phase C, with reduction of the phases of the adjacent
masses to such as satisfy the conditions of equilibrium with that
phase.

we can vary the temperature and potentials

and^c^i^A, and it will not be possible for a sheet of
the phase of C to form irnmediately, i. e., while the pressure of C is
sensibly equal to that of A and B for mechanical work equal to
But

if o'ab<^<5'ac+<5'bc5

so that ^;<A=i^B5

might be obtained by bringing the

system into its original condition, and therefore produced without
any external expenditure, unless it be that of heat at the temperature
of the system, which is evidently incapable of producing the work.
<5'ac+<5'bc o'ab per unit of surface

Trans. Conn. Acad., Vol.

III.

54

Nov., 1877.

424

J.

The

W. Gibbs

Eq^dUhrinrn of Heterogeneous
system

stability of the

in

Substances.

must therefore

respect to such a change

C commences to be
same result if we use

extend beyond the point where the presfuire af

than that of

less

We

and B.

arrive at the

Since this expression has

the expression (520) as a test of stability.

when the

a finite positive value

pressures of the phases are

equal,

all

the ordinary surface of discontinuity must be stable, and

require a finite change in the circumstances of the case to

it

must

make

it

become unstable,*
it is shown that the surface of contact
under certain circumstances, with respect

In the preceding paragraph

of phases

and

stable

is

to the formation of a thin sheet of the phase C.

To complete the

demonstration of the stability of the surface with respect to the

mation of the phase C,

it is

be formed at the surface

sary, since

it is

if

at

all,

formed, for an incipient sheet of phase

when

o'ab<^<3'ac+

o'bc,

This

in lentiform masses.

manner,

in this

for-

necessary to show that this phase cannot

is

the more neces-

that the phase

C would

be

likely to

is

evidently be unstable

would immediately break up into lentiform

antl

masses.
It will

be convenient to consider
in

meet

in a

figiire

and

which

10 represent a section

through the centers of the spherical

mass of phase

faces, the

and that of phase

a lentiform mass of phase

Let

plane surface.

of such a system

Jjj*

first

equilibrium between masses of phases

lying on the

on the right of

left

of

sur-

D E H' F G,

D E H" F G.

Let

the line joining the centers cut the spherical surfaces in

H' and H", and the plane of the surface of contact of

L Let the radii of EH'F and E H" F be

denoted by r', r", and the segments I H', I H" by x\ x".
Also let I E, the radius of the circle in which the spherBy a suitable
ical surfaces intersect, V)e denoted by K.

and

Fig.

10.

in

application of the general condition of equilibrium

may

r'

Cac

* It

is

to,

which

x'

we

are

ffhc

now

is

x"

considering

Yet the reader

is

-,

(561)

Gak,

relates to a plane surface,

supposed thoroughly stable with respect

homogeneous masses.

-J =

r"

-,

true that such a case as

discussion referred

(520)

we

easily obtain the equation

formally excluded in the

and in which the system

to the possible formation of

any

is

different

will easily convince himself that the criterion

perfectly valid in this case with respect to the possible formation of a thin

sheet of the phase

<
',

which, as

kind of surface of di.^continuity.

we have

seen,

may

be treated simply as a different

J.

which
(Tac

W. GihhsEquiUhrhim. of Heterogeneous
components parallel

signifies that the

and

are together equal to

<Tbc

EF

to

of the tension

we denote by

If

(T^b-

425

Substances.

tlie

amount of work which must be expended in order to form such ;i

lentiform mass as we are considering between masses of indefinite
extent having the phases A and B, we may write

TF

J/

iV,

(562)

where
denotes the work expended in replacing the surface between A and B by the surfaces between A and C and B and C, and
A^ denotes the work gained in replacing the masses of phases A and
B by the mass of phase C. Then

31=
where
and

6'ac, -Sge,

(T AC

Sac

'S'bc^bc

(568)

^-ab ab,

denote the areas of the three surfaces concerned

Sab

]V=

V ipc - lu) + V" ipc -

(564)

Pn),

where F' and V" denote the >'olumes of the masses of the phases
A and B which are replaced. Now by (500),
2 <5^AC
Pc-~Pa= ,

We

'^

(565)

have also the geometrical relations

F' r= f

V" =

By

^BC
pc-ps^'

-I

and

substitution

N= I
and by

we

;r

r'2 x'

%7i r"2

tt

R''

TT

7^2 (r"

- x),

(r'

(566)
x!').

obtain

o'ac r' x!

7t

c"

-^

\7i

+t

;r o-Bc /"

^"

O-Ac r' x'

+|

R^

Oac

-^
r

^'inR^

ff^,

''~^.

(567)

(561),

N=

tt (Tbc

r"

x!'

-%7T R^

(Tab.

(568)

Since
2

we may

7T r'

Sac,

'^

T?"

r" x"

Ssc,

TT

R^

Sab,

write

^= I

(o'ac *^ac

O'bc 6'bc

(569)

O'ab Sab).

(The reader will observe that the ratio of 3f and JV

is

the same as

that of the corresponding quantities in the case of the spherical mass

treated on pages 416-422.)

W=
This value

is

ij

We

(o-Ac Sac

positive so long as

have therefore

O'bc ^bc

^-ab 5ab).

(570)

42(3

Gihhs

J. ^V.

E(j[vilihritim

since

But

^s^c

at the limit,

>

by

see

and

s^b,

6^

>

6\vb.

when

G.KC

we

of Heterogeneous Substances.

O'Br

Cab,

(561) that
<*AC ^^^

anCl

^ABj

and therefore

TF

Sbc

i'*AB?

0,

should however be observed that in the immediate vicinity of the

It

which the three surfaces of discontinuity

circle in

intersect,

physical state of each of these surfaces must be affected

We

vicinity of the others.

(570) except

the

by the

cannot, therefore, rely upon the formula

when the dimensions

of the lentiform mass are of sensi-

ble magnitude.

We may

conclude that after we pass the limit at which p^ becomes

jOr (supposed equal) lentiform masses of phase C

greater thauj^A and

will not be

formed

until either o'ab=o'ac4-o'bc, or p^,

jOa

becomes so
is one

great that the lentiform mass which would be in equilibrium

of insensible magnitude.

ing values of

PcPh

is

[The diminution of the

by equation

indicated

radii with increas(565).]

Hence, no

mass of phase C will be formed until one of these limits is reached.

Although the demonstration relates to a plane surface between A
and B, the result must be applicable whenever the radii of curvature
have a sensible magnitude, since the effect of such curvature may be
disregarded when the lentiform mass

is

of sufficiently small.

equilibrium of the lentiform mass of phase

The

is

easily

proved

affords a kind of measui-e of

to be unstable, so that the quantity
contact
of the phases A and B.*
surfaces
of
plane
the stability of
*

we

If

phases

same

represent phases by the position of points in such a manner that coexistent

the sense in which the term

(in

point,

positions of

istent phases are situated

intersect.

If the

disregarded,

phases

all

is

used on pa^e 152) are represented by the

and allow ourselves, for brevity, to speak of the phases as having the
the points by which they are represented, we may say that three coex-

where three

three phases are

two cases are

intersect,

series of

all

fluid,

to be distinguished.

this is

when each

or

pairs of coexistent phases

when

the eifects of solidity

meet or

may be

Either the three series of coexistent

of the thi-ee surface-tensions is less than the

two others, or one of the series terminates where the two others intersum
The series
this is where one surface tension is equal to the sum of the others.
gect
of coexistent phases will be represented by lines or surfaces, according as the phases
of the

have one or two independently variable components. Similar relations exist when
the number of components is greater, except that they are not capable of geometrical
representation without some limitation, as that of constant temperature or pressure or
certain constant potentials.

W. Gibbs

J.

Equilibrimii of Heterogeneous Substances.

Essentially the same principles apply to the

in

which the phases

and

that their surfaces of contact

have moderately

42*7

more general problem

different pressures, so

must be curved, but the

radii of curva-

ture have a sensible magnitude.

In order that a thin film of the phase

between masses of the phases

be

C may

be

in

equilibrium

and B, the following equations must

satisfied

where

and

Cj

denote the principal curvatures of the

C2

film,

the

centers of positive curvature lying in the mass having the phase A.

Eliminating

we have

c^-\-C2,

Cbc {Pk

It is

evident that

- Pc) =

(Jkc

{Pc

- Pb\

pc has a value greater than that determined by

mass; if jt>c has a
value, such a film will tend to diminish.
Hence, when
if

this equation, such a film will develop into a larger

less

Obc

the phases

Again,

between

(^ac

if

and B have a stable surface of contact.

more than one kind of surface of discontinuity is possible
and B, for any given values of the temperature and potenbe impossible for that having the greater tension to

tials, it will

place the other, at the temperature and with the potentials

dis-

con-

Hence, when pc has the value determined by equation

sidered.

and consequently o'ac+o'bc is one value of the tension for the

surface between A and B, it is impossible that the ordinary tension
(571),

of the surface

o'ab

when equation

(571)

the phase

should be greater than

is satisfied,

this.

If (J'ab=<5'ac+0'bc5

we may presume

that a thin film of

and B, and that

make p^

greater than the

actually exists at the surface between

a variation of the phases such as would

second number of (571) cannot be brought about at that surface, as

would be prevented by the formation of a larger mass of the phase

it

C.

But

if

o'AB<C^Ac+crBc

tion does not

and B,

mark the

for the

when equation

(571) is satisfied, this equa-

limit of the stability of the surface

between

temperature or potentials must receive a

finite

428

J.

W. Gihbs

Equilihrimn of Heterogeneous Substances.

change before the film

we

of phase C, or (as

shall see in the following

paragraph) a lentiform mass of that phase, can be formed.

The work which must be expended in order to form on the surface

between indefinitely large masses of phases A and B a lentiform mass
of phase C in equilibrium, may evidently be represented by the
formula

TF=

(Tac

'*>ac

G^c >%c

Cab ^ab

- Pc Vc + Pa T^a + Pb Fb,

(573)

where /Sac, i^bc denote the areas of the surfaces formed between A and
C, and B and C, S^n the diminution of the area of the surface between
A and B, F^ the volume formed of the phase C, and V^, Fg the
diminution of the volumes of the phases A and B. Let us now suppose (Tac, O'bc, o'ab, Pa, Pb to remain constant and the external boundary of the surface between A and B to remain fixed, while pc
increases and the surfaces of tension receive such alterations as are

necessary for equilibrium.

It

is

not necessary that this should be

physically possible in the actual system

we may suppose

the changes

to take place, for the sake of argument, although involving changes

in the

fundamental equations of the masses and surfaces considered.

Then, regarding TF simply as an abbreviation for the second member

of the preceding equation, we have

Cab
dW=z Cac diS^c + ^BC
-PcdVc + pj,dVj,-\-p^dV^c^'S'bc

But the conditions of equilibrium

Cac <^^ac

C'bc

f^'^^'AB

Vcdpc.

(574)

requii'e that

dS^c

Cab

^^'^ab

pcdVc-^Pj,dVj,+pjidVB

(575)

0.

Hence,

dW=
Now

it

evident that

is

Vq.

will

Vcdpc.

(576)

diminish as

2^c

value until Vc vanishes.

W'

1F"=0.

and
Hence

W"
W" denote

is

original

a negative quantity,

(577)

the initial and final values of W.

positive.

But

this is the value of

original system containing the lentiform

work necessary

its

This will give

W=

where

Let us

increases.

integrate the last equation sup])osing pc to increase from

But
in the

mass, and expresses the

to form the mass between the phases

and B.

It is

therefore impossible that such a mass should form on a surface be-

J.

W. Gibbs

Equilibrium

tween these phases.

We

of Heterogeneous Substances.

429

must however observe the same limitation

that Pc Phi PcP^

of
the
lentiform
mass are of
dimensions
must not be so great that the
as in the less general case already discussed,

insensible magnitude.

these differences

may

It

may

also be observed that the value

of

room on the
a mass of phase C

be so small that there will not be

surface between the masses of phases

sufficiently large for equilibrium.

and

for

In this case

we may

consider a

A
mass of phase C which is
which
the
three
and B in virtue of a constraint applied to the line in
surfaces of discontinuity intersect, which will not allow this line to
become longer, although not preventing it from becoming shorter.
We may prove that the value of is positive by such an integrain equilibrium upon the surface between

tion as

we have used

Substitution

before.

of Pressures for Potent ials in Fundamental Equations

for Surfaces.

The fundamental equation of

a surface which gives the value of

the tension in terms of the temperature and potentials seems best

adapted to the purposes of theoretical discussion, especially when the

number of components is large or undetermined. But the experimental determination of the fundamental equations, or the application
of any result indicated by theory to actiial cases, will be flicilitated

by the use

of other quantities in place of the potentials, which shall

be capable of more direct measurement, and of which the numerical

expression (Avhen the necessary measurements have been made) shall

depend upon less complex considerations. The numerical value of a

potential depends not oidy upon the system of units employed, but
upon the arbitrary constants involved in the definition of the
energy and entroj^y of the substance to which the potential relates,
also

or, it

may

be, of the elementary substances of

which that substance

This fact and the want of means of

(See page 152.)

measurement may give a certain vagueness to the idea of the
potentials, and render the equations which involve them less fitted to
is

formed,

direct

give a clear idea of physical relations.

Now

the fundamental equation of each of the homogeneous masses

which are separated by any surface of discontinuity affords a relation

between the pressure in that mass and the temperature and potentials.

We

ai-e

therefore able to eliminate one or

two

potentials from the

fundamental equation of a surface by introducing the pressures in

the adjacent masses.

Again, when one of these masses

is

a gas-

430

TK Gibhs

J.

mixture which

Equilibrium of Heterogeneous Substances.

Dalton's law as

satisfies

may

potential for each siniple gas

on page 215, the

_2;iven

be expressed

in

terms of the tem-

perature and the partial pressure belonging to that gas.

introduction of these partial pressures

we may

By the
many

eliminate as

potentials from the fundamental equation of the surface as there are

simple gases

An

the gas-mixture.

in

may be regarded as a
fundamental equation for the surface of discontinuity to which it
equation obtained by such substitutions

when the fundamental equations of the adjacent masses

known, the equation in question is evidently equivalent to an
equation between the tension, temperature, and potentials, and we
must regard the knowledge of the properties of the adjacent masses
relates, for

are

as an indispensable preliminary, or

an essential part, of a complete

knowledge of any surface of discontinuity.

It is evident,

however,

that from these fundamental equations involving pressures instead

of potentials

we cannot

obtain by difterentiation (without the use of

homogeneous masses) precisely the

between the

the fundamental equations of the

same

relations as

by the

difterentiation of the equations

and potentials. It will be interesting to

more important cases, what relations may be

tensions, temperatures,
inquire, at least in the

obtained by difterentiation from the

fundamental equations just

described alone.
If there

is

but one component, the fundamental equations of the

two homogeneous masses

one relation more than

aftbrd

for the elimination of the potential.

It

is

necessary

may be convenient

to regard

the tension as a function of the temperature and the difi'erence of the

pressures.

Now we

have by (508) and (98)

(Iff

d{p'-p")

=.

7/s

dt

Fd/u

= (//v'-O + (r'-r") d^,.

<^f

Hence we derive the equation

dff

= - [iH - -yp,

which indicates the

p'

p".

Vv'

//v")) dt

differential coetticients of

-,, d (2)' -p'%

ff

with respect to

For surfaces which may be regarded as nearly

evident that .

y
sion

j.

plane,

(5 V8)

and
it

is

represents the distance from the surface of ten-

-r

to a dividing

surface located so as to

make

the superficial

density of the single ctmiponent vanish, (being positive,

when the

W. Gihhs

./

latter surface is

Equilibrium of Heterogeneous Substances.

431

on the side specified by the double accents,) and that

the coefficient o^ dt (without the negative sign) represents the superficial

i.

e.,

by the

density of entropy as determined

by

the quantity denoted

When

7/^,

latter dividing surface,

on page 397.

two components, neither of which is co))fined to

we may regard the. tension as a function
of the temperature and the pressures in the two homogeneous masses.
The values of the difterential coefficients of the tension with respect
there are

the surface of discontinuity,

may

to these variables

be represented

a simple

in

form

we choose

if

such substances for the components that in the particular state considered each mass shall consist of a single component.

This will

always be possible when the composition of the two masses

identical,

and

We

coefficients.

where the marks

and

//s

dt

F^

dfj^

d2)'

dp"

= Vv" dt + y"

7/v'

dt

-\-

y'

F^^

dfj.^

dfj.^,

component

the

homogeneous masses

dj-t^^

we

d/A^^

sjiecified

specified

by

and

'

and

to indi-

with the substance of

Eliminating d/j and

".

obtain
dff

= (?k -;

We may

7v'

^ W) dt - ^ dp' - ^
y

(//,

^' ;a'

The equation thus modified

for a plane surface.

It is

is

and

would make

that 7

two

/"^^,

surfaces, or the

the negative sign)

dis-

surfaces of which one

to a unit of the surface of discontinuity,

(without

(580)

represent the

;'

two

of dt

and write

tances from the surface of tension of the

vanish, and the other

(5 7 9)

be regarded as the equation

strictly to

evident that

the distance between these

/)",

- j} Vv") dt - (^^, + ^;^ dp.

y
F^

djy".

generally neglect the difference of p' and

da = -

cient

are used instead of the usual

^^

cate the identity of the

entropy

not

then have

da =z

ume due

is

will evidently not affiect the values of the diffi?rential

represents

diminution of voland that the coeffi-

represents the excess of

system consisting of a unit of the surface of discontinuity with a part of each of the adjacent masses above that
which the same matter would have if it existed in two homogeneous
masses of the same phases but without any surface of discontinuity.
in a

Trans. Conn. Acad., Vol.

III.

5.5

Nov.. ISTI.

432

W. Gibhs

J.

(A mass thus

JEquilihrium of Heterogeneous

existingf

without any

Siibsta)ices.

must

of

and |-t-I are ffiIV en

^
\dp/t

in

surfjice of discontinuity

course he entirely surrounded hy matter of the same phase.)*

The form

which the values of (r-)

in

\dtjp

equation (580)

adapted to give a clear idea of the relations of

is

these quantities to the particular state of the system for which they

show how they vary with the

are to be determined, but not to

For

of the system.

state

be convenient to have the

this pixrpose it will

values of these diiferential coefficients expressed with reference to

ordinary components.
If

we eliminate

df/^

* If

we

and

Let these be specified as usual by

c^/Zg from the equations

=
=
dp

df

do'

//s

dp

r]y'

dt

//v"

dt

I\

~\-

d/.(

+ r/
+ ;//'

+ / d/./^,
+ y2 ^^/'a?
+ 7/3", c?/<2,

f//<i

'

manner
)'

easily obtain,

by means

equation (580)

may be

Hs +

)f

^'

of equations (93)

Es

Now

g-

set

in like

we may

and

'3

fZ/'i

and

(T

and

(507),

- i9 F.

(d)

written

d(y=

-K.di +

Differentiating {d\ and comparing the result with

dE,

Vdp.
(e),

dHs -i)d V.

(e)

we

obtain
(/)

The quantities Ej and Hs might be called the superficial densities

entropy quite as properly as those which we denote by e^ and tj^. In
composition of both of the homogeneous masses

is

of energy and

when

the

invariable, the quantities Es

and

fact,

H are much more simple in their definition than s and ??s, and would probably be
more naturally suggested by the terms superficial density of energy and of entropy. It
would also be natural in this case to regard the quantities of the homogeneous masses
as determined by the total quantities of matter, and not by

any other dividing

surface.

But such

tlie

surface of tension or

nomenclature and method could not readily

be extended so as to treat cases of more than two components with entire generality.
In the treatment of surfaces of discontinuity in this paper, the definitions and

The object of
in some
cases with advantage, and to show the precise relations between the quantities which
are used in this paper and others which might be confounded with them, and which
may be made more prominent when the subject is treated differently.

nomenclature which have been adopted will be

this note is to suggest to the reader

how

strictly

a different

adhered

to.

method might be used

J.

we

W. Gibhs

Equilibrkmi of Heterogeneous SabKtances.

433

obtain
do'

= j^ dt

(J
-{-

-^ dp,

(581)

.A.

Ji.

where
-A

= rt"r2'-ri'r2",

B=
c= i\

ir,"

Ki'

;/v'

r2')

r^'

^^2

(582)

(583)

(ri'-

(584)

ri")-

be observed that A vanishes when the composition of the two

homogeneous masses is identical, while Ji and C do not, in general,
and that the value of ,i is negative or positive according as the mass
specified by contains the component specified by ^ in a greater or
It will

'

proportion than the other mass.

less

Hence, the values both of

become infinite when the diiFerence in the com(-^-] and of (^

di/p
V^pjt
position of the masses vanishes, and change sign when the greater
)

proportion of a component passes from one mass to the other. This

might be inferred from the statements on page 155 respecting coexistent phases which are identical in composition, from which it appears
that when two coexistent phases have nearly the same composition,
a small variation of the temperature or pressure of the coexistent

phases will cause a relatively very great variation in the composition

The same relations are indicated by the graphical

of the phases.
method represented in figure 6 on page 184.

With regard

to gas-mixtures

shall only consider the

which conform to Dalton's law, we

fundamental equation for plane surfaces, and

suppose that there is not more than one component in the liquid
which does not appear in the gas-mixture. We have already seen
that in limiting the fundamental equation to plane surfaces we can
get rid of one potential by choosing such a dividing surface that the
shall

superficial density of one of the

components vanishes.

done with respect to the component peculiar to the liquid,

is

if

there

is

no such component,

of the gaseous components.

Let this be
if

such there

be done with respect to one

Let the remaining potentials be elimlet it

inated by means of the fundamental equations of the simple gases.

We

may

thus obtain an equation between the superficial tension, the

temperature, and the several pressures of the simple gases in the

gas-mixture or all but one of these pressures. Now, if we eliminate
(?/<25 ^A'sj ^^^' fi'oni

the equations

434

J.

W. Gihbs

da

Equilihrhim. of Heterogeneous Substances.

ih^^.dt

dp 2
dp^

r2, o

= ^V2
=

f^/^2

<^<^

7/v3 ^^^

^^/^3

^zi\^

^tc.,

+ K2 ^t^2l
+

Ks

^/^35

etc.,

where the

suffix

density has been

relates to the

made

of the gases specified in

etc.

component of which the

surface-

and y^, y<,, etc. denote the densities

the gas mixture, and p^iPz-) ^^c, ?/v2) '/vs,

to vanish,

the pressures and the densities of entropy due to these several

gases,

da

we

obtain

= (//sd)

?i'-'

-~

/;v2

'/V3

etc.

dt

-AiA^dp,-^^-l-^dp,-etc.
/ 2

This equation

aftbi-ds

(585)

values of the differential coefficients of

wdth

ff

p, p^, etc., which may be set equal to those obtained

by differentiating the equation between these variables.
respect to

t,

Thermal and Mechanical lielations pertaining

to the

Extension of a

Surface of Discontinuity.

The fundamental equation of a surface of discontinuity with one

two component substances, beside its statical applications, is of
use to determine the heat absorbed when the surface is extended
or

under certain conditions.

Let us first consider the case in which there is only a single component substance. We may treat the surface as plane, and place
the dividing surface so that the surface density of the single com-

ponent vanishes. (See page 397.) If we suppose the area of the

surface to be increased by unity without change of temperatui'e or
of the quantities of liquid and vapor, the entropy of the whole will

be increased by //s(j). Therefore, if we denote by Q the quantity of

heat which must be added to satisfy the conditions, we shall have
<?

and by

= ^%(,,,

(586)

(514),

*^

d(J

dff

dt

d\ogt

^.
^

It will be observed that the condition of constant quantities of

liquid and vapor as determined by the dividing surface which we

have adopted is equivalent to the condition that

shall remain constant.

ll;ie

total

volume

W. Gibbs

./.

Again,

Hqidlihrium of Heterogeneous Substances.

the surface

if

is

435

extended Avithout application of heat, while

the pressure in the liquid and vapor remains constant, the tempera-

by condensation

ture will evidently be maintained constant

vapor.

we denote by J/ the mass

If

of the

of vapor condensed per unit of

surface formed, and by a/m' and //m" the entropies of the liquid and
vapor per unit of mass, the condition of no addition of heat will

require that

^/('/m"-Vm')

The

= %(,).

(588)

increase of the volume of liquid will be

%(i)
y' iVu"

(589)

^mT

and the diminution of the volume of vapor

(590)

/(W-'/mT

Hence, for the work done (per unit of surface formed) by the exter-

which maintain the pressure, we

nal bodies

vm

shall

y/

\/

'/u

have

and, by (514) and (131),

The work expended

equal to

da

dt

dt

dp

da
d log p'

'

directly in extending the film will of course be

a.

Let us

now

consider the case in which there are two component

.

substances, neither of which

not

dG
dp

make

is

confined to the surface.

Since

we

can-

the superficial density of both these substances vanish

any dividing surface,

it

as the dividing surface.

will be best to

We

by

regard the surface of tension

may, however, simplify the formula by

choosing such substances for components that each homogeneous

mass

shall

consist of a single component.

Quantities relating to

these components will be distinguished as on page 431.

face

is

added

extended until

its

area

is

increased

by

If the sur-

unity, while heat

is

keep the temperature constant, and the

pressure of the homogeneous masses is also kept constant, the phase
at the surface so as to

of these masses will necessarily remain unchanged, but the quantity

of one will be diminished by l\, and that of the other
T'

entropies will therefore be diminished

by

'

?/v'

and

by

r
~

/"

r/y",

Their
respect-

436

J.

W. Gibbs

JEquilibrium of Heterdgeneous Substances.

Hence, since the surface receives the increment of entropy

ively.

the total quantity of entropy will be increased

'/s

which by equation (580)

r
p

Vv

r
//

'/v

equal to

is

Therefore, for the quantity of heat

shall

7j^,

by

imparted to the surface, we

have

We

\dt/p

must notice the

difference

(593) the quantity of heat

is

\d\ogtJp

between

this

'

formula and (587).

In

determined by the condition that the

temperature and pressures shall remain constant.

In

these

(587)

conditions are equivalent and insufficient to determine the quantity

The additional condition by which Q is determined may be

most simply expressed by saying that the total volume must remain
of heat.

constant.

considering

Again, the differential coefficient in (593) is defined by

in the differential coefficient in (587) p
^9 as constant
;

cannot be considered as constant, and no condition

give the expression a definite value.

ence of the two cases,

it is

is

necessary to

Yet, notwithstanding the

differ-

quite possible to give a single demonstra-

may be done by conmethod employed by Sir

This

tion which shall be applicable to both.

sidering a cycle of operations after the

William Thomson, who first pointed out these relations.*

The diminution of volume (per unit of surface formed)

y^r.

r.

be

/do-

<^-'

\dp
-'+7'=-(i).
y"

;/'

will

and the work done (per unit of surface formed) by the external
bodies which maintain the pressure constant will be

Compare equation (592).

The values of Q and
ties relating to

W may

and (595) of the values of the

by

(581),

we

By

substitution in (593)

differential coefficients

which are given

obtain

* See Proc. Boy. Soc,

p. 61.

also be expressed in terms of quanti-

the oi'dinai*y components.

vol. ix, p. 255, (June,

1858)

or Phil. Mag., Ser. 4, vol. xvii,

W. Gihbs

./

Equilibrium of ffeterogeneous Stihstances.

W=-pj.

Q=-tj^,
where A, B^ and
It will

(584).

which

differ infiuitesimally in

When

quantity A.

the

composition,

by (582)-

and TTare

in general

surface of discontinuity between coexistent phases

for the

infinite

(596)

represent the expressions indicated

(J

be observed that the values of

43V

is

it

the

and

composition,

phases

change sign with

absolutely identical in

are

not in general possible to counteract the effect of

extension of the surface of discontinuity

by any supply

For

of heat.

the matter at the surface will not in general have the same composition as the

homogeneous masses, and the matter required

increased surface

W are

The infinite values of Q and

when the phases are nearly identical

altering their phase.

by the

fact that

for the

cannot be obtained from these masses without

the extension of the surface of discontinuity

is

explained

in composition,

accompanied by the

vaporization or condensation of a very large mass, according as the

liquid or the vapor

is

the richer in that component which

is

necessary

for the formation of the surface of discontinuity.

If,

instead of considering the

amount of heat necessary

phases from altering while the surface of discontinuity

we

consider the variation of temperatiire caused

changes sign

vanishes with this quantity,

the phases becomes the same.

ments on page

When

i.

e.,

with y

vanishes

may be

This

extended,

by the extension of

the surface while the pressures remain constant,

variation of temperature

to keep the

is

when

it

appears that this

^" y2'

'^Yi'y/

>

^^^

the composition of

inferred from the state-

155, or from a consideration of the figure on page 184.

the composition of the homogeneous masses

is

initially abso-

lutely identical, the effect on the temperature of a finite extension or

contraction of the surface of discontinuity will be the same,

of the

two

perature

The
most

is

will

effect

maximum

or

minimum

for constant pressure.

of the extension of a surface of discontinuity which

easily verified

befoi-e

either

lower or raise the temperature according as the tem-

by experiment

is

is

the effect upon the tension

complete equilibrium has been reestablished throughout the

A fresh surface between coexistent phases may be

adjacent masses.

regarded in this connection as an extreme case of a recently extended

When sufiicient time has elapsed after the extension of a
surface.
surface

originally

superficial

tension

in

equilibrium

will evidently

between

coexistent

have sensibly

its

phases,

the

original value,

unless there are substances at the surface which are either not found

438

./

W. Gihhs

Equilibrium of Heterogeneo^is Suhstances.

at all in the adjacent masses, or are

found only

newly formed or extended may have a very

But a surface

different tension.

This will not be the case, however, when there

component substance,

com-

in quantities

parable to those in which they exist at the surface.

only a single

is

since all the processes necessary for equilibrium

are confined to a film of insensible thickness, and will require no

appreciable time for their completion.

When there

are

two components, neither

of which

is

confined to the

surface of discontinuity, the reestalilishment of equilibrium after the

extension of the surface does not necessitate any processes reaching

into tlie interior of the masses except the transmission of heat between the surface of discontinuity and the interior of the masses.
It appears from equation (593) that if the tension of the surface
diminishes with a rise of temperature, heat must be supplied to the

surface to maintain the temperature uniform

tended,

i.

e.,

when the

the effect of extending the surface

is

surface

to cool

it;

is

ex-

but

if

the tension of any surface increases with the temperature, the effect
of extending the surface will be to raise
case,

face

it

is

will

be observed, the immediate

to increase its tension.

course have the opposite

its

temperature.

effect of

In either

extending the sur-

contraction of the surface will of

But the time necessary

effect.

for the re-

establishment of sensible thermal equilibrium after extension or contraction of the surface

must

most cases be very

in

short.

two
more than two components, there are two ex-

In regard to the formation or extension of a surface between

coexistent phases of

treme cases which

it

is

desirable to notice.

density of each of the components

its

is

When

the superficial

exceeding small compared with

density in either of the homogeneous masses, the matter (as well

as the heat) necessary for the formation or extension of the

normal

surface can be taken from the immediate vicinity of the surface with-

out sensibly changing the properties of the masses from which

taken.

But

if

any one of these

value, while the density of the

it is

superficial densities has a considerable

same component

is

very small

in

each

of the homogeneous masses, both absohxtely and relatively to the

densities of the other components, the matter necessary for the for-

mation or extension of the normal surface must come from a considerable distance.

Especially

if

we

consider that a small difference of

density of such a component in one of the homogeneous masses will

probably make a considerable difference in the value of the corres-

ponding potential

[see eq. (217)],

value of the potential will

make

and that a small difference

in

the

a considerable difference in the ten-

J. TF. Gihhs

Equilibrium of Heterogeneous Substances.

sion [see eq, (508)],

it

439

will be evident that in this case a consider-

able time will bo necessary after the formation of a fresh surface or

the extension of an old one for the reestablishment of the normal

value of the superficial tension.

In intermediate cases, the reestab-

lishment of the normal tension will take

with different degrees

])lace

of raj)idity.

But whatever the number of component substances, provided that

it is
is

greater than one, and whether the reestablishment of equilibrium

slow or rapid, extension of the surface will generally produce

and contraction decrease of the tension. It would evidently

be inconsistent with stability that the opposite effects should be proincrease

In general, therefore, a fresh surface between coexistent

duced.

By the use of fresh

we may sometimes avoid the

phases has a greater tension than an old one,*

surfaces, in experiments in capillai'ity,
effect

of minute quantities of foreign substances,

which

may

be

present without our knowledge or desire, in the fluids which meet at

the surface investigated.

When

the establishment of equilibrium

the tension from

its

normal value

is

rapid, the variation of

be ma.nifested especially during

will

the extension or contraction of the surface, the phenomenon resembling that of viscosity, except that the variations of tension arising

from variations

same

in

the densities at and about the surface will be the

in all directions,

while the variations of tension due to any

property of the surface really analogous to viscosity would be greatest in the direction of the

We may here

most rapid extension.

notice the different action of traces in the

homogene-

ous masses of those substances which increase the tension and of

those which diminish
are very small,

its

it.

When

the volume-densities of a component

surface-density

may have

a considerable positive

value, but caii only have a very minute negative one.f

For the

value when negative cannot exceed (numerically) the product of the

greater volume-density

by the

thickness of the non-homogeneous

* When, however, homogeneous masses which have not coexistent phases are
brought into contact, the superficial tension

The

may

increase as the potential for alcohol

is

increase with the course of time.

and water placed

superficial tension of a drop of alcohol

in a large

equaMzed throughout the room, and

room
is

will

dimin-

ished in the vicinity of the surface of discontinuity.

\ It is here supposed that

we have chosen

for

components such substances as are

incapable of resolution into other components which are independentlj' variable in the

homogeneous masses.

In a mixture of alcohol and water, for example, the compo-

nents must be pure alcohol and pure water.

Trans. Conn. Acad., Vol.

III.

56

Jan., 1878.

440

J.

W. Gihhs

Eqxdlihrium oj Heterogeneous Substances.

Each of these quantities is exceedingly small. The surfacewhen positive is of the same order of magnitude as the thickness of the non-homogeneous film, but is not necessarily small com-

film.

density

pared with other surface-densities because the volume-densities of

the same substance in the adjacent masses are small.
Now the
potential of a substance which forms a very small part of a

homo-

geneous mass certainly increases, and probably very rapidly, as the

proportion of that component

The

is

pressure, temperature, and

sensibly afiected.

But the

[See (98).]

[See (IVI) and

increased.

the other potentials, will

(21*7).]

be

not

on the tension of this

efi:ect

increase of the potential will be proportional to the surface-density,

and

will

positive.

be to diminish
[See (508).]

It

when

the tension
is

the surface-density

quite possible that a

therefore

is

very

small trace of a substance in the homogeneous masses should greatly

diminish the tension, but not possible that such a trace should greatly
increase

it.*

Impermeahle Vilms.

We have

so far supposed, in treating of suriaces of discontinuity,

that they afibrd no obstacle to the passage of any of the component

substances from either of the homogeneous masses to the other.

case,

however, must be considered, in which there

at the surface of discontinuity

which

is

impermeable to some or

* From the experiments of M. E. Duclaux, {Annales de Ghimie

vol. xxi, p. 383,) it

The

a film of matter

is

all

of

de Physique, Ser. 4,

et

appears that one per cent, of alcohol in water will diminish the

superficial tension to .933, the value for pure

water being unity.

The experiments do

not extend to pure alcohol, but the difference of the tensions for mixtures of alcohol

and water containing

and 20 per

cent,

water

is

comparatively small, the tensions

being .322 and .336 respectively.

According to the same authority (page 427 of the volume

Castile soap will reduce the superficial tension of water

cited),

one 3200th part of

by one-fourth one 800th part

;

by one-half. These determinations, as well as those relating to alcohol and

water, are made by the method of drops, the weight of the drops of different liquids
(from the same pipette) bemg regarded as proportional to their superficial tensions.
M. Athanase Dupre has determined the superficial tensions of solutions of soap by
A statical method gives for one part of common soap in 5000 of
different methods.

of soap

water a superficial tension about one-half as great as for

be measured on a

pui'e water,

jet close to the orifice, the value (for the

identical with that of pure water.

He

same

but

if

solution)

the tension
is

sensibly

explains these diflierent values of the super-

tension of the same solution as well as tlie great effect on the superficial tension
which a very small quantity of soap or other trifling impurity may produce, by the
tendency of the soap or other substance to form a film on the surface of the liquid.
(See Annales de Chiinie et de Physiiiup, Ser. 4, vol. vii, p. 409, and vol. ix, ]). .'i79.)

ficial

W. Gihbs

J.

Equilibrhim

of Heterogeneous

when

when

the film

a film of

oil is

may

Such

the components of the contiguous masses.

for example,

Stthstances.

be the case,

spread on a surface of water, even

too thin to exhibit the properties of the

is

441

oil in

mass.

communication between the contiguous

masses through other parts of the system to which they belong, such
that the components in question can pass freely from one mass to the
other, the impossibility of a direct passage through the film may be
In such cases,

there

if

is

regarded as an immaterial circumstance, so far as states of equilibrium are concerned, and our formula^ will require no change. But
when there is no such indirect communication, the potential for any
component for which the film is impermeable may have entirely
difterent values on opposite sides of the film, and the case evidently
requires a modification of our usual method.

single consideration

suggest the proper treatment of such

Avill

component which

If a certain

cases.

is

found on both sides of a film

cannot pass from either side to the other, the fact that the part of the
component which is on one side is the same kind of matter with the

may be disregarded. All the general relations

which would hold if they were really different submay therefore write //j for the potential of the com-

part on the other side

must hold

true,

We

stances.

ponent on one side of the

film,

substance (to be treated as

other side

ni\ for

for the potential of the

j-i^

were a

different substance)

same

on the

the excess of the quantity of the substance on the

side of the film

first

and

if it

above the quantity which would be on that side

determined by the surface of

of the dividing surface (whether this is

tension or otherwise)

if

the density of the substance were the same

near the dividing surface as at a distance, and

tity relating to the other side of the film

the same principle,

wi^j

we may

and m% per unit of

use 1\ and

siirface,

and

(juantities of the substance

and
its

m%

for a similar quan-

and dividing

I^

to denote

sm-face.
tlie

On

values of

m/, y ^^

y^' to denote the

densities in the

two homogeneous

??ii',

masses.
a notation, which may be extended to cases in which
impermeable to any number of components, the equations
relating to the surface and the contiguous masses will evidently have
the same form as if the siibstances specified by the different suffixes

With such

the film

is

were

all

of

and

//j

really different.
//g,

components, and

/',, i

cients with respect to

tions

The

superficial tension will

be a function

with the temperature and the jiotentials for the other

/^j

^^'il^

and

//g.

equal to

^^^

its

In a word,

which have been demonstrated

may

all

differential coeffi-

the general rela-

be applied to this case,

if

442

J.

W. Gihhs Equilibrium of Heterof/eneous

we remember always
according as

to treat the

component

^Substances.

as a different substance

found on one side or the other of the impermeable

it is

film.

When
fixes

there

and

in the film,)

is

free passage for the

component

specified

by the sufany flaws

throiigh other parts of the system, (or through

we

have

shall

in case of equilibrium //^m/Zg.

If

we wish

to obtain the fundamental equation for the surface wlien satisfying

this condition,
face,

we may

without reference to other possible states of the sur-

set a. single

symbol

for /<i

and

//g in

the more general

form of the fundamental equation. Cases may occur of an impermeability which is not absolute, but which renders the transmission of

some of the components exceedingly slow.

In such cases,

it

may be

necessary to distinguish at least two different fundamental equations,

one relating to a state of approximate equilibrium which

may

be

quickly established, and another relating to the ultimate state of

complete equilibrium.

The former may be derived from the

latter

by

such substitutions as that just indicated.

Conditions of Internal Equilibrium for a System of Hetero-

T7ie

geneous Fluid Classes without neglect of the Influence of the

Surfaces of Discontinuity or of Gravity.

Let us

now

seek the complete value of the variation of the energy

of a system of heterogeneous fluid masses, in which the influence of

gravity and of the surfaces of discontinuity shall be included, and

deduce from it the conditions of internal equilibrium for such a sysIn accordance with the method which has been developed, the
tem.
intrinsic energy, (/. e., the part of the energy which is independent of
of gravity,) the entrojDy, and the quantities of the several components must each be divided into two parts, one of which we regard as
belonging to the surfaces which divide approximately homogeneous
masses, and the other as belonging to these masses. The elements

of intrinsic energy, entropy,

Ds

etc.,

will be denoted by De^, Drf,

-Z^f^,

etc.

We

Ds and Dv

resjiectively.

is,

Dm^
Din''

The

and those relating

;/_/>y to denote the total

quantities of matter relating to the elements

That

etc.,

D'f, Dm\, Dml,

volume Dv, by
use Dm^ or FDs and Diti'^ or

to an element of
shall also

relating to an element of surface

Dm\, Dm%,

= rDs = Dm\ + Z>m| -f

yDv Din\ + Duil +

part of the energy which

is

etc.,

(597)

etc.

(598)

due to gravity must also be divided

J.

into

W. Gihhs

two

parts,

Eqmlihrhmi of Heterogeyworis Suhs:tances

443

one of which rehites to the elements Dm^, and|the

The complete value of the variation of

other to the elements Urn".

the energy of the system will he represented by the expression

d/Be"

+ 6/ Dt^ + 6fg z Dm" + dfg z Dm^,

which g denotes the force of gravity, and

ment above a fixed horizontal plane.

in

It will

z tlie

(599)

height of the

ele-

be convenient to limit ourselves at first to the consideration

This will exclude the formation of new

of reversible variations.

masses or surfaces.

We may

therefore regard

any infinitesimal

variation in the state of the system as consisting of infinitesimal

variations of the quantities relating

bring the sign of variation

of integration.

If

the values given

we then

in the

to

its

elements, and

several

preceding formula after the sign

substitute for f5Z>% dJJt^, SDni", 6Din^,

by equations

(i;5),

(497), (597), (598),

we

shall

have

for the condition of eciuilibrium with respect to reversible variations

of the internal state of the system

ft dBif

-fp 6Bv +fl.ii 6Dm\

+./"//2

f^Uml

etc.

SBml + etc.
4- fg 6z Bm"+fg z dBm\ + /// z 8Bm\ + etc.
+ yV ^^ Dm^ + fg z dBni\ -^fg z 6Bra\ -\- etc. =

+ /7 SBif +/(J (SlJs+fji^ (UJm\ +.//' o

0,

(600)

Since equation (497) relates to surfaces of discontinuity which are

might seem that this condition, although

always necessary for equilibrium, may not always be sufticient. It is
evident, however, from the form of the condition, that it includes the

initially in equilibrium, it

particular conditions of equilibrium relating to every possible deformation of the system, or reversil)le variation

entropy or of the several components.

relations

between the

difl:erent

in the

distribution

of

It therefore includes all the

parts of the system which are neces-

sary for equilibrium, so far as reversible variations are concerned,

(The necessary relations between the various quantities relating to

each element of the masses and surfaces are expressed by the fundamental equation of the mass or surface concerned, or may be immediately derived from it.
See pp. 140-144 and 391-393.)

The

variations in (600) are subject to the conditions which arise

from the nature of the system and from the supposition that the
changes in the system are not such as to affect external bodies. This
supposition

is

necessary, unless

we

the state of the external bodies, and

are to consider the variations in

is

evidently allowable in seeking

the conditions of equilibrium which relate to the interior of the sys-

444

J.

W. Gihhs

Equilibrium of Heterogeneous Substances.

But before we consider the equations of condition

tern.*

we may

in detail,

divide the condition of equilibrium (600) into the three condi-

tions

ft

- fjy SDv + f o//^i rfl>m\

diJt,''

SlJs

+ft dlJif =

+ fg

+//', 6Dm\

(601)

0,

6z Bni'-^fg 6z Bnv^

-\-fgz6I)rn^\

0,

(602)

+fgz6Dm\

+ //73 dDm\+fi.(2 6I))n%-\-fgz6Dml^fgzdI>m%

+ etc. =

(603)

0.

For the variations which occur

in

independent of those which occur

of condition

will relate

any one of the three are evidently

the other two, and the equations

in

to one or another of these conditions sepa-

rately.

The

variations in condition (601) are subject to the condition that

the entropy of the whole system shall remain constant.

This

maybe

expressed by the equation

fdJJif -i-fSBtf

To

satisfy the condition thus limited

t

it is

(604)

0.

necessary and sufficient that

= const.

throughout the whole system, which

(605)
is

thermal

the condition of

equilibrium.

The

conditions of mechanical equilibrium, or those that relate to

the possible deformation of the system, are contained in (602), which

may

also be written

y> SIJv -{-fff dJ)s+fg y 6z I)v -\-fg FSz Ih

It will

be observt>d that

this condition

difterent fluids wei-e separated

has the same form as

by heavy and

elastic

We

(606)
if

the

membranes with-

out rigidity and having at every point a tension uniform in

all direc-

The

variations in this formula.

have sometimes given a physical expression

to a supposition of this kind, in

tions in
*

0.

the plane of the surface.

problems in which the peculiar condition of matter in the vicinity of surfaces of

continuity

was

to

dis-

be neglected, by regarding the system as surrounded by a rigid and

impermeable envelop.

But the more exact treatment which we are now

problem of equilibrium would require us

envelop on the immediately adjacent matter.

to take accoimt of tlie

to give the

influence of the

Since this involves the consideration of

surfaces of discontinuity between-solids and fluids, and

we wish

present to the consideration of the equilibrium of fluid masses,

to limit ourselves at

we

shall give

up the

conception of an impermeable envelop, and regard the system as bounded simply by a

imaginary surface, which

is

not a surface of discontinuity.

system must be such as do not deform the surface, nor

The

variations of the

affect the matter external to

it.

J. IV.

Gibhs

Equilibriuni of Ileterogeiieons Suhstances.

beside their necessary geometrical relations, are

tions that tlie external snrface of the system,

the surfaces of discontinuity meet

it,

are fixed.

siil)ject

and the

445

to the condi-

lines in

which

The formula may be

reduced by any of the usual methods, so as to give the particular

Perhaps the following method

conditions of mechanical equilibrium.

will lead as directly as
It

Avill

any

to the desired result.

be observe<l the quantities aftected by 6

in (606) relate

exclusively to the position and size of the elements of volume and

is divided, and that the variations 6p
and 6a do not enter into the formula either explicitly or implicitly.
The equations of condition which concern this formula also relate

surface into which the system

exclusively to the variations of the system of geometrical elements,

and do not contain either 6p or Sff. Hence, in determining whether

first member of the formula has the value zero for every possible

the

variation of the system of geometrical elements,

we may

assign to

6p and 6a any values whatever, which may simplify the solution of

the problem, without inquiring wdiether such

values are physically

possible.

NoAV when the system

the pressure jo, in each

divided by the surfaces of tension, is a function of the co-ordinates which determine the position of
the element Dv, to which the pressure relates.
In the varied state
is

in its initial state,

of the parts into Avhich the system

is

of the system, the element I)v will in general have a diflferent position.
Let the variation 6}) be determined solely by the change in position
of the element

Dv.

This

may

be expressed by the equation

i:
which J^? are determined by the function mentioned
ax
ay
dz
and f^a', ^y, 6z by the variation of the position of the element Dv.
Again, in the initial state of the system the tension o", in each of

in

'

the different surfaces of discontinuity,

a?,,

GJ.^,

which determine

is

the' position

two co-ordinates
of the element Ds.
In the

a function of

varied state of the system, this element will in general have a diffei-ent position.
The change of position may be resolved into a com-

ponent lying

in the surface

and another normal to

it.

Let the varia-

6a be determined solely by the first of these components

motion of Ds. This may be expressed by the equation
tion

r>^

da

P.

da

of the

446

W. Gihhs

J.

in wliieli

Eqxdlihrmm of Meter ogeneoris Substances.

are determined

doo^

by

the function mentioned, and

doo

6 00^, by the component of the motion of J)s which

(5^Cc5j,

lies in

the

plane of the surface.

With this understanding, which is also to apply to Sp and 6

when contained implicitly in any expression, w^e shall proceed to the
reduction of the condition (606).

With

respect to any one of the volumes into which the system

by

divided

the surfaces of discontinuity,

is

write

= Sfp Dv f dp Dv.

/"p 6I)v

But

we may

evident that

it is

6j'pI)v=fp6NDs,
where the second integral

relates to the

surfaces of discontinuity

bounding the volume considered, and 6]Sf denotes the normal component of the motion of an element of the surface, measured outward.
Hence,

fp 6Dv
Since this equation

system

is

divided,

fp
where

j)'

Ds, and

is

= fp dNiJs ~ fd'p iJv.

true of each separate volume into Avhich the

we may

write for the whole system

dJDv =f{p'^2^")

dNI)s - fS2} Dv,

(609)

and p" denote the pressures on opposite sides of the element

measured toward the side specified by double accents.

<^iV^is

Again, for each of the surfaces of discontinuity, taken separately,

/
and

dfaJJs
where

c^

(positive,

(J

dDs = Sfo'Bs fSff Ds,

/o- (c, + Cg) SNDs +fG 6TDI,

and c^ denote the principal curvatures

when

of the surface,

the centers are on the side opposite to that toward

which (JiVis measured,) Dlaw element of the perimeter of the surface,

and 7' the component of the motion of this element which lies in the
plane of tlie surface and is perpendicular to the perimeter, (positive,
(5^

when

it

extends the surface).

fG6nsz=fa{c^

-f-Cg)

Hence we have

for the

whole system

SNDsi-f2{(rST)Dl-fd(rDs,

(6 JO)

where the integration of the elements Dl extends to all the lines in

which the surfaces of discontinuity meet, and the symbol 2 denotes
a summation with respect to the several surfaces which meet in such
a line.

By

equations (609) and (610), the general condition of mechanical

equilibrium

is

i-educed to the form

J.

W. Glhbs

Eqidlibriaiu of Heterogeneous /Substances.

-Ap' -p") SNDs ^fdpDv +fG (c,

-VJ'2{ff

447

+C2) 6NIJS

ST) Dl -^/SffBs+fg y dzDv

+fg rSzUs

0.

Arranging and combining terms, we have

J'{g

y 6z -\-

d]))

Dv

+ /[{p"-p')SJV+0 {,+,) SJ^+gr6z^6ff]Us

+/:^{ffST)Diz=o.
To satisfy

this condition,

of Dv, Ds, and

Dl

evidently necessary that the coefficients

it is

shall vanish

throughout the system.

In order that the coefficient of

sufficient that, in

by the

Dv

shall vanish,

it is

necessary and

each of the masses into which the system

surfaces of tension,

(611)

shall

be a function of

is

z alone,

divided

such that

'-t=-gy.

(612)

dz
In oi-der that the coefficient of

necessary and sufficient that

gential

movements of the

it

Ds

shall vanish in all cases,

shall vanish for

surface.

P^'or

it is

normal and for tan-

normal movements

we may

write

and

6 (1=0,

3 dN,

6z =z cos

where 3 denotes the angle which the normal makes with a

line.

The

first

y_y' =

(T(.-.-f.',)+^rcos5,

which must hold true at every point

The condition with

in

is

movements shows that

coefficient

= .,1.
of

Dl

(614)
in

for every point in every line in

tinuity meet, and for

any

in

a function of z alone, such that

-^
In order that the

(613)

every surface of discontinuity.

respect to tangential

each surface of tension o

must have,

vertical

condition therefore gives the equation

(611)

shall

we

vanish,

which surfaces of discon-

infinitesimal displacement of the line,

:^{g6T)=0.

(615)

This condition evidently expresses the same relations between the tensions of the surfaces meeting in the line

and the directions of

per-

pendiculars to the line drawn in the planes of the various surfaces,

which hold

for the

magnitudes and directions of

foi-ces in

equilibrium

in a plane.

In condition (603), the variations which relate to any component are

to be regarded as

having the value zero in any part of the system

Trans. Conn. Acad., "Vol.

III.

57

Jan., IS'ZS.

in

448

W. GIbbs

J.

Equilibrhmi of Heterogeneous Substances.

which that substance

is

not an actual component.*

The same

is

true

with respect to the equations of condition, wliich are of the form

f6I>ml-J^fdDm\=0,

fdDml^fSI)ml

0,

etc.

(616)

here supposed that the various components are independent,

(It is

i. e.,

that none can be formed out of others, and that the parts of the sys-

tem

in

which any component actually occurs are not entirely sepain which it does not occur.)
To satisfy the condition

by parts

]-ated

(603), subject to these equations of condition,

.

it

is

necessary and

sufficient that the conditions

fx^-\-gz=z3I^,

etc.,
(71/ J,

(617)

J/gj 6tc. denoting- constants,) shall each hold true in those parts

of the system in which the substance specified

We

may

an actual component.

is

here add the condition of equilibrium relative to the possible

absorption of any substance (to be specified by the suffix

of the system of which

it

is

not an actual component,

by parts

viz.,

that the

expression jA^gz must not have a less value in such parts of the

system than

contiguous part

in a

in

which the substance

an actual

is

component.

From

equation (613) with (605) and (617)

we may

easily obtain

the differential equation of a surface of tension (in the geometrical

sense of the term),

when p\ p" and

ff

Cg

temperature and potentials.

terms of the

first

and second

For

Cj

are

known

in

terms of the

and S may be expressed

differential coefficients of z

in

with respect

and p\ p'\ <J, and F in terms of the

But the temperature is constant, and for
we may substitute gz increased by a constant.

to the horizontal co-ordinates,

temperature and potentials.

each of the potentials

We

thus obtain an equation in which the only

first

and second

differential coefficients

A'^ariables

are z and its

with respect to the horizontal

But it will rai-ely be necessary to use so exact a method.

Within moderate differences of level, we may regard ;/', y" and a as
We may then integrate the equation [derived from (612)]
constant.
co-ordinates.

d{p'-.p")
*

Tbe term

and the
that

if

actual component has been defined for

definition

may be extended

a substance

is

face of discontinuity,

well as

when

= g{y"^y')dz,

it

homogeneous masses on page

to surfaces of discontinuity.

It will

an actual component of either of the masses separated by a

it

must be regarded as an actual component

117,

be observed
sur-

for that surface, as

occurs at the surface but not in either of the contiguous masses.

W. Oibhs

J.

EqriUibrium of Heterogeneous iSubstances.

449

whicli will give

j/^p"

= c/{y"-/)z,

(018)

z
to be measured from the horizontal plane for which p'=p".
Substituting this value in (<>i:^), and neglecting the term containing

where

is

we have

/ \

c,+c,=^iz'---Zl).,
where the

coefficient of 2 is to be

(619)

regarded as constant.

Now the value

of z caimot be very large, in any surface of sensible dimensions, unless

y"~}/'

is

We

very small.

may

therefore consider this equation as

practically exact, unless the densities of the contiguous masses are

very nearly equal.

we

If

substitute for the

sum

of the curvatures

value in terms of the differential coefficients of z with resi)eot to

its

the horizontal rectangular co-ordinates, x and y,

,

dz'^\ d'^z

.,

.,

dz dz d'z

dxdydxdy

dy^jdx'-

dx^

A
\

dz'^\

dx'^

(/(y"7')

z.

(G20)

of the root in the denominator of the

to the sign

fraction,

to be observed that, if

is

d'z

) dy''-

dy'^ I
dy'

With regard
it

we have

we always

take the positive

value of the root, the value of the whole fraction will be positive or
is turned upward or
But we wish the value of the fraction to be positive
when the greater concavity is turned toward the mass specified by a

negative according as the greater concavity

downward.

single accent.

We

should therefore take the positive or negative

value of the root according as this mass

The
last

is

above or below the

surface.

particular conditions of equilibrium which are given in the

paragraph but one

may be regarded

in general as the conditions

of chemical equilibrium between the different parts of the system,

since they relate to the separate components.*
tion

is

not entirely appropriate unless the

greater than one.

But such a designa-

number

of comisonents

is

In no case are the conditions of mechanical equi-

librium entirely independent of those which relate to temperature

and the potentials. For the conditions (612) and (614) may be regarded as consequences of (605) and (617) in virtue of the necessary
relations (98) and (508).
* Concerning another kind of conditions of chemical equilibrium, which relate to
the molecular arrangement of the components, and not to their sensible distribution in
space, see pages 197-203.
f

Compare page

206,

where

a similar

ence of the surfaces of discontinuit_y.

problem

is

treated without regard to the infiu-

450

J. TFT Cxlhhs

Equlllhriam of Heterogeneous Snhstances.

The mechanical
cial

conditions of equilibrium, however, have an espe-

we may always regard them

importance, since

mass

liquid (and not decidedly viscous)

In such a mass,

are observable.

in

when

as satisfied in

any

which no sensible motions

isolated, the attainment of

mechanical equilibrium will take place very soon; thermal and chemical

equilibrium will follow more slowly.

The thermal equilibrium

approximate attainment than

the chemical but the processes by which the latter is produced will
generally cause certain inequalities of temperature until a state of
will generally require less

time for

its

complete equilibrium

When

which do not occur

in

potentials for these

may

is.

reached.

a surface of discontinuity has

more components than one

the contiguous masses, the adjustment of the

components

accordance with equations (617)

in

take place vei-y slowly, or not at

mobility

in

all,

the components of the surface.

want of sufficient
But when this surface

for

has only one component which does not occur in the contiguous
masses, and the temperature and potentials in these masses satisfy
the conditions of equilibrium, the potential for the component peculiar to the surface will

since this

(617),

very quickly conform to the law expressed in

necessary consequence of the condition

is

mechanical equilibrium
relating to temperature

to be satisfied.

connection

the

of

conditions

distribution of the substance peculiar

brought about by ex])ansions and contractions

If the surface meets a third

of the surface.

with

and the potentials which we have supposed

The necessary

to the surflice will be

in

(614)

component and no other which

is

mass containing

this

foreign to the masses divided

by

the surface, the potential for this component in the surface will of
course be determined

The

by

tliat in

the mass which

it

meets.

particular conditions of mechanical equilibrium (6I2)-(615),

which may be regarded as expressing the relations 'which must subbetween contiguous portions of a fluid system in a state of
mechanical equilibrium, are serviceable in determining whether a
But the mechanical theogiven system is or is not in such a state.
sist

rems which relate to finite parts of the system, although they may
be deduced from these conditions by integration, may generally be

more

easily obtained

by a

suitable application of the general condi-

tion of mechanical equilibrium (606), or

by the application of

ordi-

nary mechanical principles to the system regarded as subject to the

forces indicated
It

will

by

this equation.

be observed that the conditions of equilibrium relating to

temperature and

tlic

iiotciitials

arc

not affecteil by

tlie

surfaces of

J.

W. Gihhs

Equilihriiitii

[Compare

discontinuity.

(228)

<>f

and

451

Ileterogeiieous Siih.stances.
(2:U).] *

Since a phase cannot

vary continuously without variations of the temperature or the

potentials,

follows from these conditions that the phase at any

it

point in a fluid system which has the same independently variable

components throughout, and is in equilibrium under the influence of

gravity, must be one of a certain number of phases which are completely determined by the phase at any given point and the dirt'erence
If the phases thi'oughout the
of level of the two points considered.
fluid system satisfy the general condition of practical stability for
phases existing in large masses

that the pressure shall be the least

(viz.,

consistent with the temperature and potentials), they will be entirely

determined by the phase

at any given point and the differences of

(Compare page 210, whei'e the subject is treated without

level.

regard to the influence of the surfaces of discontinuity.)

Conditions of equilihriuni rdati^uj to irreversible changes.
conditions of equilibrium relating to the absorption

The
by any part of

the system of substances which are not actual components of that part

have been given on page 448.

Those relating to the formation of new

masses and surfaces are inchided

in the conditions of stability relat-

ing to such changes, and are not always distinguishable from them.

They

are evidently independent of the action of gravity.

We

have

already discussed the conditions of stability with respect to the for-

mation of new
surface

fluid

masses within a homogeneous

when two such masses meet

(see

fluid

and at the

pages 416-429), as well as

the condition relating to the ])ossibility of a change in the nature of

a surface of discontinuity.

(See pages 400-403, where the surface

plane, but the result

considered

is

surfaces.)

We shall

may

easily be

hereafter consider, in

extended to curved

some of the more import-

ant cases, the conditions of stability with respect to the formation of

new masses and

surfaces which are peculiar to lines in which several

surfaces of discontinuity meet,

and

])oints in

which several such

lines

meet.

Conditions of stabiUty relating

to the

whole system.

Beside

the

conditions of stability relating to very small parts of a system, which

are substantially independent of the action of gravity, and are dis-

cussed elsewhere, there are other conditions, which relate to the

* If the fluid system

permeable to

all

is divided into separate masses by solid diaphragms which are

the components of the fluids independently, the conditions of equi-

librium of the fluids relating to temperature and the potentials wUl not be affected.

(Compare page
extended

139.)

to this case.

The propositions which follow

in the

above paragraph

may

be

452

W. Gihbs

J.

Equilibrium of Heterogeneous Substances.

whole system or to considerable parts of it.

To determine the quesstability of a giA^en fluid system under the influence of

tion of the

when

gravity,

all

the conditions of equilibrium are satis6ed as well

which relate to small parts of the sysuse the method desci'ibed on page
413, the demonstration of which (pages 411, 412) will not require
any essential modification on account of gravity.
When the variations of temperature and of the quantities 3/j, M,
etc. [see (617)] involved in the changes considered are so small that
they may be neglected, the condition of stability takes a very simple
as those conditions of stability

tem taken

form, as

tem

separately,

we may

we have already

seen to be the case with respect to a sys-

uninfluenced by gravity.

We

(See page 415.)

have to consider a varied state of the system in which the

and the total quantities of the various components are

and
all variations vanish at the exterior of the system,
unchanged,

total entropy

in which,

moreover, the conditions of equilibrium relating to tem-

perature and the potentials are satisfied, and the relations expi-essed

by the fundamental equations

regarded as

satisfied,

complete equilibrium.

of the masses and surfaces are to be

although the state of the system

is

not one of

Let us imagine the slate of the system to vary

continuously in the coui'se of time

in

accordance with these condi-

and use the symbol d to denote the simultaneous changes which

take place at any instant. If we denote the total energy of the
system by E^ the value of clE may be expanded like that of 6E in
(699) and (600), and then reduced (since the values of t, /.t^+gz,
^t^'- ^^'^ uniform throughout the system, and the total entropy
h2~\'U
tions

'^1

and

total quantities of the several comjjonents are constant) to the

form

dE=i -y> dl)v ^fg dz Bm^+fo' dDs -{-fg dz Dm^

fp dDv +fg y dz Dv f a dDs ^fg T dz Ds,
-\-

(62

where the integrations relate to the elements expressed by the symbol

D. The value of p at any point in any of the various masses, and
any of the various surfaces of discontinuity
by the temperature and potentials at the
If the variations of t and J/,, il/g, etc. are to be
point considered.
neglected, the variations of p and a will be determined solely by the
change in position of the point considered. Therefore, by (612) and

that of

o'

at

any point

in

are entirely determined

(614),

dp-=.

and

gy

dz.,

da = g Fdz

W. Gibbs

J.

Equilibrixui of Heterogeneous Substances.

453

dE= -^fp cWv -/dp Dv-\-f(3 dDs +fda Ds

= - dfp I)v + d/G Ds.
we now

If

integrate with respect to

state of the system,

we

commencing

given

at the

obtain

AE=
where

f/,

(622)

- Afp JJv { AJ'G Ds,

(623)

denotes the vahxe of a quantity in a varied state of the sys-

tem diminished by
variations,

and

is

its

value in the given state.

This

is

true for finite

without

therefore true for infinitesimal variations

The condition of

neglect of the infinitesimals of the higher oi'ders.

stability is therefore that

Afp Dv Afff Ds <0,

(6 24)

fpDv-^j'ffDs

(625)

or that the quantity

has a

maximum

value, the values of

p and

o',

for each different

or surface, being regarded as determined functions of

ary cases

0"

may

z.

mass

(In ordin-

be regarded as constant in each surface of discon-

and jt? as a linear function of z in each different mass.) It

may easily be shown (compare page 416) that this condition is always
sufficient for stability with reference to motion of surfiices of discon-

tinuity,

tinuity, even

when

the variations of

t,

M^, M2,

etc.

cannot be neg-

lected in the determination of the necessuri/ condition of stability

with respect to such changes.

0)1

the Possibility

of

the Forination

of a Heic Surface of Discon-

tinuity where several Surfaces of Discontinuity meet.

When more

than three surfaces of discontinuity between homo-

geneous masses meet along a

may

line, Ave

conceive of a

new

surface

being formed between any two of the masses which do not meet
sui'face in the original state of the

system.

The condition of

in a

stability

with respect to the formation of such a surface maj^ be easily obtained

by

the consideration of the limit between stability and instability, as

exemplified

by a system which

surface of the kind

To

our ideas,

fix

is

equilibrium when

a very small

us suppose that there are four

homogeneous

is in

formed.

let

masses A, B, C, and D, which meet one another

which we
along a

may

line L.

call

in four

A-B, B-C, C-D, and D-A, these surfaces

This

is

indicated in figure 11

by

all

surfaces,

meeting

a section of the sur-

454

J.

W. Gibbs^ Equilibrium of Heteroge^ieous

faces cutting the line

ISubstances.

at right angles at a point O.

tesimal variation of the state of the system,

small surface being formed between

and C

(to

U.

Fig.

infini-

be called A-C),

so that the section of the surfaces of discontimiity

plane takes the form indicated in figure 12.

In an

we may conceive of a
by the same

Let us suppose that

Fig. 12.

is satisfied both for the line L in

which the surfaces of discontinuity meet in the original state of the
system, and for the two such lines (which we may call L' and L") in the
varied state of the system, at least at the points O' and O" where they
We may therefore form a quadriare cut by the plane of section.
lateral of which the sides af5, f:iy, yd, 6(x are equal in numerical

the condition of equilibrium (615)

value to the tensions of the several surfaces A-B, B-C, CD, D-A,
and are parallel to the normals to these surfaces at the point O
in

In like manner, for the varied

the original state of the system.

state of the system

we can

construct two triangles having similar

surfaces of discontinuity meeting at O' and O".

But the directions of the normals to the surfaces A-B and B-C
at O' and to C-D and D-A at O" in the varied state of the system
diifer infinitely little from the directions of the corresponding norrelations to the

mals at

in the initial state.

two
and yd^ da
as

We

may

therefore regard afi, f3y

sides of the triangle representing the surfaces

meeting

as

at O".

two

meeting at

O',

sides of the triangle representing the surfaces

Therefore,

if

we

join ay, this line will represent the

direction of the normal to the surface A-C, and the value of its tenIf the tension of a surface between such masses as A and C had
sion.

been greater than that represented by ay,

it is

evident that the initial

state of the system of surfaces (represent ed in figure 11)

would have

been stable with respect to the possible formation of any such surIf the tension had been less, the state of the system would
face.

have been
unstable

ill

at least

practically unstable.

To determine whether

the strict sense of the term, or whether or not

it is

it is

prop-

W. Gihbs

J.

Equilibrium of Heterogeneous Substances.

erly to be regarded as in equilibrium,

analysis than

The

result

would require a more

we have used.*
which we have obtained may be

455

refined

generalized as follows.

When more

than three surfaces of discontinuity in a fluid system meet

in equilibrium along a line, with respect to the surfaces and masses

immediately adjacent to any point of this line we may form a polygon

of which the angular points shall correspond in order to the different
masses separated by the surfaces of discontinuity, and the sides to
these surfaces, each side being perpendicular to the corresponding

and equal

surface,

new

With

to its tension.

respect to the formation of

surfaces of discontinuity in the vicinity of the point especially

considered, the system

is stable, if every diagonal of the polygon is

and practically unstable, if any diagonal is greater, than the
tension which woidd belong to the surface of discontinuity between

less,

the corresponding masses.

In the limiting case,

when

the diagonal

exactly equal to the tension of the corresponding surface, the sys-

is

tem may often be determined to be unstable by the application of

the principle enunciated to an adjacent point of the line in which the

in

points of the line, no diagonal

remark that a nearer approximation

might be attained, by taking special account,

which surfaces

lines in

We

all

We may here

stability

manner

But when,

of discontinuity meet.

surfaces

structed for

is

in the

the polygons con-

any case greater

in

theory of equihbrium and

in our general equations, of the

These lines might be treated in a

which we have treated surfaces of discontinuity.

of discontinuity meet.

entirely analogous to that in

might recognize linear densities of energy, of entropy, and of the several sub-

With respect

stances which occur about the line, also a certain linear tension.

to

these quantities and the temperature and potentials, relations would hold analogous to

those which have been demonstrated for surfaces of discontinuity.

If the

sum

of the tensions of the lines L' and L", mentioned above,

(See pp. 391-393.)

is

greater than the

tension of the line L, this line will be in strictness stable (although practically unstable)

with respect to the formation of a surface between

a surface

The

is

little less

and

C,

when

different use of the

term practically unstable

in different parts of this

not create confusion, since the general meaning of the term

system

is

the tension of such

than that represented by the diagonal ay.

is

paper need

in all cases the same.

caUed practically unstable when a very small (not necessarily indefinitely

small) disturbance or variation in

its

condition will produce a considerable change.

In the former part of this paper, in which the influence of surfaces of discontinuity

was

neglected, a system

would be produced by

was regarded

as practically unstable

when such

a result

same order of magnitude as the quantities

discontinuity which were neglected.
But where surfaces of

a disturbance of the

relating to surfaces of

discontinuity are considered, a system

is

not regarded as practically unstable, unless

the disturbance which will produce such a result

quantities relating to surfaces of discontinuity of

Trans. Conn. Acad., Vol.

III.

58

is very small compared with the

any appreciable magnitude.

March,

1878.

456

J.

W. Gibhs

Equilibrium of Heterogeneous /Substances.

than the tension of the corresponding

is

equal to the tension

siirface, biit

a certain diagonal

the polygons constructed for a finite portion

in

of the line, farther investigations are necessary to determine the

For

stability of the system.

page 413

is

this pui-pose, the

may be

similar proposition

enunciated in

spect to a point about which the angular space

angles by surfaces of discontinuity.

rium,

method described on

evidently applicable.

we can always form

If these

many
is

cases with re-

divided into solid

surfaces are in equilib-

a closed solid figure without re-entrant

angles of which the angular points shall correspond to the several

masses, the edges to the surfaces of discontinuity, and the sides to

the lines in which these edges meet, the edges being perpendicular
to the corresponding surfaces, and equal to their tensions, and the

Now

sides being perpendicular to the corresponding lines.

solid angles in the physical

system are such as

may

if

the

be subtended by

the sides and bases of a triangular prism enclosing the vertical point,
or can be derived from such

by deformation,

the figure representing

the tensions will have the form of two triangular pyramids on oppo-

same base, and the system will be stable or practicwith respect to the formation of a surface between the

site sides of the

ally unstable

masses which only meet

in a point,

face between such masses

is

according as the tension of a sur-

greater or less than the diagonal joining

the corresponding angular points of the solid representing the ten-

This will easily appear on consideration of the case

sions.

in

which

a very small surface between the masses would be in equilibrium.

The Conditions of Stability for Fluids relating to the Formation

of a New Phase at a Litie in which Tliree Surfaces of
Discontinuity meet.

With regard

to the formation of

new phases

there are particular

conditions of stability which relate to lines in which several surfaces

of discontinuity meet.

We may

limit ourselves to the case in

which

there are three such surfaces, this being the only one of frequent occur-

and may treat them as meeting

rence,

in a straight line.

It

will

be

convenient to commence by considering the equilibrium of a system

in

which such a

line is replaced

by a filament of a

Let us suppose that three homogeneous

are separated
at first

being

by

A, B, and C,

cylindrical {or plane) surfaces, A-B, B-C, C-A, which

meet in a straight

less

difterent phase.

fluid masses,

line,

each of the surface-tensions Cab? ^bcj <^ca

Let us suppose that the

than the sum of the other two.

W. Gibhs

J.

system

which

is

is

Equilibriutn of Heteroge^ieous Substances.

457

then modified by the introduction of a fourth fluid mass D,

is separated from them by
D-A, D-B, D-C meeting A-B, B-C, and C-A in
The general form of the surfaces is shown by figure

placed between A, B, and C, and

cylindrical surfaces
straiglit lines.

which the full lines represent a section perpendicular to all the

The system thus modified is to be in equilibrium, as well
as the original system, the position of the surfaces A-B, B-C, C-A
being unchanged. That the last condition is consistent with equili14, in

surfaces.

brium

will

appear from the following mechanical

Fig. 14.

considerations.

Fig. 16.

Fig. 15.

Let Vd denote the volume of the mass D per unit of length or the area
ab c. Equilibrium is evidently possible for

of the curvilinear triangle

any values of the surface-tensions (if only Cab, o'bc? ^ca satisfy the conmentioned above, and the tensions of the three surfaces meeting at each of the edges of D satisfy a similar condition) with any
dition

if the edges of D are constrained to remain

A-B, B-C, and C-A, or these surfaces extended,

value (not too large) of Vp,

in the original surfaces
if

necessary, without change of curvature.

by only two

We

cylindrical surfaces.)

system as maintained

(In certain cases one of

D-C may disappear and

the surfaces D-A, D-B,

in

equilibrium

by

may

will

be bounded

therefore regard the

forces applied to the edges

The same forces

would keep the system in equilibrium if D were rigid. They must
therefore have a zero resultant, since the nature of the mass D is immaterial when it is rigid, and no forces external to the system Avould
be required to keep a corresponding part of the original system in
But it is evident from the points of application and
equilibrium.
directions of these forces that they cannot have a zero i-esultant unless
each force is zero. We may therefore introduce a fourth mass D
without disturbing the parts which remain of the surfaces A-B, B-C,
of

and acting

at right angles to

A-B, B-C, C-A.

C-D.
It will

be observed that

are entirely determined

<?'db5

O'dc-

[See (615).]

all

the angles at ,

b, c,

and d

in figure 14

by the six surface-tensions Cak, Cbc, o'ca, (5'da,

The angles may be derived from the tensions

458

W. Gibhs

J.

Equilihriwm of Heterogeneous Substances.

by the following construction, which will also indicate sorae important

properties. If we form a triangle a ft y (figure 15 or 16) having sides
equal to

^ca, the angles of the triangle will

(Tab, o^bc?

be supplements

we may suppose the sides of the

triangle to be perpendicular to the surfaces at d.
Upon p y we may
then construct (as in figure 16) a triangle ft y 6' having sides equal
to Cbc, ^dc? ^db, upon y a
triangle ;/ a 6" having sides equal to
of the angles at

To

d.

our ideas,

fix

2i

oTda,

^CA,
<5'ab,

ft

a,

<-!'

a triangle ^^(y'" having sides equal to

/i

These triangles are to be on the same sides of the

cTda.

<3'db5

y,

antl iipon

Cdc,

respectively, as the triangle

ft,

ft

lines

The angles

y.

of

these triangles will be supj^lements of the angles of the surfaces of

discontinuity at a,

Now
a

ft

6'"

y,

we

case

and d"

if S'

will

ft

curvilinear triangle

in

(3',

ft

6", 6'"

y,

do not

ft

y d'=.da

in a single

b,

and a y S"=zdb

a.

point d within the triangle

the same point, as in figure 15.

y 6 -\-a y 6-=.a y ft, and the three

a db will be together equal to two

The same will be true

bdc, cda, and hence
if

Thus

c.

together

fall

have

shall

and

b,

fall

In this

angles of the
right angles.

of the three angles of each of the triangles

But

of the three angles of the triangle abc.

fall

together in the same point within the triangle

either possible to bring these points to coincide within

it is

the triangle by increasing some or

all

of the tensions Cda, Cdb,

<5'dcj

the same result

by diminishing some or all of these tensions.

(This will easily appear when one of the points S', 6", 6'" falls
within the triangle, if we let the two tensions which determine this
point remain constant, and the third tension vary. When all the
or to

eflfect

points

6',

S", 6'" fall

without the triangle

a ft

y,

we may suppose

the

greatest of the tensions Cd^, Cdb, ^dc the two greatest, when these
are equal, and all three when they all are equal to diminish until

one of the points

In the

first

case

6',

S", 6'"

we may

brought within the triangle a

is

say that the tensions of the

too small to be represented

by the distances of an

new

ft

y.)

surfaces are

internal point from

the vertices of the triangle representing the tensions of the original

surfaces (or, for brevity, that they are too small to be represented as
in the second case we may say that they are too great
be
thus
to
represented.
In the first case, the sum of the angles in
each of the triangles adb, bdc, cda is less than two right angles
in figure 15)

(compare figures 14 and 16):

triangles
sions
figure

bdc,

a ft 6'",

(Tda, Cdb,
1

6,

cda

ft

in

yd", y a 6"

Cdc are only a

the second case, each pair of the

will overlap, at least

little

when

the ten-

too great to be represented as in

and the sum of the angles of each of the triangles adb,

will be greater than two right angles.

W. Gihhs

J.

Equilibrium of Heterogeneous Substances.

Let us denote by

Va, ^b? ^c the portions of

v^y

459

which were originally

occupied by the masses A, B, C, respectively, by

Sj,a, ^db?

by Sab, *bc5 ^caj the

by the mass D per

the

dc

areas of the surfaces specified per unit of length of the mass D,

and

areas of the surfaces specified which were replaced

In numerical value, v^^ Vb, Vq

unit of its length.

be equal to the areas of the ctirvilinear triangles h cd, cad^

will

ahd', and
ah, c

d,

"'^S ^^^

Sqa, ^db, ^dc? ^ab? bc, ^ca

ad,b d.

Also

<5da ^DA "T

^DB ^DB

and

TFv

The general

to the lengths of the lines 6c, ca,

let

"T" '^'dC

=^^d ^d

*DC

^AB ^AB

<5'bc

S^q

Oqa

^Ca?

i?A "a - IH "b Pc ^c-

(626)
(627)

condition of mechanical equilibrium for a system

of

homogeneous masses not influenced by gravity, when the exterior of

the whole system

is

fixed,

may

be written

2{(}6s)-:S{pdv)
[See (606).]

If

we apply

tliis

Q.

(628)

both to the original system consisting

by the

of the masses A, B, and C, and to the system modified

intro-

duction of the mass D, and take the difference of the results, suppos-

ing the deformation of the system to be the same in each case,

shall

have

^da

(^da

<^Sab -~ O'bc ^Hc

+ O-db (^Sdb + Cdc <^dc
(TcA ^ScK - Pt> ^Vj) + Pj, Svj, -f ps <Svb + Pc ^Vc =
(5'ab

In view of this relation,

all

we

if

we

differentiate (626)

quantities except the pressures as variable,

0.

and (627) regarding

we

obtain

dWs dWv = SdA ^^O-da + Sdb f^O-DB + DC ^ffj^c

- AB C^O'aB **BC t?0'BC CA f^^-cALet us

now suppose

the system to vary in

similar to itself in form,

(629)

size,

(630)

remaining always

and that the tensions diminish in the same

Such changes

ratio as lines, while the pressures remain constant.

will evidently not impair the equilibrium.

DA, <^DA ^DB,

<?'db?

tc.

Vary in the same

S^B (^^mi

SDA<?<?'DA=if^(^DA*'DA),

We
TFs

Since

all

the quantities

ratio,

=^

d{(^I,B Sdb),

CtC.

(631)

have therefore by integration of (630)

TTv

= i (0'dada+ CdbSdb + Cdc^dc O'abSab -

O'bcSbc

- C^ca^ca),

(632)

whence, by (626),
TFs

The

= 2 Wy,

condition of stability for the system

(633)

when

the pressures and

tensions are regarded as constant, and the position of the surfaces

460

J.

W. Gibbs

A-B, B-C, C-A as

Eqidlibriuni of Heterogeneous Substances.

the tensions and of

varies, the

[See (549).]

pj^^ jOg,

p^,

system remaining

W^
Now

he a minimum under
any constant values of
we may make Wp so small that when it

fixed, is that Wl^

the same conditions.

in

equilibrium, (which will in general

reqiiire a variation of p^,,)

we may

d a, d b, d c, and regard

the figure

For the

itself.

total curvature

degrees) of each of the lines a

stant,

shall

for

neglect the curvatures of the lines

abed

(^. e.,

b,

as remaining similar to

the curvatui*e measured in

be, c

may

be regarded as con-

being equal to the constant difierence of the sum of the angles

of one of the curvilinear triangles

angles.

Therefore,

when

Vi,

is

adb,bdc,cda

and two right

very small, and the system

deformed that equilibrium would be preserved

variation, but this pressure as well as the others

and

all

remain constant, Wg, will vary as the lines in the figure

Wy

as the square of these lines.

so

is

had the proper

if j^d

the tensions

ab c d, and

Therefore, for such deformations,

This shows that the system cannot be stable for constant pressures

and tensions when v^ is small and TFy is positive, since Ws Wy

It also shows that the system is stable
will not be a minimum.
when Wy is negative. For, to determine whether TP^ Wy is a
minimum for constant values of the pressures and tensions, it will
evidently be sufiicient to consider such varied forms of the system as
give the least value to W^ IVy for any value ot v-d in connection
with the constant pressures and tensions. And it may easily be
shown that such forms of the system are those which would preserve equilibrium if j^d had the proper value.
These results will enable us to determine the most important questions relating to the stability of a line along which three homogeneous fluids A, B,
fluid
in

D.

meet, with respect to the formation of a different

The components

the surrounding bodies.

determined by

tliat

D must of course be such as are found

We shall regard p^ and o'da, Cdb, o'oq as

of

phase of

which

satisfies

librium with the other bodies relating

potentials.

to

the conditions of equi-

temperature and

the

by means
and of the surfaces D-A,

These quantities are therefore determinable,

of the fundamental equations of the mass

D-B, D-C, from the temperature and potentials of the given system.
Let us first consider the case in which the tensions, thus determined, can be represented as in figure 15, and
sistent with the equilibrium of a small

considering.

It

pj)

has a value con-

mass such as we have been

appears from the preceding discussion that when v^

is

W. Gibbs

J.

Equilibrium of Heterogeneous Substances.

sufficiently small the figure

that

its

d may be regarded as rectilinear, and

by its tensions. Hence the

angles are entirely determined

ratios of Wa? ^b,

'^c,

^d, foi* sufficiently small values

mined by the tensions

we may suppose

figure

abed

it is

y^,

We

manner.

Pc to be equal, which will make the

jOa? i>B5

We

may

make

equal to the other

jOp

this quantity

supposed that

sary for equilibrium.

of Wp, are deter-

for convenience in calculating these

absolutely rectilinear, and

pressures, since

of

and

alone,

ratios,

ratios

ab

461

has the value neces-

obtain a simple expression for the

^d in terms of the tensions in the following

shall write [D B C], [D C A], etc., to denote the areas
^b,

^c,

of triangles having sides equal to the tensions of the surfaces between

the masses specified.
Vf^

?'b

triangle

bdc.

be sin bed
sin

bac sin bed sin abc sin acd

:

sin y6/:l sin

sin

ySp

da/J sin

Sfi

sin

y 6 fi

triangle

[D

udc

ac sin acd

triangle

yda sin Spa

yda 6a

triangle

y 6a

B C] [D C A].
:

Hence,

yA:yB:^^c:^D::[DBC]:[DCA]:[DAB]:[ABC],

(634)

where
4V[(0'ab+<5'bc+0'ca)(0'ab+0'bc 0'ca)(0'bc+0-ca~0-ab) (o'ca+O'ab-

may be

written for [A

O'ec)]

C], and analogous expressions for the other

symbols, the sign \/ denoting the positive root of the necessarily positive expression

which

case of equilibrium,

follows.

when the

This proportion will hold true in any

tensions satisfy the condition mentioned

and v-D is sufficiently small. Now if pA=i-*B =/>c5 I^d will have the
same value, and we shall have by (627) Wy := 0, and by (633) Ws
0.
But when Vq is very small, the value of TFg is entirely determined by
the tensions and Vo.
Therefore, whenever the tensions satisfy the
condition supposed, and ?Jd is very small (whether pj^, p^, p^ are

equal or unequal,)

=: TFs

= TFv =^D "d

i?A ?^a

- IH Vb - Pc Vc,

(635)

which with (634) gives

_ [DBC]^A+ DCA ^3+[DAB]pe

^^ ""
Since this

is

[D B C]

[D C A]

[D

A B]

'

the only value ofp^ for which equilibrium

is

possible

when

462

W. Gihhs

J^.

Equilibrium of Heterogeneous Substances.

the tensions satisfy the condition supposed and v^

that
is

when

jy^

small,

it

follows

has a less value, the line where the fluids A, B,

C meet

is

When p^

stable with respect to the formation of the fluid D.

a greater value,

if

practically unstable,

should be formed

Let

new

us

next

must be
only a very small mass of the

such a line can exist at

it

if

e.,

/.

would tend to

all, it

has

at least
fluid

increase.

consider the case

in

which the tensions of the

surfaces are too small to be represented as in figure 15.

If

the pressures and tensions are consistent with equilibrium for any

very small value of

angles

the angles of each of the curvilinear

v-q,

adb, bdc, cda

and the

a b,b

lines

be together

will

tri-

than two right angles,

For

be convex toward the mass D.

c , will

c,

less

given values of the pressures and tensions, it will be easy to deterFor the tensions will give the total
mine the magnitude of v-^.
curvatures (in degrees) of the lines ab, be, ca; and the pressures
will give the radii of curvature.

In order that

determined.

necessary that

p-o shall

tensions of the

new

be

p-r,

case

is

only a

when the

These

shall

lines

are thus completely

be very small

evidently

is

it

Yet

than the other pressures.

less

if

the

surfaces are only a very little too small to be

represented as in figure
of

v-d

15,

may be

Vp

quite small

when

the value

than that given by equation (636).

little less

new

tensions of the

In any

surfaces are too small to be repre-

sented as in figure 15, and v^ is small, W^ is negative, and the equiMoreover, TFg
is stable.
W^, which reprelibrium of the mass
sents the work necessary to form the mass D with its surfaces in

place of the other masses and siu'faces, is negative.

With respect to the stability of a line in which the surfaces A-B,

B-C C-A meet, when the

be

new surfaces are too small to

we first observe that when the pressures
to make Wp moderately small but not so
[this will be when p-o is somewhat smaller

tensions of the

represented as in figure 15,

and tensions are such as

small as to be neglected,
than the second
the tensions

member

differ

of (636),

more

more or

less smaller

according as

or less from such as are represented in

figure 15,] the equilibrium of such a line as that supposed (if it is

capable of existing at all) is at least practically unstable. For greater

p^ (with the same values of the other pressures and the

the same will be true. For somewhat smaller values of pn,

values of
tensions)

the mass of the phase

which

will

be formed will be so small, that

we may

neglect this mass and regard the surfiices A-B, B-C,

meeting

in

/)o,

we may

a line in stable equilibi'ium.

For

still

C-A

as

smaller values of

likewise regard the surfaces A-B, B-C,

C-A

as capable

W. Gibbs

J.

Equilibrium of Heterogeneous Substances.

of meeting in stable equilibrium.

determined

as

?'d,

the conception of a

may

It

be observed that when

by our equations, becomes quite insensible,

small mass D having the properties deducible

from our equations ceases to be accurate, since the matter

vicinity of a line

be

in

But

463

in

the

where these surfaces of discontinuity meet must

a peculiar state of equilibrium not recognized by our equations.*

this cannot affect the validity of

our conclusion with respect to

the stability of the line in question.

The

case remains to be considered in which the tensions of the

pose that they are not very

When

much

new

Let us sup-

surfaces are too great to be represented as in figure 15.

too great to be thus represented.

make

the pressures are such as to

Vq moderately small (in case

of equilibrium) but not so small that the mass

to

which

relates

it

when
somewhat greater than the second member of (636), more or
greater according as the tensions differ more or less from such as

ceases to have the properties of matter in mass, [this will be

is

Pj)

less

where the surfaces A-B, B-C,

are represented in figure 15,] the line

C-A meet

will

be in stable equilibrium with respect to the formation

of such a mass as
tive.

The same

we have

W^ Wy

considered, since

will be true for less values of

will be posi-

For greater values

jOr,.

of jOp, the value of TFg - TFy, which measures the stability with respect
to the kind of change considered, diminishes.

according to our equations, for

tions

ai*e

finite

values of

It
p-^.

does not vanish,

But these equa-

not to be trusted beyond the limit at which the mass

ceases to be of sensible magnitude.

But when the tensions are such

as

we now

consider the possible formation of a mass

suppose,

we must

also

within a closed figure in

which the surfaces D-A, D-B, D-C meet together (with the surfaces
in two opposite points.
If such a figure is to be in
equilibrium, the six tensions must be such as can be represented by

A-B, B-C, C-A)

* See note on page 455.

may have

We may here

a negative value.

add that the linear tension there mentioned

This would be the case with respect to a line in which

three surfaces of discontinuity are regarded as meeting, but where nevertheless there

reaUy exists in stable equilibrium a filament of different phase from the three surrounding masses.

The value

nearly equal to the value of

of the linear tension for the supposed line,

W^

exact value of the linear tension

it

would be

W^. for the actually existing filament.

would be necessary

The reader

(For the

add the sum of the

We may

tensions of the three edges of the filament.)

adhering together as an example of this case.

to

linear

regard two soap-bubbles

will easily convince himself

that in an exact treatment of the equilibrium of such a double bubble

we must

recog-

nize a certain negative tension in the line of intersection of the three surfaces of
discontinuity.

Teans. Conn. Acad., Vol.

III.

59

March,

1878.

464

W. Gibbs Equillbrmm of Heterogeneous

'L

ISubstances.

the six distances of four points in sjjace (see page 455),

condition

which evidently agrees with the supposition which we have made.

we denote by mv
and form
?0s
it

the work gained in forming the mass

as to be in equilibrium) in place of the other masses,

the work expended in forming the

may

D (of such

new

If
size

and by

surfaces in place of the old,

be shown by a method similar to that used on page 459

From this we obtain ^s~^v=i^'v This is evidently

easily

that wJs=f^vpositive

when p-^ is

with increase of

^s- Hence
B-C, C-A is

be

it

diminishes

as easily appears from the equivalent expression

the line of intersection of the surfaces of discontinuity A-B,

stable for values of pj^ greater than the other pressures

(and therefore for

garded

But

greater than the other pressures.

jf^,

all

as accurate,

in equilibrium

values of

which

will

px))

be so long as

has a sensible

method is to be rethe mass D which would

so long as our

size.

In certain cases in which the tensions of the

new

much

surfaces are

too large to be represented as in figure 15, the reasoning of the two

last

paragraphs will cease to be applicable.

These are cases

in

which

the six tensions cannot be represented by the sides of a teti*ahedron.

not necessary to discuss these cases, which are distinguished

It is

the different shape which the mass

formed, since

it

the results which

(J'da,

(^TiYit

would take

if

it

by

should be

evident that they can constitute no exception to

is

we have

obtained.

For an increase of the values of

Cdc cannot favor the formation of D, and hence cannot im-

pair the stability of the line considered, as deditced from our equa-

Nor

tions.

can an increase of these tensioris essentially affect the

fact that the stability thus

jt>D is

demonstrated

may

fail

to be realized

when

considerably greater than the other pressures, since the a priori

demonstration of the stability of any one of the surfaces A-B, B-C,

C-A, taken singly,

is

subject to the limitation mentioned.

(See

page

426.)

The Condition of Stability for Fluids relating to the Formation

of a New Phase at a Point lohere the Vertices of
Four Different Masses meet.
Let four different

fluid

masses A, B, C,

to form the six surfaces of discontinuity

D-C, which meet

lines

meeting

mass E.

meet about a point, so as

A-B, B-C, C-A, D-A, D-B,

A-B-C, B-C-D, C-D-A, D-A-B, these

Let us suppose the system stable

and consider the conditions of stability for the ver-

in the vertical point.

in other respects,
tical point

in the four lines

with respect to the possible formation of a different fluid

W. Gibbs

J.

Equilihrhim of Heterogeneous Svbstcmces.

system can be

If the

been replaced by a mass

in

equilibrium

when the

465

vertical point has

against which the four masses A, B, C,

abut, being truncated at their vertices,

it

is

evident that

will

have

four vertices, at each of Avhich six surfaces of discontinuity meet.

(Thus at one vertex there

and

be the surfaces formed by A, B, C,

will

tensions of each set of six surfaces (like those of the

The

E.)

six surfaces formed by A, B, C, and D) must therefore be such that

they can be represented by the six edges of a tetrahedron. When
the tensions do not satisfy these relations, there will be no particular

condition of stability for the point about which A, B, C, and

meet,

would distribute itself along

some of the lines or surfaces which meet at the vertical point, and it
is therefore sufficient to consider the stability of these lines and surWe shall suppose that the relations mentioned are satisfied.
faces.
If we denote by TP^^ the work gained in forming the mass E (of
since

if

a mass

should be formed,

such size and form as to

it

equilibrium) in place of the portions

l)e in

of the other masses which are suppressed, and

pended

in

forming the new surfaces

by W^ the work

in place of the old, it

may

ex-

easily

be shown by a method similar to that used on page 459 that

TTgrrfTTv,

W^,- Wy=^W.,;

whence
also, that

when

the

volume

(638)

small, the equilibrium of

is

will

be

W^ and W^

are negative or positive.

critical relation for the tensions is that

which makes equilibrium

stable or unstable according as

(637)

when

possible for the system of the five masses A, B, C, D, E,

The ten
magnitude and direction by the

the surfaces are plane.

tensions

may

all

then be represented in

ten distances of five points in space

A-B and the direction of its normal

The point f will lie within the tetrahedron
formed by the other points. If we write i'e for the volume of E, and
a,

/?,

y,

by the

6, , viz.,

a /5,

line

^A? Vb, Vc, Vj) for

the tension of

etc.

the volumes of the parts of the other masses which

are suppressed to

make room

for E,

we have evidently

Wy =Pe v^-2)j, Wa ^b '-'B-i^c'-'c- ;>d Vj).

Hence, when

all

the surfiices are plane, Wy=zO, und

(639)

Wg,=

0.

Now

always possible for a given small value of v^ with any

given values of the tensions and oi' p^, j^^-, 2^c, Pt>- When the tensions
equilibrium

is

satisfy the critical relation,

v^
Pb,

is

W^ =

0, if

p^

=Pb =Pc =Pd-

But when

small and constant, the value of TP^ must be independent of

Pc

Pt>i

since the angles of the surfaces are determined

tensions and their curvatures

may be

neglected.

jo^,

by the

Hence, TT>;=:0, and

466

J.

W. Gibbs

Equilibriuiin of Heterogeneous Substances.

TFv=:0, when the

relation

critical

and

satisfied

is

v^.

This

small.

gives
P^.

In calculating the ratios of

Then

the vertices of which

may

be the volumes

of

E
is

we may suppose

a, b, c, d,

it

^^b,

The

e.

proportional to those of the five

ai'e

a fd y S e,
common to the

^d will
divided

^c?

may be

edges and an interior point

its

volumes of these tetrahedra

(each vertex being

not found there,) and v^,

the tetrahedra into which

by planes passing through

the

all

have the form of a tetrahedron,

will

be called

mass which

after the

v^, Vc, ^d, ^e?

?.>a,

surfaces to be plane.

named

(640)

we

tetrahedra of the figure

as will easily appear if

that the line a b

surfaces C-D, D-E, E-C, and there-

is

common

fore perpendicular to the surface

yS

to the lines

recollect

y6.,6s,ey,

and so in other cases, (it will be observed

that y, 6, and are the letters which do not correspond to a or b)
also that the surface abc is the surface D-E and therefore perpendic-

i.e.,

to the surface

ular to 6

^,

Let tetr abed, trian abc,

f, etc.

etc.

denote the volume of

the tetrahedron or the area of the triangle specified, sin (ab, be),
ein (abc, dbc), sin (abc, ad), etc. the sines of the angles

lines

and surfaces

specified,

and [B

CD E],

[C

D E A],

made by
etc.,

the

the vol-

umes of tetrahedra having edges equal to the tensions of the surfaces

Then, since we may express the
between the masses specified.
volume of a tetrahedron either by ^ of the product of one side, an edge
leading to the opposite vertex, and the sine of the angle w^hich these
make, or by f of the product of two sides divided by the common
edge and multiplied by the sine of the included angle,
v^

t'B

bcde

tetr

acde

tetr

be

sin (ba, ac) sin (be, cde)

sin {ySe, (56s) sin [aSe, a/J)

sin (be, cde)

tetr y/3de tetr

pade

trian fids trian

:

tetr yfide

[B

C D E]

tetr
:

[C

ac sin (ac, cde)

aSe

sin (ab, be) sin (ac, cde)

tetr
'

sin {ySs,

aSs)

sin (/i^^f,

(i^f:i)

yaSs tetr a/iSe

trian

ade

trian fJSe

yade

D E A].

Hence,

^-'a:Wb:^>c:'-'d::[BCDE]:[CDEA]:[DEAB]:EABC],(641)
and (640)
^'^

may be

written

_ [BCDE];>^+[CDEA]/>B+[DE AB]pc+[EABClgg
[BCDE]-f[CDEAJ + [DEAB] + [EABC]

,^^^.

J.

Wi Gihhs

If the value of />

Equilihriutn of Heterogeneous Substances.

is less

than

this,

when the

467

tensions satisfy the critical

D meet is
any mass of the nature of E.
But if the value of p-^, is greater, either the masses A, B, C, I) cannot
meet at a point in equilibrium, or the equilibrium will be at least
point where vertices of the masses A, B, C,

relation, the

stable with respect to the formation of

practically unstable.

When

new

the tensions of the

critical relation

vex toward

when

surfaces are too small to satisfy the

with the other tensions, these surfaces will be contheir tensions are too great for that relation,

the surfaces will be concave toward E.

In the

case,

first

71 y

is

negative, and the equilibrium of the five masses A, B, C, D,

is stable,

is

impossible or at least practically unstable.

when

ject to the limitation that

which

but the equilibrium of the four masses A, B, C,

at a point

will

form

only be the case

Avill

/>e is

be so small that

when p-^

is

smaller

it

in

meeting

This

sufficiently small the

may

be neglected.

sub-

is

mass

This will

general considerably smaller

than the second number of (642). In the second case, the equilibrium
of tlie five masses A, B, C, D, E will be unstable, but the equilibrium
of the four masses A, B, C,

the case of the five masses)

only be the case when

than the second

jt>E is

member

will

is

be stable unless v^ (calculated for

of insensible magnitude.

greater

in general

This will

considerably greater

of (642).

JAquid Films.

When

a fluid exists in the form of a thin film

the great inequality of

its

between other

extension in different directions

rise to certain peculiar properties,

even when

its

thickness

films,

fluids

we

shall

are

suppose that the film

gaseous.

The

fre-

and the remarkable properties which

they exhibit, entitle them to particular consideration.

ideas,

give

is sufficient

for its interior to have the properties of matter in mass.

quent occurrence of such

fluids,

Avill

The reader

is

will

To

fix

our

liquid and that the contiguous

observe our results are not

dependent, so far as their general character

is

concerned, upon this

supposition.

Let us imagine the film to be divided by surfaces perpendicular to

sides into small portions of which all the dimensions are of the

its

same order of magnitude

to be called elements

of

as the thickness of the film,

the film.., \t

is

such portions

evident that far less time will

in general be required for the attainment of

approximate equilibrium
between the difierent parts of any such element and the other fluids
which are immediately contiguous, than for the attainment of equi-

468

W. Gihbs

J.

librium between

Equilibrium of Heterogeneous Substances.

all

the diiFerent elements of the film.

There

will

accordingly he a time, commencing shortly after the formation of the

elements

film, in Avhich its separate

may be regarded

as satisfying the

conditions of internal equilibrium, and of equilibrium with the con-

may

tigiaous gases, while they

librium with each other.

not satisfy

It is M^ien the

all

the conditions of equi-

changes due to

this

want

oi

complete equilibrium take place so slowly that the film appears to be

at

rest,

except so far as

it

accommodates

external conditions to which

is

it

itself to

any change

in the

subjected, that the characteristic

properties of the film are most striking and most sharply defined.

Let us tlierefore consider the properties which will belong to a film

have the properties of matter in

sufticiently thick for its interior to

mass, in virtue of the approximate equilibrium of

taken separately, when

the matter contained in

all

its

elements

each element

is

regarded as invariable, with the exception of certain substances

which are components of the contiguous gas-masses and have their
potentials thereby determined.

The occurrence

cisely satisfies these conditions

may

somewhat

sion of this

ideal case will enable us to understand the

laws which determine the

principal

of a film which pre-

be exceptional, but the discusbehavior of liquid

films

in

general.

Let us

first

consider the properties which will belong to each

ele-

under the conditions mentioned. Let us suppose

ment
while the temperature and the potentials
extended,
the element
which are determined by the contiguous gas-masses are unchanged.
If the film has no components except those of which the potentials
are maintained constant, there will be no variation of tension in its
of the film

The same

surfaces.

will

be true when the

ponent of which the potential

that this

is

is

film has only

one com-

not maintained constant, provided

a component of the interior of the film and not of

face alone.

If

we regard

its sur-

the thickness of the film as determined

by

dividing surfaces which make the surface-density of this component vanish, the thickness will vary inversely as the area of the ele-

ment of the

film,

but no change will be produced

in the

nature or

the tension of its surfaces. If, however, the single component of

which the potential is not maintained constant is confined to the surfaces of the film, an extension of the element will generally produce
a decrease in the potential of this component, and an increase of tension.

This will certainly be true

in those cases in

nent shows a tendency to distribl^te

density.

itself

which the compo-

with a uniform superficial

J.

When

W. Gibhs

Equilibriurn of Heterogeneous Substances.

the film has two or more components of which the potentials

are not maintained constant

by the contiguous gas masses, they

not in general exist in the same

on

its sui-faces,

be found

469

will

proportion in the interior of the film as

but those components which diminish the tensions will

in greater proi>ortion

When

on the surfaces.

the film

is

ex-

tended, there will therefore not be enough of these substances to keep

up the same volume- and surface-densities as before, and the deficiency

The value

will cause a certain increase of tension.

the film.,

{i.

e.,

of the elasticity

the infinitesimal increase of the united tensions of

by the

surfaces divided

of
its

infinitesimal increase of area in a unit of sur-

may

be calculated from the quantities which specify the nature

of the film, when the fundamental equations of the interior mass, of

face),

the contiguoixs gas-masses, and of the two surfaces of discontinuity

are

We may

known.

illustrate this

by

a simple example.

Let us suppose that the two surfaces of a plane film are entirely
alike, that

the contiguous gas-masses are identical in phase, and that

they determine the potentials of

Let us

except two.

call these

all the components of the film

components S^ and S2, the latter

denoting that which occurs in greater proportion on the surface than

Let us denote by y

in the interior of the film.

of these components in the interior of the film,

the film determined

by such dividing

surfaces

and

j/g ^^he

densities

by A the thickness of
as make the surface-

by I^^n) ^^^ surface-density of

determined by the same surfaces, by ff and s

density of S^ vanish (see page 397),

the other component as

the tension and area of one of these sui'faces, and

of the film

when extended under

by ^the

elasticity

the supposition that the total quan-

and So in the part of the film extended are invariable, as

temperature
and the potentials of the other components.
also the
tities

From

of

/Nj

the definition of JS

we have
2dff

= B-,

(643)

and from the conditions of the extension of the

d{X

ds

)/j)

d{X y^

^ri

film

2 -^2(1))

(644)

^X3+2/'2(i)

Hence we obtain
\ y^

=. y

+ 2 ^2( 1)) =

A dy^.,

d\

ds

(^

r2

and eliminating dX,

72

<^^

'^

(h'2

2 f?^2(i)

470

J.

W.

(xibbs

Equilihriimi of Heterogeneous Substances.

(645)

-^Vi'^^^^d^rJ^2^v-=-^ri(b'2-\-^r-i^b'i
s
If

we

set

we have

.j,

= ll,

(646)

'

^ y^dy^nXldy,

(647)

y.'
ds

and

= \ y^dr 2d^2^^,.

2 I\^^^

With

tliis

equation

eliminate dcf

we may

eliminate ds from (643).

by the necessary

Avill

We may

also

relation [see (514)]

dff =^

This

-(648)

^2(1)^^2-

give
4 / 2^2 ^^,^

^ (A ^^ dr-^2 dP^,,,),

(649)

or

~+

^^4^= A y,
where the

differential coefficients are to

tions that the temperature

are constant,

and

all

and that the pressure

-%^\

(650)

he determined on the condi-

the potentials except

may he

//g

The

latter con-

expressed by the equation

ir i-Vi') '^Mi
in

and

in the interior of the film shall

remain equal to that in the cootiguous gas-masses.

dition

/u^

-f-

which y^' and y2' denote the

tiguous gas-masses.

densities of

[See (98).]

of the film and the pressures in

(r2 -rs') ^hh

When

its interior

/S^

(65i)

o,

and S^

in

the con-

the tension of the surfaces

and

in

the contiguous gas-

masses are known in terms of the temperature and potentials, equation (650) will give the value of

together with
If

E in

terms of the same variables

A.

we write G^ and G^

unit of area of the film,

for the total quantities of S^

and

S.^

per

we have

G,=:ly

(652)

G,=Ay,-\-2r,,,,^,

(653)

Therefore,

G^=G,r+2l\^,

=A;.,i^+2^i^lll,

(p)

(654)

where the difierential coefficients in the second member are to be

determined as in (650), and that in the first member with the additional condition that

is

constant.

Therefore,

J.

W. Gibbs

Equilibrmim of Heterogeneous Substances.

471

2(1)

\ dfi^

k-

the last differential coefficient being determined by the same condiIt will be observed that the

tions as that in the preceding equation.

will be positive in any ordinary case.

These equations give the elasticity of any element of the film when
the temperature and the potentials for the substances which are found
in the contiguous gas-masses are regarded as constant, and the poten-

value of

tials for the

other components,

yu,

and

themselves throughout the element

tension immediately after

ju.^,

have had time to equalize

The

considered.

increase

of

a rapid extension will be greater than that

given by these equations.

The

existence of this elasticity, which has thus been established

from a priori considerations, is clearly indicated by the phenomena

which liquid films present. Yet it is not to be demonstrated simply
by comparing the tensions of films of different thickness, even when
they are made from the same liquid, for difference of thickness does
not necessarily involve any difference of tension. When the phases
within the films as well as without are the same, and the surfaces of
the films are also the same, there will be no difference of tension.

Nor

will the tension of the

rior drains

away

same

be altered,

in the course of time,

stance

/S'j,

tension.)

a part of the inte-

without affecting the surfaces.

in

Yet

the case
it

is

we have

may

easily be

would diminish the

shown that extension increases the

just considered,

tension of a film and contraction diminishes

is

if

reduced by evaporation, the tension

be either increased or diminished. (The evaporation of the sub-

In case the thickness of the film

may

film

it.

When

a plane film

held vertically, the tension of the upper portions must evidently

be greater than that of the lower.

may be reduced to
By restoring the
tion.

film

tensions, or nearly so.

equality

The tensions in every part of the

by turning it into a horizontal posi-

original position
It

is

we may

restore the original

evident that the same element of the

film is capable of supporting very unequal tensions.

Nor

can this be

always attributed to viscosity of the film. For in many cases, if we

hold the film nearly horizontal, and elevate first one side and then an
other, the lighter portions of the film will dart from one side to the
other, so as to

show

a very striking mobility in the film.

ences of tension which cause these rapid

Trans. Conn. Acad., Vol.

III.

60

movements

The

differ-

are only a very

March,

1818.

472

J.

W. Gihhs

Equilihrium of Heterogeneous Substances.

small fraction of the difference of tension in the upper and lower

portions of the film
If

we account

when held
power

for the

increase of tension

by

vertically.

of an element of the film to support an

viscosity,

it

will

be necessary to suppose that

the viscosity offers a resistance to a deformation of the film in which

surface is enlarged and its thickness diminished, which is enormously great in comparison with the resistance to a deformation in
which the film is extended in the direction of one tangent and con-

its

tracted in the direction of another, while

of

surfaces remain constant.

its

This

is

its

thickness and the areas

not to be readily admitted

as a physical explanation, although to a certain extent the

phenomena

resemble those which would be caused by such a singular viscosity.

The only natural explanation

(See page 439.)

of the

that the extension of an element of the film, which

is

phenomena

is

the immediate

result of an increase of external force applied to its perimeter, causes

an increase of

its

tension,

by which

it is

brought into true equilibrium

Avith the external forces.

The phenomena

to

which we have referred are such as are apparent

In the following experiment, which

to a very cursory observation.

is

described

by M. Plateau,* an

increased tension

film while contracting after a previous extension.

is

manifested in a

The warmth

finger brought near to a bubble of soap-water with glycerine,

is

thin enough to

show

colors, causes a spot to

When

a diminution of thickness.

returns to

would be

its

original color.

resisted

by any

the finger

is

of a

which

appear indicating

removed, the spot

This indicates a contraction, which

viscosity of the film, and can only be due

to an excess of tension in the portion stretched on the return of its

original temperature.

We have

so far supposed that the film is thick enough for its intehave the properties of matter in mass. Its properties are then
entirely determined by those of the three phases and the two surfaces

rior to

of discontinuity.

From

these

we can

also determine, in part at least,

the properties of a film at the limit at which the interior ceases to

have the properties of matter in mass. The elasticity of the film,

which increases with its thinness, cannot of course vanish at that
limit, so that the film cannot become unstable with respect to extension

and contraction of

its

elements immediately after passing that

limit.

Yet a

certain kind of instability will probably arise,

which we

may

* " Statique experimentale et theorique des liquides soumis aux seules forces moleculaires," vol.

i,

p.

294.

W. Gihhs

J.

Equilibrium, of Seterogeneous Substances.

here notice, although

it

473

changes in which the condition of

relates to

the invariability of the quantities of certain components in an element

of the film

is

bution of

its

not

With

satisfied.

components, a film

respect to variations in the distriin

will

general be stable,

when

its

interior has the properties of matter in mass, with the single exception

of variations afiecting

its

thickness without any change of phase or of

the nature of the surfaces.

With

may be brought about by

a current in the interior of the film, the

equilibrium

is

neutral.

But when the

perties of matter in mass,

will generally

respect to this kind of change, which

it

is

become unstable

interior ceases to

have the pro-

to be supposed that the equilibrium

in this respect.

For

it is

not likely

that the neutral equilibrium will be unaffected by such a change of

circumstances, and since the fihn certainly becomes unstable

is

reduced

sufficiently

the

first effect

in tliickness,

it is

most natural

to

when

it

suppose that

of diminishing the thickness will be in the direction of

instability rather tlian in that of stability.

(We

are here considering

In certain other cases, the

between gaseous masses.
opposite supposition might be more natural, as in respect to a film of

liquid films

water between mercury and

when

sufficiently

Let us

enough

now

reduced

air,

which would certainly become stable

in thickness.)

return to our former suppositions

for the interior to

that the film

have the properties of matter

that the matter in each element

is

in

is

thick

mass, and

invariable, except with respect to

those substances which have their potentials determined by the con-

tiguous gas-masses

and

consider what conditions are necessary for

equilibrium in such a case.

In consequence of the supposed equilibrium of

such a film

may

its

several elements,

be treated as a simple surface of discontinuity

between the contiguous gas-masses (which may be similar or different),

whenever its radius of curvature is very large in comparison with its
thickness,
a condition which we shall always suppose to be fulfilled.

With

respect to the film considered in this light, the mechanical

conditions of equilibrium will always be satisfied, or very nearly so,

as soon as a state of approximate rest

cases in which the film

is

attained, except in those

exhibits a decided viscosity.

relations (613), (614), (615) will hold true,

That

is,

the

when by a we understand

the tension of the film regarded as a simple surface of discontinuity

sum of the tensions of the two surfaces of

mass per unit of area diminished by the mass
of gas which would occupy the same space if the film should be suppressed and the gases should meet at its surface of tension. This
(this is

equivalent to the

the film), and

by

/" its

474

W. Gihbs

J.

Equilibrium of Heterogeneous Substances.

surface of tension of the flni will evidently

between the surfaces of tension

divide the distance

two surfaces of the film taken

separately, in the inverse ratio of their tensions.
For practical purposes, we may regard F simply as the mass of the film per unit of
area.
It will be observed that the terms containing Fin (613) and
for the

(614) are not to be neglected in our present

application of these

equations.

But the mechanical conditions of equilibrium for the film regarded

homogeneous mass in the form of a thin sheet
bounded by two surfaces of discontinuity are not necessarily satisfied
when the film is in a state of apparent rest. In fact, these conditions
cannot be satisfied (in any place where the force of gravity has an
appreciable intensity) unless the film is horizontal. For the pressure
as an approximately

in

the interior of the film cannot satisfy simultaneously condition

which requires

(612),

to vary rapidly "wdth the height

it

tion (613) applied separately to the difierent surfaces,

z,

and condi-

which makes

it

a certain

mean between the

Nor can

these conditions be deduced from the general condition

pressures in the adjacent gas-masses.

of mechanical equilibrium (606) or (611), without supposing that the

interior of the film

which

is

free

is

contrary to what

to

move independently

of the surfaces,

we have supposed.

Moreover, the potentials of the various components of the film will

not in general satisfy conditions (617), and cannot (when the temperature

is

were

tions

uniform) unless the film

satisfied,

is

horizontal.

For

if

these condi-

equation (612) would follow as a consequence.

(See page 449.)

We may here remark

that such a film as

we

are considering cannot

form any exception to the principle indicated on page 450, that

when a surface of discontinuity which satisfies the conditions of
mechanical equilibrium has only one component which is not found
in the contiguous masses, and these masses satisfy all the conditions
of equilibrium, the j^otential for the component mentioned must satisfy
the law expressed in (617), as a consequence of the condition of
mechanical equilibrium (614). Therefore, as we have just seen that
it is

impossible that

all

the potentials in a liquid film which

zontal should conform to (617)

follows that

if

when

a liquid film exhibits

the temperature

is

is

not hori-

uniform,

any persistence which

is

it

not due

to viscosity, or to a horizontal position, or to diiferences of temperature,

is

it

must have

nioi-e

than one component of which the potential

not determined by the contiguous gas-masses in accordance with

(617).

J.

The

W. Gihbs

Equilibrium of Heterogeneous Substances.

difficulties of

475

the quantitative experimental verification of the

properties which have been described would be very great, even in

cases in which the conditions

Yet the general

filled.

effect

tions will be easily perceived,

we have imagined were

entirely ful-

of any divergence from these condi-

and when allowance

is

made

for such

divergence, the general behavior of liquid films will be seen to agree

with the requirements of theory.

most symmetrically
The
rises to the top of a mass of the liquid.
motion of the liquid, as it is displaced by the bubble, is evidently
such as to stretch the two surfaces in which the liquid meets the air,
This will cause an
where these surfaces approach one another.
increase of tension, which will tend to restrain the extension of the
The extent to which this effect is produced will vary with
surfaces.

The formation of a
when a bubble of air

liquid film takes place

Let us suppose that the case is one in

which the liquid contains one or more components which, although
constituting but a very small part of its mass, greatly reduce its tension.
Such components will exist in excess on the surfaces of the
liquid.
In this case the restraint upon the extension of the surfaces
will be considerable, and as the bubble of air rises above the general

the nature of the liquid.

level of the liquid, the

motion of the

latter will consist largely of a

running out from between the two surfaces.

the liquid will be greatly retarded

reduced to the thickness of a

the

surfaces

increasing

in

more permanent

film,

their

by

its

and the

But

this

running out of

viscosity as soon as

it is

effect of the extension of

tension will

become greater and

which is avail-

as the quantity of liquid diminishes

able for supplying the substances which go to form the increased surfaces.

We

may form

rough estimate of the amount of motion which

possible for the interior of a liquid film, relatively to its exterior,

is

by

calculating the descent of water between parallel vertical planes at

which the motion of the water is reduced to zero. If we use the

coefficient of viscosity as determined by Helmholtz and Piotrowski,*

we

obtain

V= 581 Z)3,
where

V denotes

the

mean

velocity of the water

(656)
[i. e.,

that velocity

* Sitzungstaerichte der Wiener Akademie, (mathemat.-natiirwiss. Classe), B.

607.

The

xl, S.

calculation of formula (656) and that of the factor (5) applied to the formula

to adapt it to a current between plane surfaces, have been made by

means of the general equations of the motion of a viscous liquid as given in the
memoir referred to.

of Poiseuille,

476

W. Gihbs

J.

which,

if it

fixed planes,

Equilibrium, of Heterogeneous Siihstances.

Avere uniform throiighout the

whole space between the

would give the same discharge of water as the actual

variable velocity) expressed in millimetres per second, and

D denotes

the distance in millimetres between the fixed planes, which

posed to be very small

in

proportion to their other dimensions.

for the temperature of 24.5 C.

experiments of Poiseuille * give

is

Vfor the descent of

water

in

equation

between

difi^ers

sup-

This

For the same temperature, the

337 Z>3

long capillary tubes, which

F=r
for descent

is

is

equivalent to

899 Z>2

parallel planes.

(657)

The numerical

coeflicient in this

considerably from that in (656), which

exj^eriments of an entirely different nature, but

is

derived from

we may

at least con-

clude that in a film of a liquid which has a viscosity and specific

gravity not very ditferent from those of water at the temperature

mentioned the mean velocity of the interior relatively to the surfaces

This is a velocity of .1""" per
will not probably exceed 1000 D^.
,06"'
.01""",
per minute for a thickness of
second for a thickness of
.001

(which corresponds to the red of the

fifth

order in a film of

water), and .036'" per Jiour for a thickness of .0001"' (which corre-

sponds to the white of the first order). Such an internal current

evidently consistent with great persistence of the film, especially
those cases in which

On

tenuity.

tlie

is

in

film can exist in a state of the greatest

the other hand, the aljove equations give so large a

value of T^for thicknesses of

1"'"'

or .1"\ tliat the film can evidently

be formed without carrying up any great weight of liquid, and any

such thicknesses as these can have only a momentary existence.

A little

consideration will show that the phenomenon is essentially

same nature when films are formed in any other way, as by
dipping a ring or the mouth of a cup in the liquid and then withdrawing it. When the film is formed in the mouth of a pipe, it may
of the

sometimes be extended so as to form a large bubble. Since the elasticity {i. e., the increase of the tension with extension) is greater in
the thinner parts, the thicker parts will be most extended, and the
effect of this process (so far as it is not modified by gravity) will be
to diminish the ratio of the gre'atest to the least thickness of the film.
During this extension, as well as at other times, the increased elas-

due to imperfect communication of heat, etc., will serve to protect the bubble from fracture by shocks received from the air or the
ticity

* Ibid., p. 653

or Memoires des Savants Strangers, vol.

ix, p. 5.32.

W. Gibbs

J.

Eqidlibrhnn of Heterogeneous Substances.

bubble

pipe.

If the

tion

(613) will

477

noAv laid upon a suitable support, the condi-

is

The bubble

be realized almost instantly.

tend toward conformity

will then

Avith condition (6l4j, the lighter portions ris-

ing to the top, more or less slowly, according to the viscosity of the

The

film.

resulting diflterence of thickness between the upper

and

due partly to the greater tension to

which the upper parts are subject, and partly to a diflerence in the
matter of which they are composed. When the film has only two
components of which the potentials are not determined by the con-

the lower parts of the bubble

is

tiguous atmosphere, the laws which govern the arrangement of the

elements of the film

may

be very simply expressed.

If Ave call these

components S^ and S.^, the latter denoting (as on page 469) that
which exists in excess at the surface, one element of the film will
tend toward the same level with another, or a higher, or a lower
level,

according as the quantity of S^ bears the same ratio to the

quantity of

aSj

in the first

element as

in the second, or a gi*eater, or a

less ratio.

When
and

a film, however formed, satisfies both the conditions (613)

(614), its thickness being sufficient for its interior to

properties of matter in mass, the interior will

slow current which

ever great
this

its

process

have the

be subject to the

we have already described, if it is truly fluid, howmay be. It seems probable, however, that

viscosity

often totally arrested l)y a certain gelatinous consist-

is

ency of the mass in question,

fluid in its

still

in virtue of

which, although practically

beha\nor with reference to ordinary stresses,

it

may have

the properties of a solid with respect to such very small stresses as

those which are caused by gravity in the interior of a vejy thin film

which

satisfies

However
potent

in

the conditions (613) and (614).

this

may

be, there

producing changes

is

another cause which

a film,

in

when the

often

is

more

conditions just men-

tioned are approximately satisfied, than the action of gravity on

This will be seen

interior.

where the

film is terminated.

if

its

we turn our attention to the edge

At such an edge we generally find a

liquid mass, continuous in phase with the interior of the film,

is

bounded by concave

less

surfaces,

and

than in the interior of the

in

film.

which
which the pressure is therefore
This liquid mass therefore

exerts a strong suction upon the interior of the film, by which

thickness

is

rapidly reduced.

which has been formed

This

efiect

is

best seen

when

in a ring is held in a vertical position.

its

a film

Unless
diminished thickness near the edge causes
a rapid upwai'd current on each side, Avhile the central portion slowly

the film

is

very viscous,

its

478

W. Gibbs

J.

Equilibrium of Heterogeneotis Sxibstances.

Also at the bottom of the

film, where the edge is nearlywhich have become thinned escape from their
position of unstable equilibrimn beneath heavier portions, and pass
upwards, traversing the central portion of the film until they find a
position of stable equilibrium.
By these processes, the whole film is
rapidly reduced in thickness.

descends.

horizontal, portions

The energy of the

inferred from the

suction which

produces these

following considerations.

slender liquid rnass which encircles the film

effects

may be

The pressure
is

the

in

of course variable,

being greater

in the lower portions than in the upper, but it is everywhere less than the pressure of the atmosphere. Let us take a point
where the pressure is less than that of the atmosphere by an amount
represented by a column of the liquid one centimetre in height.
(It

is

much

probable that

point near

by

At

greater diflerences of pressure occur.)

in the interior of the film the pressure is that of the

Now if the difference of pressure of these two points

were distributed uniformly through the space of one centimetre, the
intensity of its action would be exactly equal to that of gravity.
But since the change of pressure must take place very suddenly (in
atmosphere.

a small fraction of a millimetre),

limited

space must be

its effect in

producing a current

enormously great compared with

in a

that of

gravity.

Since the process just described

the

liquid

in

the

another example of the

film.

There

when

the

is

a third

principal

through the

air.

is

connected with the descent of

film, we may regard it as

downward tendency of the interior of the
way in which this descent may take place,

mass encircling the

component of the

interior

is

volatile,

Thus, in the case of a film of soap-water,

viz.,
if

we

suppose the atmosphere to be of such humidity that the potential for

water at a level mid-way between the top and bottom of the film has

may

be
and
condensation in the lower. These processes, if the atmosphere were
otherwise undisturbed, would occasion currents of diffusion and other
currents, the general effect of which would be to carry the moisture
downward. Such a precise adjustment would be hardly attainable,
and the processes described would not be so rapid as to have a practhe same value in the atmosphere as in the film,

shown that evaporation

tical

it

easily

will take place in the U])per portions

importance.

But when the

potential for water in the atmosphere differs con-

siderably from that in the film, as in the case of a film of soap-water

in a

dry atmosphere, or a

film of soap-water with glycerine in a moist

W. Gihhs

J.

atmospliere,

tlie

Equilibrium of Heterogeneous Substances.

In the

neglected.

evaporation or condensation

cftfct of
tirst

is

479

not to be

case, the diminution of the thickness of the

be accelerated, in the second, retarded. In the case of the

film containing glycerine, it should be observed that the water confilm will

densed cannot

in

all

down by

respects replace the fiuid carried

the

internal current but that the two processes together will tend to
,

the glycerine from the film.

wash oiit
But when a com])onent which greatly diminishes the tension of the
although forming but a small fraction of

film,

existing in excess at the surface,)

its

mass, (therefore

evaporation

volatile, the effect of

is

when the mean value

of
and condensation may
the
sui-the
film
as
in
the potential for that component is the same in
rounding atmosphere. To illustrate this, let us take the simple case
of two components /S'j and xS'^, as before. (See page 469.) It appears
from equation (508) that the potentials must vary in the film with
the height 3, since the tension does, and from (98) that these varia-

be considerable, even

must (very nearly)

tions

;/j

and y^ denoting the

The

film.

satisfy the relation

and

densities of S^

S.^

to another

is

therefore as

much more

density in the interior of the film

is

in the interior of the

we pass from one

variation of the potential of S2 as

rapid than that of

less.

aS'j,

level

as its

If then the resistances

restraining the evaporation, transmission through the atmosphere,

and condensation of the two substances are the same, these processes
It will be
will go on much more rapidly with respect to S^.
observed that the values of

-^

and

the tendency of S^ being to pass

that of S

to pass up.

So,

it

will

may

the atmosphere, and

easily be

shown that the

produce a very much greater

These

efi'ects

are really of the

same kind.

of S^ takes place at the top of the film,

tension,

which
/Sj.

sigiis,

than the evapcu-ation or condensation of the same quantity of

effect

S^.

have opposite

down through

Moreover,

evaporation or condensation of

will

dz

dz

For

if

will cause a

condensation

diminution of

and thus occasion an extension of this part of the film, by

thickness will be reduced, as it would be by evaporation of

its

We may

infer that

it is

a general condition of the persistence of

liquid films, that the substance

in the

it

which causes the diminution of tension

upper parts of the film must not be

But apart

volatile.

from- any action of the atmosphere,

Trans. Conn. Acad., Vol.

III.

61

we have

seen that a
April, 1878.

48C
filiii

J.

W. Gibbs

which

is

EquUlhria))) of Ileterof/eneotis /Substances.

truly fluid in its interior

tinual diminution of thickness

by the

is in

general subject to a con-

internal currents due to gravity

and the suction at its edge. Sooner or, later, the interior wall somewhere cease to have the properties of matter in mass. The film will
then probably become unstable with respect to a flux of the interior

page 473), the thinnest parts tending to become still more thin
any external cause) very much as if there were an
attraction between the surfaces of the film, insensible at greater dis(see

(apart from

tances, but

becoming sensible when the thickness of the

ciently reduced.

We

the film, and such

is

film is

suffi-

should expect this to determine the rupture of

doubtless the case with most liquids.

In a film

of soap-water, however, the rupture does not take place, and the
processes which go on can be watched.
superficial observation that a film of

It is

apparent even to a very

which the

the black exhibits a remarkable instability.

of tint

is

interrupted

black spots.

That

by

tint is

approaching

The continuous change

the breaking out and rapid extension of

the formation of these bright spots a separa-

in

tion of different substances takes place,

of a part of the film,

shown by the

is

and not simply an extension

fact that the film is

made

when a

single

thicker at the edge of these spots.

This

is

very distinctly seen in a plane vertical

film,

black spot breaks out and spreads rapidly over a considerable area
Avhich was before of a nearly uniform tint approaching the black.
The edge of the black spot as it sj^reads is marked as it were by a

which unite together on touching, and thrus

Under
across the bands of color below.
favorable circumstances, there is often quite a shower of these bright
string of bright beads,

becoming
spots.

ently

larger, glide

They

many

down

are evidently small spots very

times thicker

they are formed.

Now

than

if

much

thicker

appar-

the part of the film out of which

the formation of the black spots were due

to a simple extension of the film,

it is

evident that no such appear-

The thickening of the edge of the film

ance would
For an extension of the
for
by
contraction.
cannot be accounted
film
and
contraction of the lower and thicker
upper portion of the
portion, with descent of the intervening portions, would be far less
resisted by viscosity, and far more favored by gravity than such
extensions and contractions as would produce the appearances
But the rapid formation of a thin spot by an internal
described.
be presented.

current would cause an accumidation at the edge of the spot of the

material forming the interior of the film, and necessitate a thickening
of the film in that place.

J.

W. Gibbs

That which
black spots
ner.

Equilibrium of Heterogeneous Substances.

most

is

difficult to

account for

arrest of the process

is tlie

by

fonuatiou of the

iu the

wliich the fihn

seems most natural to account for

It

this,

481

grows

if possible.,

thin-

by passive

resistance to motion due to a very viscous or gelatinous condition of

For
unstable by the

the film.

does not seem likely that the film, after becoming

it

flux of

matter from

its interioi-,

would become stable

resistance) l)y a continuance of the

(without the support of such

same process. On the other hand, gelatinous properties are very

marked in soap-water which contains somewhat more soap than is
best for the formation of films, and it is entirely natural that, even
when such properties are wanting in the interior of a mass or thick
film of a liquid, they may still exist in the immediate vicinity of the
surface (wdiere we know that the soap or some of its conii)onents
exists in excess), or throughout a film which is so thin that the
interior has ceased to have the })roperties of matter in mass.*
But
these considerations do not amount to any a priori probability of an
arrest of the tendency toward an internal current between adjacent
elements of a black spot which may differ slightly in thickness, in
time to prevent rupture of the

For, in a thick film, the increase

film.

of the tension Avith the extension, which

with respect to extension,

is

necessary for

is

connected with

an

its

stability

excess

of

the

components) at the surface as compared with

soap (or of some of

its

the interior of the

film.

With

respect to the black spots, although

the interior has ceased to have the properties of matter in mass, and

any quantitative determinations derived from the surfaces of a mass

of the liquid
stability with

not be applicable,

Avill

general difterence of composition

for the

arrest

of

soap or some of
still

its

components

and surface of the

The preceding

natural to account for the

by supposing that the same

still exists.

currents

by

If therefore

the increasing

in the interior of

suppose that the characteristic

interior

gas.

internal

is

it

extension

reference to

diftei-ence of

film has not

we account
density

the film,

of

we must

composition

in the

been obliterated.

discussion relates to liquid films between masses of

Similar considerations will apply to liquid films between other

liquids or

between a liquid and a gas, and

to films of gas

between

* The experiments of M. Plateau (chapter VII of the work already cited) show that
this is the case to a very remarkable degree with respect to a solution of saponine.

With respect

to soap-water,

however, they do not indicate

we

are considering,

is

anj^ greater

superficial

But the resistance to an internal current, such as

not necessarily measured by the resistance to such motions

viscosity than belongs to pure water.

as those of the experiments referred

to.

482

J.

W. Gibbs

masses of

Equilibrium of Heterogeneous Substances.

The

liquid.

liquid drop upon

This

liquid.

may

latter

may

be formed by gently depositing a

the surface of a

be done

mass

of the

same or a

tinuity of the air sepai'ating the liquid drop and mass

but a film of air

is

is

not broken,

formed, which, if the liquids are similar, is a

counterpart of the liquid film which

is

formed by a bubble of

ing to the top of a mass of the liquid.

volume

different

(with suitable liquids) so that the con-

as the drop, the films will

(If

air ris-

the hul)ble has the same

have precisely the same form, as

bound the l)ubl)le and the

well as the rest of the surfaces which

Sometimes, when the weight and

drop.)

carry

it

momentum

through the surface of the mass on which

surrounded by a comj^lete spherical film of

which

air,

of the

is

the counter-

part on a small scale of a soap-bubble hovering in air.*

ever, the substance to

drop

appears

it falls, it

Since,

how-

which the necessary differences of tension

the film are mainly due

is

component of

tlie

in

liquid masses on each

side of the air film, the necessary differences of the potential of this

substance cannot be permanently maintained, and these films have

little

persistence

compared with

films of soap-water in air.

respect, the case of these air-films

is

an atmosphere containing siibstances by which

in

greatly reduced.

Compare page

their tension

is

479.

Surfaces of Discontinuity between Solids

We

In this

analogous to that of liquid films

and

Fluids.

have hitherto treated of surfaces of discontinuity on the sup-

position that the contiguous masses are fluid.

This

is

by

far the

any rigorous treatment, since the masses are

necessarily isotropic both in nature and in their state of strain.
In

most simple case

for

this case, moreover, the mobility of the

masses allows a satisfactory

experimental verification of the mechanical conditions of equilibrium.

On

the other hand, the rigidity of solids

is

in general so great, that

any tendency of the surfaces of discontinuity to variation in area or

form may be neglected in comparison with the forces which are pi"oduced in the interior of the solids by any sensible strains, so that it
is

not generally necessary to take account of the surfaces of discon-

But we
must take account of the nature of the surfaces of discontinuity
tinuity in determining the state of strain of solid masses.

* These spherical air-films are easily formed in soap-water.

They

are distinguish-

able from ordinary air-bubbles by their general behavior and by their appearance.

The two concentric spherical surfaces are

ing to be about three-quarters
optical illusion,

distinctly seen, the diameter of

as large as that of the other.

depending upon the index of refraction of

one appear-

Tliis is of

tlie li(j\iid.

course an

J. TF.

between

Gihhs

Equillbriinti of

and

solids

fluids

483

IIeteroge)ieoiis Stihstances.

with reference to the tendency toward

solidification or dissolution at such surfaces,

and also with reference to

the tendencies of different fluids to spread over the surfaces of solids.

Let us therefore consider a surface of discontinuity between a fluid

and a

solid, the latter

line structure,

being either isotropic or of a continuous crystal-

and subject to any kind of

stress

compatible with a

We

state of mechanical equilibrium with the fluid.

shall not exclude

the case in which substances foreign to the contiguous masses are

present in small quantities at the surface of discontinuity, but

suppose that the natiire of this surface

shall

{i.

we

of the non-hoiiio-

e.^

geneous film between the approximately homogeneous masses),

by the nature and

entirely determined

state of the masses wliich

is
it

and the quantities of the foreign substances which may be

])resent.
The notions of the divkUng surface^ and of the superficial
densities of energy, entropy, and the several components, which we
have used with respect to surfaces of discontinuity between fluids
separates,

(see

pages 380 and 386), will evidently ^pply without modification to

We shall use the suffix with reference to the

the present case.

substance of the solid, and shall suppose the dividing surface to be

determined so as to make the superficial density of this substance

The

vanish.

suj)erficial

densities of energy, of entropy,

may

other com})onent siibstanees

bols (see

and of the

then be denoted by our usual sym-

page 397),
^S(l)5

Let the quantity

ff

VhDI

^ 2(1)J

^ 3(1)5

6tc.

be defined by the equation

^=^S(i)-^Vs(i,-/^2 ^2U)-/^3^^3(l)-etC.,
in

which

denotes the temperature, and

yUg? /^s?

^^c.

(659)

the potentials

for the substances specified at the surface of discontinuity.

As
0'

two fluid masses, (see page 421,) we may regard

work spent in forming a unit of the surfiice
under certain conditions, which we need not here

in the case of

as expressing the

of discontinuity
specify

but

it

cannot properly be regarded as expressing the tension

of the surface.

The

latter quantity

depends upon the work spent in

stretching the surface, while the quantity

spent

m forming

the surface.

With

G depends upon

the

work

respect to perfectly fluid masses,

these processes are not distinguishable, unless the surface of discontinuity has com2:)onents which are not found in the contiguous masses,

and even

in this case, (since the surface

must be supposed

to be

formed

out of matter supplied at the same potentials which belong to the matter in the surface,) the

work

S]ient in increasing the surfiice infinitesi-

W. Gibbs Equilibr'm^n of Heterogeneous

484

J.

nially

by stretching

which must be spent in

But when one

identical with that

is

Substances.

forming an equal infinitesimal amount of new surface.

of the

masses

there

is

and

is solid,

of strain are to be distinguished,

its states

no such equivalence between the stretching of

surface

tlie

and the forming of new surface.*

With

we now

these preliminary notions,

proceed to discuss the

condition of equilibrium which relates to the dissolving of a

the surface where

meets a

it

fluid,

when

conditions of equilibiinm are satisfied.

sf>lid

at

the thermal and mechanical

It will

be necessary

for us to

consider the case of isotropic and of crystallized bodies separately,

since in the former the value of

the surface, excei)t so far as

is

independent of the direction of

may be

it

of the solid, while in the latter the value of

direction of

by the

influenced

state of strain

varies greatly with the

surface with respect to the axes of crystallization, and

tlie

such a manner as to have a large number of sharply defined

in

minima.f

may

This

be inferred from the phenomena which crystal-

bodies present, as will appear more distinctly in the following

line

discussion.

Accordingly, while a variation in the direction of an

* This will appear more distinctly

if

we

consider a particular case.

a thin plane sheet of a crystal in a vacuum (which

of a very attenuated

By applying

alike.

vanish in
forces,

fluid),

and

let

may

us suppose that the two surfaces of the sheet are

the proper forces to the edges of the sheet,

The

its interior.

Let us consider

be regarded as a limiting case

tensions of the

two

But the tensions of the

and are measured by them.

we

can

make

all stress

surfaces, are in equilibrium with these

surfaces, thus determined,

evidently have different values in different directions, and are entirely different

may

from the quantity which we denote by a, which represents the work required to form
a unit of the surface by any reversible process, and is not connected with any idea of
direction.

In certain cases, however,

superficial tension will

it

appears probable that the values of c and of the

not greatly

differ.

bodies which, although generally (and for

are really very viscous fluids.
actual temperature,

the body was

if its

fluid,

Even when a body

is

especially true of the

numerous
as solids,

exhibits no fluid properties at

its

surface has been formed at a higher temperature, at which

and the change from the

insensible gradations,
ficial

This

many purposes properly) regarded

we may

fluid to the

solid state

has been by

suppose that the value of a coincided with the super-

was decidedly solid, and that they will only differ so far
by subsequent variations of temperature and of tlie
Moreover, when an amorphous solid is in a state of
the solid.

tension until the body

as they

may be

differently affected

stresses applied to

equilibrium with a solvent, although

it

may have no

fluid properties in its interior,

it

seems not improbable that the particles at its surface, which have a greater degree of
mobility, may so arrange themselves that the value of a will coincide with the superficial

tension, as in the case of fluids.

The

differential coefficients of a

with respect to the direction-cosines of the surface

appear to be discontinuous functions of the

latter quantities.

W.

J.

Gihhi<

E(pdlihriam of Jleterof/eneous Substances.

element of the surface

may

be neglected (with respect to

the value of g) in the case of isotropic solids,

with crystals.

Also,

and soluble isotropic

being

on

its effect

quite otherwise

it is

the surfaces of equilibrium between fluids

without discontinuities of direction,

solids are

general curved, a crystal in a state of equilibrium with a

in

fluid in

Avdiile

485

which

can dissolve

it

bounded

is

in

general by a broken sur-

face consisting of sensibly plane portions.

For

isotropic solids, the conditions of equilibrium

as follows.

we suppose

If

that the solid

is

may

be deduced

unchanged, except that an

is dissolved at the surface where it meets the

and that the fluid is considerable in quantity and remains
homogeneous, the increment of energy in the vicinity of the siirface

infinitesimal portion
fluid,

will

be represented by the expression

where

Ds

])Osition
is

denotes an element of the surface, dJSf the variation in

its

(measured normally, and regai'ded as negative when the solid

dissolved),

and

e^

Cg

principal

its

curvatures

on the same side as the

(positive

when

%!, the surfacedensity of energy, e^' and y" the volume-densities of energy in the
solid and fluid respectively, and the sign of integration relates to the
elements Ds. In like manner, the inci-ements of entropy and of the
quantities of the several components in the vicinity of the surface
their centers

will

lie

solid),

be

.fVh'-Vv"

(<''l4-''3) '/SU)]

S^^J^S,

etc.

The entropy and the matter of different kinds represented by these

expressions we may suppose to be derived from the fluid mass.
These expressions, therefore, with a change of sign, will represent
the increments of entropy and of the quantities of the components
in
is

the

space

wdiole

occupied

by the

immediately contiguous to the

solid.

fluid

except

that

Since this space

which

may be
may be

regarded as constant, the increment of energy in this space

obtained [according to equation (12)] by multiplying the above
expression relating to entropy

yw^",

components by
* The potential
is

//

"

is

by t, and those

|^2^ tc.,*

marked by double accents

to be determined in the fluid mass,

relating

and taking the sum.

to

the

If to this

in order to indicate that its value

and to distinguish

it

from the potential

fi

486

W. Gibbs

J.

we add

Equilihrhiui of Heterogeneous Substances.

the above expression for

increment of energy near the

energy for the whole system.

tlie

surface, Ave obtain the increment of

Now

by

(93)

we have
r=

//'

By

f,"

t ,1,"

+ ///' ;//' +

//^

y/ +

etc.

and (659), our expression for the total increment of

the system may be reduced to the form

this equation

energy

in

^//v' /^"rl' + K + (Cl+c3)ff]fJ.YXs.

/[fv'

In order that this shall vanish for any values of

that

coefHcient of dJSf Ds shall vanish.

tlie

6N^

it

(660)

is

necessary

This gives for the condi-

tion of equilibrium

^,,^eV-tv.J+if + i^e,+e.^a^
y
This equation
containing

(7,

(061)

identical Avith (387), with the exception of the term

is

which vanishes when the surface

We may also observe

that

when

tlie solid

isotropic pressure, if the quantity represented

tension of the surface, p"

-|(<^'i

c^) ^

^^'^^^

the interior of the solid, and the second

plane.*

is

has no

by

sti'esses

ff is

except an

equal to the true

represent the pressure in

member

of the equation will

represent [see equation (93)] the A'alue of the potential in the solid
for the substance of

which

it

In this case, therefore, the

consists.

equation reduces to

that

is, it

expresses the equality of the potentials for the substance of

the solid in the two masses

the same

if

both masses were

o"

may not represent the true tension

Moreover, the compressibility of

the true pressure in the solid
tities v' a"tl V\' if

condition which would subsist

fluid.
all solids is

when

so small that, although

of the surface, woy p"-\its stresses

calculated for the pressure

(Cj -\-<-2)

jo"

+ (c^ +^2) ^

the actual temperature will have sensibly the same values as

Hence, the second
lated for the true pressure of the solid.
relatina; to tlie solid

shall see,

may

mass (when

with

if calcu-

member

this is in a state of isotropic stress), which, as

The other

not always liave the same value.

o"

are isotropic, the quan-

potentials

fi^, etc.,

we

have

the same values as in (659), and consist of two classes, one of which relates to sub-

stances which are components of the fluid mass, (these might be marked by the double
accents.)

and the other

The expressions

to

relates to substances

found only at the surface of discontinuity.

be multiplied by the potentials of this latter class

all

have the

is

therefore

value zero.

* In equation (387), the density of the solid

equivalent to

7/

in (661).

is

denoted by

T,

which

W. Gibbs

J.

E<piilibrhiiii
when the

of eciuatioii (661),
tropic,

of Il'eterogeneovs

stresses of the solid are sensibly iso-

sensibly eqiial to the potential of the

is

487

Stibstauces.

same temperature but with the pressure p"

same body at the

Co) ff, and the

-\- {ci -{

condition of equilibrium with respect to dissolving for a solid of

may be

isotropic stresses

exi)i-essed with sufficient

accuracy by saying

that the potential for the substance of the solid in the fluid must
have this value. In like manner, when the solid is not in a state of
isotropic stress, the difterence of the

two

not sensibly affect the values of

aud

second

member

of the ecpiation

v'

may be

pressures in question will

?/v',

and the value of the

calculated as iip"-{- (c,

c^)

ff

represented the true pressure in the solid in the direction of the norTherefore,

mal to the surface.

quantity

we had taken

for

granted that the

represents the tension of a surface between a solid and a

ff

fluid, as it

if

does

luasses are fluid, this assumption

when both

would

not have led us into any })ractical error in determining the value of
the potential

hand,

if

which

/<,"

is

necessary for equilibrium.

On

in the case of any amorphous body the value of

the other

differs

notably from the true surface-tension, the latter quantity substituted

for

0'

in (661) will

make the second member of the equation equal to

when the stresses are isotropic, but this will not

the true value of yu/,

be equal to the value of

/./

," in

case of eqixilibrium, unless Cj

-\-

c^

0.

When

the stresses in the solid are not isotropic, equation (661)

be regarded as exi)ressing the condition of equilibrium with
respect to the dissolving of the solid, and is to be distinguished from

may

the condition of equilibrium

matter, since the

crystalline bodies,

in a state

(The case would of course be different with

of isotropic stress.

jj^"

with respect to an increase of solid

new matter would doubtless be deposited

which are not considered

here.)

The value of
new

necessary for equilibrium with respect to the formation of

matter

is

a little less than that necessary for equilibrium with respect

to the dissolving of the solid.

the solid and fluid,

certainty

is

In regard to the actual behavior of

that the theory enables us to predict with

all

that the solid will not dissolve

if

the value of the poten-

by the equation for the solid with

its distorting stresses, and that new matter will not be formed if the
value of /<i" is less than the same equation would give for the case of
tial yu/' is

greater than that given

the solid with isotropic stresses.*

* The possibility that the
original solid

is

here

left

new

seems probable, however, that

It

solid matter

out of account.

might

differ in

composition from the

This point has been discussed on pages

134-137, but without reference to the state of strain of the solid or the influence of
the curvature of the surface of discontinuity.

Trans. Conn. Acad., Vol.

III.

62

The statement made above may be

April, 1878.

488
if

tT.

W. Gibhs

Equilibrium of Ileterogeneoiis Substances.

the fluid in contact with the solid

not renewed, the system will

is

generally find a state of equilibrium in which the outermost portion

of the solid will be in a state of isotropic stress.

should dissolve, this would supersaturate the

is

If at first the solid

perhaps until a state

reached satisfying the condition of equilibrium with the stressed

and then,

solid,

isotropic stress
is

fluid,

not before, a deposition of solid matter in a state of

if

would be

commence and go on

likely to

until the fluid

reduced to a state of equilibrium with this new solid matter.

The

action of gravity will not affect the nature of the condition of

equilibrium for any single point at which the fluid meets the solid,

but

p" and yu/' in (661) to vary according

If we suppose that the
(612) and (6] 7).
in a state of isotropic stress, which is the

will cause the values oi

it

to the laws expressed

by

oiiter part of the solid is

most important

case, since

the only one in which the equilibrium

it is

every sense stable, we have seen that the condition (661)

is in

sensibly equivalent to this

least

that

is

at

the potential for the sub-

stance of the solid which would belong to the solid mass at the

temperature
Or,

if

and the pressure ^^"+

we denote by

temperature

{p'^

{Ci-^-c.^)

G must be equal

to ///'.

the pressiire belonging to solid with the

and the potential equal to

/ij",

the condition

may be

expressed in the form

(y)z=y'+(c,+

Now

if Ave

write

;/"

(662)

C2)(7.

for the total density of the fluid,

we have by

(612)

dp)"=-gy"dz.

By

d{p')^y^di.i^\

(98)

and by (617)

d^i^' =z

d {p')

whence

=1

</

dz

</

^^^

'

Accordingly we have

d{p')^dp"

= g{y"~.y,')dz,

and
z being

measured from the horizontal plane for which {p')=p".

Substituting this value in (662),

we

obtain

c,+c^= ^^^'"~^''h
generalized so as to hold true of the formation of

the surface as follows

that new solid matter

of

the surface (with more than insensible thickness),

culated for such

new matter

is

new

solid matter of

any kind
if

(663)

will not

the second

any kind on

be formed upon

member

of (661) cal-

greater than the potential in the fluid for such matter.

J. TF.

Equilibrium of Heterogeneous Substances.

Gibhs

precisely as if both musses were fluid,

common

their

489

and G denoted the tension of

surface, and {p) the true pressure in the mass specified,

[Compare (6 19).
The obstacles

to an exact experimental realization of these rela-

from the M'ant of absolute uniformity

solids, and on account of the
amorphous
in the internal structure of
are necessary to bring
which
processes
passive resistances to the
tions are very great, principally

about a state satisfying the conditions of theoretical equilibrium,

but it may be easy to verify the general tendency toward diminution
of surface, which

is

implied in the foregoing equations.*

Let us apply the same method to the case

The surface between the solid and
a crystal.

now

fluid will

may

of plane portions, the directions of which

which the

in

solid is

consist

be regarded as invari-

* It seems probable that a tendency of this kind plays an important part in

phenomena which have been observed

of the

some

w^ith respect to the freezing together

of pieces of ice.

(See especially Professor Faraday's " Note on Regelation" in the

Proceedings of

Royal

vol. xxi, p.

tlie

takes place

vi'hich

440

Society, vol. x, p.

Although

146.)

ser.,

and the action

by the directions
phenomena have not been observed

depend upon the orientation of the pieces of

its

crystalline structure,

doubtless influenced to a certain extent

is

the axes of crystallization, yet, since the

far as

or in the Fhilosojjhical Magazine, 4th

body of

this is a

general character

is

concerned,

is

ice, v?e

may

conclude that the

such as might take place

vsfith

effect,

of
to

so

an isotropic

In other words, for the purposes of a general explanation of the phenomena

body.

we may

neglect the differences in the values of ciw (the suffixes are used to indicate

that the symbol relates to the surface between ice and water) for different orientations
of the axes of crystallization,

and also neglect the influence of the surface of discon-

tinuity with respect to crystalline structure,

together of the two masses of ice

are not similarly directed.
of such a surface
to their union,

if

reality, this surface

measured by a quantity

when one

the orientations of the

to the

which must be formed by the freezing

the axes of crystallization in the two masses

or the necessity of the formation

must exert an influence adverse

the pieces of ice freeze together

the same principles as

and

In

when

surface.

of

ctu,

which

is

determined for this surface by

two contiguous masses

is fluid,

two systems of crystallographic axes

and varies with

relatively to each other

But under the circumstances of the experiment, since we may

two systems of axes having precisely the same directions,

neglect the possibility of the

this influence is

probably of a tolerably constant character, and

cient to alter the general nature of the result.

tendency of pieces of

case
of

ice to freeze together,

and without pressure,

faces

is

ffn

it

evidently not

is

suffi-

In order wholly to prevent the

when meeting

water with curved sur-

in

would be necessary that ffn

2(Tiw,

except so far as the

modified by passive resistances to change, and by the inequality in the values

and

It vdll

(Tjw for different directions of

the axes of crystallization.

be observed that this view of the phenomena

opinion of Professor Faraday,

With

indirect consequence of pressure, see

Royal Society

is

in

harmony with the

respect to the union of pieces of ice as an

page 198 of volume

or the Philosophical Magazine, 4th

xi of the Proceedingn of the

ser., vol. xxiii, p.

407.

490

J.

W. Gibhs

Eqidlibrium of Heterogeneous Substances.

grows on one

If the crystal

able.

side a distance SN', without other

change, the increment of energy in the vicinity of the surface will be

{e^'

y") s 6N'+ ^''(fs(j/ V cosee 6j' %!)

I'

cot

oo') SJST,

where fy' and fy" denote the volume-densities of energy in the crystal
and fluid respectively, s the area of the side on which the crystal
grows, (1) the surface-density of energy on that side, s(i) the surfacedensity of energy on an adjacent side, go' the external angle of these
two sides, I' their common edge, and the symbol 2' a summation
with respect to the different sides adjacent to the

first.

The

incre-

ments of entropy and of tbe quantities of the several components will

be represented by analogous formulas, and if we deduce as on pages 485,
486 the expression for the increase of energy in the whole system due
to the growth of the crystal without change of the total entropy or
volume, and

set this expression

equal to zero,

we

shall obtain for the

condition of equilibrium

{es'-tn.'-li,"y,'+p")s6N

+ :^"
where G and

= fy'

will be

It

cosec Gj'(f

7k'

I'

cot

same

go')

6N=

sides as

fg.^,

(G64)

0,

and

fsd)' i"

This gives

{ p"

'2'i a'

I'

cosec

vr^^-

gV cot go'\

go

(')

jy-'

observed that unless the side especially considered

small or narrow,

which

0-' /'

g' relate respectively to the

the preceding formula.

/'.

we may

will then give the

is

neglect the second fraction in this equation,

same value of

//," as equation

(387), or as

equation (661) applied to a plane surface.

Since a similar equation must hold true with respect to every other
side of the crystal of which the equililirium

not affected by meet-

is

ing some other body, the condition of equilibrium for the crystalline
foi-m

(when unaffected by gravity)

is

that the expression

^'(o"'/' cosec &9'o'^' cot

gl)')

/rfifi^

shall

have the same value for each side of the crystal.

any side of the crystal is meant

of this expression for

G and

s ai-e

in

connection with the

This condition will not be affected by a change

while

value

when

determined by that side and the other quantities by the

surrounding sides in succession

tal

(By the value

its

its

projjortions remain the same.

similar crystals

toward the form required by

in

first side.)

the size of a crys-

Bvit the tendencies

this condition, as

of

mea-

sured by the inequalities in the composition or the temperature of

W. Gihbs

J.

Equ'ilihriv.m of Heterogeneous Substances.

the surrounding fluid whicli would counterbalance them, will

491

be

inversely as the linear dimensions of the crystals, as ap})ears from the

preceding equation.
If

we

s) for the sum

by the corresponding

write v for the volume of a crystal, and 2{ff

of the areas of

all

sides multiplied each

its

value of c, the numerator and denominator of the fraction (666),

multiplied each by 6N, may be represented by 6^{gs) and (3v

The value

respectively.

of the fraction

is

therefore equal to that of

the differential coeflicient

d2{o' s)

dv
as determined
ai-e fixed.

sides
tal

by the displacement of a particular side while the other

The condition of equilibrium for the form of a crys-

(when the influence of gravity may be neglected)

is

that the

value of this differential coeflicient must be independent of the particular side which

is

supposed to be displaced.

of the crystal, ^^((T

condition of equilibrium

satisfied, as

is

constant volume

Foi- a

minimum

has therefore a

s)

may

value

easily be

when the

proved more

directly.

When

there are no foreign substances at the surfaces of the crystal,

and the surrounding

^{o's)

represents the

crystal,

and the

resents the

fluid

indefinitely

is

work required

coeflicient of s

work gained

to

extended, the quantity

form the surfaces of the

dJSfm (664) with

its

sign reversed rep-

forming a mass of volume unity

in

crystal but regarded as without surfaces.

We may

like the

denote the work

required to form the crystal by

W^

denoting the work required to form the surfaces

and

Wy

the

the surfaces.

work gained

in

\J.e., ^'((Ts)],

forming the mass as distinguished from

Equation (664)

may

then be written

6Wy+l:{0 6s)z::zO.
Now

(667)

would evidently continue to hold true if the crystal were

diminished in size, remaining similar to itself in form and in nature,
if the values of o' in all the sides were supposed to diminish in the
(664)

same ratio as the linear dimensions of the crystal.

W^s, would then be determined by the relation

d TFs =
and that of

Wy by

(667).

d:^{ff s)

= I 2{0 ds),

Hence,

dW^=^dWy,

The

variation of

492

J.

W. Gibhs

EquiUbrimn of Heterogeneous Substances.

and, since TT^ and

Wy

vanish together,

TTs- TFv

= iWs==iTFv,

(668)

the same relation which we have before seen to snbsist with respect
to a spherical

mass of

fluid as well as in other cases.

(See pages 421,

425, 465.)

The equilibiium of the crystal is unstable with respect to variations

when the surrounding fluid is indefinitely extended, but it
may be made stable by limiting the quantity of the fluid.
To take account of the influence of gravity, we must give to yUj"
and p" in (665) their average values in the side considered. These
in size

coincide

(when the

fluid is in a state of internal equilibrium)

Yx'i

^y'l Vv'

gravity

is

with

The values of

their values at the center of gravity of the side.

w^^y ^^ regarded as constant, so far as the influence of

Now

concerned.

by

since

(612) and (617)

= -gr"dz,
=. g dz,
d{r,'M^"-2n = ^{r"~ri')(^^'
dp"

and

d/.i^"

we have
Comparing

(664),

we

see that the upper or the lower faces of the

crystal will have the greater tendency to grow, (other things l)eing
equal,) according as the crystal

When

the form of the crystal

on

is

lighter or heavier than the fluid.

two masses

the densities of the

may

are equal, the effect of gravity

be neglected.

In the preceding paragraph the fluid

internal equilibrium.

If

we

is

regarded as

sujipose the composition

in

a state of

and tempera-

ture of the fluid to be uniform, the condition which will

effiect

make

the

of gravity vanish will be that

d(r,'^i,"-p")

Q^

dz
wlien the value of the differential coefficient

ance with this supposition.

(^

which, by equation (92),

is

is

determined

in

accord-

This condition i-educes to

dp))t,m

}//'

equivalent to

{X
=J_.
\drn^Jt,p,m

(669)

y^'

may

suffixed

is

used to represent

occur in the differential

coefficient.

all

the symbols m,, m^,

etc.,

except such as

W. Gibbs

J.

The tendency of

EquUlhrhmi of Heterogeneous Substwuces.

a crystal to

lower parts of the

grow

be greater^in the

will

493
or

upijei*

according as the growth of a crystal at con-

fluid,

stant temperature and pressure will produce expansion or contraction.

may suppose

Again, we

the composition

vary with the pressure, that

temperature

by the

tions express a state

and

?/v'

fluid

in

no

?;v'

foi'

will

in

(664) as constant, but

di^;'

mean temperature

the

may

=.

same crystal
These condifluid is

we cannot

we may regard

t dti^'.

its

then

also suppose the

to the differences of temperature

real loss of generality,) Ave

Therefore,

their
if

we

of the fluid, (which involves

treat

e^'

-t

have for the condition that the

shall then

may

contact with them.

variations as subject to the relation

make

We

z.

and

fluid

which may perhaps be realized when the

Owing

gently stirred.
fy'

the

of different crystals or different parts of the

to be determined

regard

with

is,

of

The temperature

entropy per unit of mass to be uniform.

t/y'

as constant.

effect of

We

gravity shall

vanish
dz

which

signifies in the present case that

or,

by

dp Jii,m~ ^i"

(90),

=^.

i^)'
Since the entropy of the crystal

is

(670)

zero, this equation ex[)resses that

the dissolving of a small crystal in a considerable quantity of the

fluid will

sure

is

produce neither expansion nor contraction, when the pres-

maintained constant and no heat

is

supplied or taken away.

which crystals actually grow or dissolve is often

principally determined by other differences of phase in the surrounding fluid than those which have been considered in the preceding

The manner

paragraph.

in

This

is

When

when the

crystal

is

growing

the great mass of the fluid

is

consider-

especially the case

or dissolving rapidly.

ably supersaturated, the action of the crystal keeps the part immediately contiguous to

it

nearer the state of exact saturation.

The

most exposed
grow most rapidly.

farthest projecting parts of the crystal will therefore be

to the action of the supersaturated

The same

flixid,

and

will

parts of a crystal will dissolve most rapidly in a fluid con-

siderably below saturation.*

* See 0. Lehmami "Debar das Wachsthum der Krystalle,"
lographie unci Mineralogie, Bd.
Beibldtter,

Bd.

ii,

S. 1.

i,

S.

453

Zeitschrift. fllr Krystai-

or the review of the paper in

Wiedemann's

494

J. TF.

Gibbs

Equilibrium of Heterogeneous Substances.

But even when the

fluid

is

supersaturated

necessary in order that the crystal shall

expected that the form in which 2{o'

such a modification of that form as

grow

as

is

not to be

all, it is

minimum

has a

s)

may

much

only so
at

value (or

be diie to gravity or to the

body supporting the crystal) will always be the

For we cannot imagine a body of the internal
structure and external form of a crystal to grow or dissolve by an
entirely continuous process, or by a process in the same sense continuinfluence of the
iiltimate

result.

ous as condensation or evaporation between a liquid and gas, or the

corresponding processes betw^eeu an amorphous solid and a

Tlie process

fluid.

rather to be regarded as periodic, and the formula

is

cannot properly represent the true value of the quantities

(664)

intended unless

6N

is

equal to the distance between two successive

layers of molecules in the crystal, or a multiple of that distance.

we can only

Since this can hardly be treated as an infinitesimal,

con-

clude with certainty that sensible changes cannot take place for

which the expression (664) would have a positive value.*

* That

it is

Becessary that certain relations shall be precisely satisfied in order that

may

equilibrium

between a liquid and gas with respect

subsist

explained (see Clausius " Ueber die Art der Bewegung, welche wir
Fogg. Ann., Bd.

c, S.

353

or Abhancl. ilher die mech. Wdrmetheorie,

to evaporation,

Warme

XIV,) by suppos-

ing that a passage of individual molecules from the one mass to the other

taking place, so that the slightest circumstance

many

cases, to the equilibrium

from one mass

the solid.

continually

between amorphous

case of crystals in equilibrium with

cules

is

give the preponderance to the

The same supposition may be applied, at least

solids and fluids.
Also in the

passage of matter in either direction.

in

may

is

nennen,"

fluids,

there

may be

a passage of individual mole-

to the other, so as to cause insensible fluctuations in the

If these fluctuations are

mass of

such as to cause the occasional deposit or removal

of a whole layer of particles, the least cause

would be

sufficient to

of one kind of change prevail over that of the other,

and

it

make

the probability

would be necessary for

equilibrium that the theoretical conditions deduced above should be precisely satisfied.

But

this supposition

seems quite improbable, except with respect

to a

very small

side.

The following view of the molecular state of a crystal when in equilibrium with
Since the molecules at
respect to growth or dissolution appears as probable as any.
the corners and edges of a perfect crystal would be less firmly held in their places
than those in the middle of a
theoretical equilibrium (6G5)

on each side

side,

is satisfied

we may

suppose that when the condition of

several of the outermost layers of molecules

of the crystal are incomplete

toward the edges.

The boundaries

of these

imperfect layers probably fluctuate, as individual molecules attach themselves to the

crystal or detach themselves, but not so that a layer is entirely

of considerable size), to be restored again simply

of the individual molecules.

b}-

removed (on any side

the irregularities of the motions

Single molecules or small groups of molecules

may

indeed attach themselves to the side of the crystal but they will speedily be dislodged,

and

if

any molecules are thrown out from the middle of a

surface, these deficiencies

W. Gihhs

J.

JEqalUhrimn of iTeteroc/eneous Substances.

495

Let us now examine the special condition of equilibrium which

which three

relates to a line at

more of these masses

is

we apply

to a system containing such a line,

in the

masses meet, when one or

diiferent

If

solid.

it

method of page 685

we shall obtain

the

evident that

is

expression corresponding to (660), beside the integral relating

term of the form

to the surfaces, a

f^{GST)Dl
to

be interpreted as the similar term

definition of

ff

has been modified

in its

except so far as the

in (611),

extension to solid masses.

order that this term shall be incapable of a negative value

will also soon

be made good

nor will the frequency of these occurrences be such as

greatly to affect the general smoothness of the surfaces, except near the edges
the surfaces

fall off

/i

new

of the formation, the necessary value of

except

when

the side

growth of the crystal

will

is

however be

the whole,

it

new layer is at or near

^ " may be independent
,

The value

of

/^

"

which

the case

is

2((7 s) shall

finite quantity.

commencement

of the area of the

is

necessary for the

different for different kinds of surfaces,

and

is least.

principally determined

is

by equation

(665),

by the

[i. e.,

be a minimxim for the volume of the crystal except so far as

modified by gravity or the contact of other bodies,) but as they grow

more sujjersaturated than

larger (in a solvent no

all),

the

seems not improbable that the form of very minute crystals in

equilibrium with solvents

condition that

by a

(665)

probably will generally be greatest for the surfaces for which a

On

This will require a

layers can be formed.

very small.

where

a continued growth on any

which may exceed that given by equation

"
I

Since the difficulty in the formation of a

side,

Now

somewhat, as before described.

side of a crystal is impossible unless

value of

In

neces-

it is

new matter on

the deposition of

is

the nature (orientation) of the surfaces and less

surrounding surfaces.

As

necessary to

at

more

Vjy

by

their size

and

relations to the

a final result, a large crystal, thus formed, will generally

be bounded by those surfaces alone on which the deposit of

with small, perhaps insensible truncations.

least readily,

make them grow

the different surfaces will be determined

new
If

matter takes place

one kind of surfaces

bounded by

satisfying this condition cannot form a closed figure, the crystal will be

two or three kinds

of surfaces

determined by the same condition.

The kinds

of

surface thus determined will probably generally be those for v/hich g has the least
values.

But the

relative

development of the different kinds of

by gravity or the contact

minimum. The growth of the
fied

It

of other bodies, will not

crystal

wiU

finally

sides,

even

if

be such as to make

unmodi2(cts)

be confined to sides of a single kind.

does not appear that any part of the operation of removing a layer of molecules

presents any especial difficulty so marked as that of commencing a

new

layer

yet

the values of ^ " which wiU just allow the different stages of the process to go on
must be slightly different, and therefore, for the continued dissolving of the crystal
,

the value of
It

//

"

must be

seems probable that

the least values.

as possible)

is

The

less (by a finite quantity)

this

than that given by equation

would be especially true of those

effect of dissolving a crystal (even

(665).

which a has
done as slowly

sides for

when

it is

therefore to produce a form which probably differs from that of

theoretical equilibrium in a direction opposite to that of a

Trans. Conn. Acad., Vol.

III.

ca

growing

crystal.

June, 1878.

496

J.

W. Gihhs

Equilibrium of Heterogeneoiis Substances.

sary that at every point of the line

2(o-fJr)^0

(671)

Those displacements are to

any iwssible displacement of the line.

be regarded as possible which are not prevented by the solidity of
the masses, when the interior of every solid mass is regarded as
for

incapable of motion.

At the

surfaces

between

solid

and

fluid masses,

the processes of solidification and dissolution will be possible in some

and impossible

cases,

The

simplest case

in others.
is

when two masses

and insoluble. Let us denote the

and B, and the angles filled by these

are fluid and the third

solid

solid

fluids

tively.

If the surface of the solid

meets the two

fluids,

respec-

continuous at the line where

is

a=

(Tbs

where these masses meet

condition of equilibrium

and

fluids
/5

it

the condition of equilibrium reduces to

Cab cos

If the line

by S, the
by a and

is

by

is

- G k^.
at an

is

(672)

edge of the

solid, the

that

Cab cos

^V

Cab cos

/i

^ Cbs O'as,
^ Cas O'bs

((573)

which reduces to the preceding when a-\-fi=z7t. Since the displacement of the line can take place by a purely mechanical process,
this condition is capable of a more satisfactory experimental verification than those conditions

and

Yet the

dissolution.

the line

is

which relate to processes of

frictional

solidification

resistance to a displacement of

enormously greater than

in

the case of three

fluids,

since the relative displacements of contiguous portions of matter are

enormously greater.

Moreover, foreign substances adhering to the

and cannot be distributed by extensions

and contractions of the surface of discontinuity, as in the case of
solid are not easily displaced,

fluid masses.

Hence, the distribution of such substances

is

arbitrary

to a greater extent than in the case of fluid masses, (in which a single

foreign substance in any surface of discontinuity

is

uniformly

buted, and a greater number are at least so distributed as to

distri-

make the

tension of the surface uniform,) and the presence of these substances

will

in a more irregular manner.

more of three surfaces of discontinuity which meet in a
divides an amorphous solid from a fluid in which it is soluble,

modify the conditions of equilibrium

If one or
line

such a surface

is

to be regarded as movable, and the particular condi-

tions involved in (671) will be accordingly modified.

solid is a crystal, the case wnll

used on page 490.

The condition

If the soluble

properly be treated by the method

of equilibrium relating to the line

W. Gibbs

J.

EqxdUhrium, of HeterogeMeons Substances.

497

be entirely separable from those relating to the

will not in this case

adjacent surfaces, since a displacement of the line will involve a displacement of the whole side of the crystal which is terminated at this

But the expression for the total increment of energy in the

system due to any internal changes not involving any variation in
the total entropy or volume will consist of two parts, of which one
relates to the properties of the masses of the system, and the other

line.

may be

expressed in the form

8:2{(js),

the summation relating to all the surfaces of discontinuity. This

indicates the same tendency toward changes diminishing the value of
^((Ts), which appears in other cases.*

General Relations.
of the solid,

For any constant state of strain of the surface

we may

write

f?fs(,)=:d^/;s(,)H-/'2^^^^2Ci)

since

relation

tliis

From

involved.

implied

is

in

the

+ A<3f^^'3(i)+

etc.,

(674)

of the quantities

definition

and (659) we obtain

this

= -7h(^)dt- l\(^)d^i^- l\(^)dH^ eic,

subject, in strictness, to the same limitation that
do-

which

is

(675)

the state

But

of strain of the surface of the solid remains the same.

may

limitation

in

most cases be neglected.

(If the

quantity

<J

this

repre-

sented the true tension of the surface, as in the case of a surface

fluids, the limitation would be wholly unnecessary.)
Another method and notation. We have so far supposed that we
have to do with a non-homogeneous film of matter between two
homogeneous (or very nearly homogeneous) masses, and that the
nature and state of this film is in all respects determined by the

between

The freezing together

wool and

of

ice

may be mentioned

here.

The

fact that

a fiber of wool which remains in contact with a block of ice under water will become
attached to

it

seems to be

strictly

into such a position that

analogous to the fact that

if

a solid body be brought

just touches the free surface of water, the

it

water will

generally rise up about the point of contact so as to touch the solid over a surface of

some

extent.

The condition

of the latter plienomenon is

"S A

where the
like

suffixes

s,

a,

and

+ (TwA ^ Csw

refer to the solid, to air,

manner, the condition for the freezing of the

the seolotropic properties of the

and to water, respectively.

ice to the wool,

if

we

In

neglect

ice, is

<Jsw +ffiw ]> Csi,

where the

suffixes

p,

w; and

Proc. Roy. Soc, vol. x, p. 447

relate to wool, to water,

;

and

to ice, respectively.

or Phil. Mag., 4th ser., vol. xxi. p. 151.

See

498

W. Gibbs

./.

Equilibrium of Heterogeneous Substances.

nature and state of these masses together with the quantities of the

may be

foreign substances which

Problems relating

(See page 483.)

and dissolution seem

present in the fihu.

to processes of

solidification

hardly capable of a satisfactory solution, except on this supposition,

which appears in general allowable with respect to the surfaces produced by these processes. But in considering the equilibrium of
an unchangeable

fluids at the surface of

neither necessary nor convenient.

solid,

such a limitation

The following method of

is

treating

the subject will be found more simple and at the same time more
general.

Let us suppose the superficial density of energy to be determined

by the excess of energy in the vicinity of the surface over that which
would belong to the solid, if (with the same temperature and state
of strain) it were bounded by a vacuum in place of the fluid, and to
the

extended with a uniform volume-density of enei*gy just

fluid, if it

up to the surface of the

any case

solid, or, if in

this does not suffi-

ciently define a surface, to a surface determined in

by the

denote the superficial energy

some

definite

Let us use the symbol

exterior particles of the solid.

tJtus defined.

density of entropy to be determined in a

way

(fg)

to

Let us suppose a superficial

manner

entirely analogous,

and be denoted by (?/). In like manner also, for all the components
of the fluid, and for all foreign fluid substances which may be present
be determined, and denoted
These superficial densities of the fluid components
All matter
relate solely to the matter which is fluid or movable.
which is immovably attached to the solid mass is to be regarded as a
Moreover, let ? be defined by the equation
part of the same.
at the surface, let the su2:)erficial densities

by

{l\), {l\),

t'tc.

?=(fs)-^(A;s)-/<o(ro)~/^3(r3)-etc.

d{e^)

d?=z-

d{t/s)

(7s)

+yM3

(676)

following general relations

will satisfy the

These quantities

(7(i 2)

+ Ms (Kf\) +

dt-{l\) d;j2U\) (^M3-

etc-,

(Qll)

etc.

(678)

In strictness, these relations are subject to the same limitation as

(674)

and

(675).

But

In fact, the values of

affected

by

this
?,

limitation

(fg),

etc.

may

must

generally be neglected.

in general

than those of

(7,

The quantity
It

less

fg^,, etc.
?

evidently represents the tendency to contraction in

that portion of the surface of the fluid which

solid.

be much

variations in the state of strain of the surface of the solid

may be

vnth the solid.

called the superficial tension

Its value

may be

is

of

in contact with the

the fluid in contact

either positive or negative.

J.

It will

Wl Glbbs

Eqallihriimi of Heterogeneous Substances.

be observed that for the same solid surface and for the same

temperature but for different fluids the values of G

which the definition of

those of

499

by a constant,

quantity

this
viz.,

is

(in

all

cases to

applicable) will differ from

the value of

for the solid surface in

a vacuum.

For the condition of equilibrium of two

the surface of the solid,

we may
O-AB

cos

a line on

difiei'cnt fluids at

easily obtain

?BS

(679)

^AS,

being used as in (672), and the condition being

subject to the same modification when the fluids meet at an edge of
the suffixes,

etc.,

the solid.

must

It

at the

be regarded as a condition of theoretical equilibrium

(679), to limitation on account

also

line considered, [subject, like

if there are any foreign subA-S and B-S, the potentials for these subhave the same value on both sides of the line or, if

of passive resistances to motion,] that

stances in the surfaces

stances shall

any such substance

is

found only on one side of the

potential for that substance

must not have a

that the

line,

less value

on the other

and that the potentials for the components of the mass A, for
example, must have the same values in the surface B-C as in the
mass A, or, if they are not actual components of the surface B-C, a
side

value not less than in A.

of the surface-tensions of

Hence, we cannot determine the difterence

two

fluids in contact

with the same

bringing them together upon the surface of the

conditions are satisfied, as well as those which

solid,

by

solid, unless these

art;

necessary to pre-

vent the mixing of the fluid masses.

The

investigation on pages 442-448 of the conditions of equilibrium

for a fluid

system under the influence of gravity

extended to the case

solid

masses,

dissolution.

in

which the system

is

may

easily

be

bounded by or includes

when these can be treated as rigid and incapable of

The general condition of mechanical equilibrium would

be of the form

y> 6Dv

-I-

fg y6zDv+fG SI)s -^fg F Sz Ds

+ /g SzDm + /iSDs+/g{r) 6zJJs=0,

(680)

where the first four integrals relate to the fluid masses and the surfaces which divide them, and have the same signification as in
equation (606), the fifth integral relates to the movable solid masses,
and the sixth and seventh to the surfaces between the solids and
fluids, (r) denoting the sum of the quantities (i^g), (^3), etc.
It
should be observed that at the surfiice where a fluid meets a solid

500

J.

dz and

W. Gibhs

6z,

and the

Equilibrium of Heterogeneous Substances.

which indicate respectively the displacements of the solid

may have different values, but the components of

fluid,

these displacements which are normal to the surface must be equal.

From this equation, among other

we may derive the following

particular conditions of equilib-

rium,

cU

= g{r)dz,

(681)

[compare (614),] which expresses the law governing the distribuon the surface of a solid, when there are no

tion of a thin fluid film

passive resistances to

By

its

motion.

applying equation (680) to the case of a vertical cylindrical tube

containing two different fluids, we may easily obtain the well-known

theorem that the product of the perimeter of the internal surface by
the difference 5' ?" of the superficial tensions of the upper and lower

with the tube

fluids in contact

matter

in the

equal to the excess of weight of the

is

tube above that which would be there,

if

the boundary

between the fluids were in the horizontal plane at which their presIn this theorem, we may either include or
sures would be equal.
exclude the weight of a film of fluid matter adhering to the tube.
is usually applied to the column of fluid in mass
between the horizontal plane for which p':^p" and the actual
boundary between the two fluids. The superficial tensions 5' and s"

The proposition

are then to be measured in the vicinity of this column.

But

Ave

may

weight of a film adhering to the internal surface of

For example, in the case of water in equilibrium with its
the tube.
own vapor in a tube, the weight of all the water-substance in the
tube above the plane p'=/)", diminished by that of the water-vapor
also include the

which would

fill

by the difference
plane p'=: p".

the same space,

in

If

is

the values of

equal to the perimeter multiplied

at the top of the tube and at the

the height of the tube

is infinite,

the value of

at

the top vanishes, and the w^eight of the film of water adhering to the

tube and of the mass of liquid water above the plane p'=.2')" diminished by the weight of vapor which would fill the same space is
equal in numerical value but of opposite sign to the product of the
perimeter of the internal surface of the tube multiplied by ?", the
superficial tension of liquid water in contact with the tube at the
pressure at which the water and

a plane surface.

its

vapor would be in equilibrium at

weight of water which can

In this sense, the total

be supported by the tube per unit of the perimeter of its surface is

directly measured by the value of ? for water in contact with the
tube.

W. Gibhs

J.

Equilibrium of Heterogeneous Substances.

501

Modification of the conditions of equilibrium by ei-ectroMOTivE force. Theory of a perfect electro-chemical

APPARATUS.

We

know by

ductors) there

experience that in certain fluids

The quantitative

substances and that of electricity.

these fluxes

(electrolytic

con-

a coiniection between the fluxes of the component

is

may

relation

between

be expressed by an equation of the form

Dm^

De

Dm^,
H

Dm

+ etc.

Dm,.

etc.,

((,82)

where De, Dtn^, etc. denote the infinitesimal quantities of electricity

and of the components of the fluid which pass simultaneously through
any same surface, which may be either at rest or in motion, and
a^,

o-i,,

etc.,

rt-g,

Dm^,

regard

o-h,

For,

another.

etc.

JDrn^,,

if

We may

denote positive constants.

etc.,

Dm^, Dm^,,

they were not

so,

etc.,

evidently

as independent of one

one or more could be expressed

terms of the others, and we could reduce the equation to a shorter

foi-m in which all the terms of this kind would be independent.
in

Since

tlie

motion of the

fixes

must

satisfy the relation

~+ +
Yi

These

whole will not involve any eleccomponents

the
specified by the suf-

fluid as a

trical current, the densities of

Vh

densities, therefore,

densities of the

etc.

y
Vh
=^
+^
+

etc.

(683)

are not independently variable, like the

components which we have employed

in other cases.
account for the relation (682) by supposing that electricity (positive or negative) is inseparably attached to the diflerent
kinds of molecules, so long as they remain in the interior of the fluid,
in such a way that the quantities a^, 0-5, etc. of the substances speci-

We may

fied are

each charged with a unit of positive electricity, and the quanix^, etc. of the substances specified by these suflixes are each

tities a^,

charged with a unit of negative electricity.

accounted for by the fact that the constants

The
cr^,

o-^,

relation (683)
etc.

is

are so small

that the electrical charge of any sensible portion of the fluid varying
sensibly from the law expressed in (683) would be enormously great,
so that the formation of such a

mass would be

resisted

by a very

great force.
It will

be observed that the choice of the substances which we

regard as the components of the fluid

that the

same physical

relations

may

is

to

some extent

arbitrary,

and

be expressed by different equa-

502

TK Gibhs

J.

form

tions of the

Eqidlihriuni of Heterogeneous Suhstances.

which the fluxes are expressed with referIf the components chosen are

(682), in

ence to diflerent sets of components.

we

such as represent what

believe to be the actual molecular consti-

tution of the fluid, those of which the fluxes appear in the equation of

the form (682) are called the lons^ and the constants of the equation

For our present pur-

are called their electro-cheynical equivalents.

pose, which has nothing to do with any theories of molecular consti-

we may choose such

tution,
ient,

and

call

a set of components as

may be

conven-

those ions, of which the fluxes appear in the equation of

the form (682), without farther limitation.

Now,

components of
do not necessitate any electrical currents, all the
conditions of equilibrium which relate to the movements of these
components will be the same as if the fluid were incapable of the
electrolytic process. Therefore all the conditions of equilibrium which
since the fluxes of the independently variable

an electrolytic

fluid

we have found without

apply to an electrolytic

But we have

nents.

reference to electrical considerations, will

fluid

and

its

independently variable compo-

to seek the remaining conditions of equili-

still

brium, which relate to the possibility of electrolytic conduction.

For

simplicity,

we

suppose that the fluid

shall

is

without internal

homogeneous except so far as

by gravity), and that it meets metallic

surfaces of discontinuity (and therefore

it

may

be slightly aftected

conductors {electrodes)

parts of

in diflTerent

wise l)ounded by non-conductors.

it is

its surface,

being other-

Tlie only electrical currents

which

necessary to consider are those which enter the electrolyte at

one electrode and leave

at another.

it

the conditions of equilibrium are fulfilled in a given state of

If all

the system, except those which relate to changes involving a flux of

electricity,

and we imagine the

state of the system to be varied

by

the passage from one electrode to another of the quantity of electricity de

accompanied by the quantity

d^a^ of tlie

component

specified,

without any flux of the other components or any variation

total entropy, the total vaiiation of

energy

in the

in

the

system will be rep-

resented by the expression

(

in

which

V"

V)

V, V"

6e

(//,"

IJ,!)

Sm^

(2"- T")

dm,,

denote the electrical potentials in pieces of the same

kind of metal connected with the

tional potentials at the

two

two

electrodes, T', T", the gravita-

electrodes,

potentials for the substance specified.

and

The

/y/,

///',

first tei*m

the intrinsic

represents the

incremen*; of the ))otential energy of electricity, the second the incre-

W. Gihbs

J.

ment of

Equilibrium of Heterogeneous Substances.

tlie intrinsic

energy of the ponderable matter, and the third

But by

the increment of the energy due to gravitation,*

6771^

(682)

=z a^ 6e

therefore necessary for equilibrium that

It is

V"
To extend

-V' +

a^ (//."

^^:

cx^ (//,'

T')

V"

a^

{ia:'

a,

each of the other cations (specified

by

and

ilar condition,

V-

a^ (/.;

V'"

two

^")

we may
- T")
(//,'"

etc.)

(684)

0-

write

F'")

etc.

T')

= V"

the eiFect of gravity

- a,

V'"

may

(/.,"

(685)

there will be a sim-

for each of the anions a condition of the

When

T"

this relation to all the electrodes

V'

For

503

form

T")

a^ (Ms"

- r")

(686)

etc.

be neglected, and there are but

electrodes, as in a galvanic or electrolytic cell,

we have

for

any

cation

V" and

for

a,

{/J.J

a^

(/V

or electrolytic

(687)

V'

- mA

(688)

conditio7is

cell,

of equilibrium,

the electrodes 7mdtiplied

ion, the greater 2)otential

i7i

Let us apply

i7%

the surfaces

by the electro-cheniiecd eqmvale7it of that

a7i anion being at the sa)7ie electrode as

and the

reverse being true

of a

catio7i.

this principle to different cases.

If the ion is an independently variable

by

a galvanic

of

the g7'eater electrical pote^itial,

trode, or

fulfilled

ai-e

the electro77iotive force is equal to the differe7ice

of the potential for any ion or apparent ion at

the values

(in

/<;'),

V denotes the electi'omotive force of the combination.

where V"
That is:
Whe7i all the

(I.)

any anion

V"

of

V=

itself constitutes

component of an

elec-

an electrode, the potential for the ion

any case of equilibrium which does not depend upon passive

resist-

ances to change) will have the same value within the electrode as on
its surface,

and

trode with

its

by a

cell

will be

determined by the composition of the

temperature and pressure.

with electrodes of mercury containing certain quantities of

zinc in solution (or with one such electrode

*

It is

elec-

This might be illustrated

here supposed that the gravitational potential

for each electrode.

When

and the other of pure

may be regarded as constant
may be applied to small

this is not the case, the expression

parts of the electrodes taken separately.

TRA.NS. Conn. Acad., Vol. III.

64

June, 1878.

5C4
zinc)

tT.

W. Gibhs

aud an

Equilibrhim of Heterogetieous Stihstances.

electrolytic fluid containing a salt of zinc, but not capa-

We may regard a cell in which

hydrogen acts as an ion between electrodes of palladium charged with
hydrogen as another illustration of the same principle, but the solidity of the electrodes and the consequent resistance to the diffusion
of the hydrogen Avithin them (a process which cannot be assisted by
ble of dissolving the mercury.*

Qonvective currents as in a liquid mass) present considerable obstacles

to the experimental verification of the relation.
(II.)

Sometimes the ion

soluble (as an independently variable

is

Of course its condition in the

when thus dissolved must be entirely diflierent from its condition when acting on an ion, in which case its quantity is not independently variable, as we have already seen. Its difiusion in the
component)

in the electrolytic fluid.

fluid

fluid in this state of solution is not necessarily

and

electrical current,

connected with any

in other relations its properties

may

(witli respect to its

fundamental equation, for example,)

necessary to treat

as a different substance.

if

the process

electrode,

may

be entirely

In any discussion of the internal properties of the fluid

changed.

it

by which the charge

and the ion

is

it

would be
But

(See page 117.)

of electricity

dissolved in the electrolyte

passes into the

is reversible,

we

evidently regard the potentials for the substance of the ion in

(687) or (688)
electrolyte.

relating to the substance thus

as

dissolved in the

In case of absolute equilibrium, the density of the sub-

stance thus dissolved would of course be uniform throughout the

fluid, (since it

move independently

can

of any electrical current,) so

that by the strict application of our principle

somewhat barren

we only

obtain the

any of the ions are soluble in the fluid

without their electrical charges, the electromotive force must vanish
in any case of absolute equilibrium not dependent upon passive resistNevertheless, cases in which the ion is thus dissolved in the
ances.
electrolytic fluid only to a very small extent, and its passage from
result, that if

one electrode to the other 1iy ordinary diffusion is extremely slow,

regarded as approximating to the case in which it is incapable

may be

of diffusion.

we may regard

such cases,

In

the relations (687),

(688) as approximately valid, although the condition of equilibrium

* Tf the electrolytic
could only subsist

fluid

when

electrodes identical.

dissolved the mercury as well as the zinc,

the electromotive force

is

zero,

equilibrium

and the composition

For when the electrodes are formed of the two metals

of the

in differ-

ent proportions, that which has the greater potential for zinc will have the less potential for

mercury.

[See equation (98).]

ing to the principle mentioned above,

if

This

is

inconsistent with equilibrium, accord-

both metals can act as cations.

W. Gihhs

J.

Equilibriam of Heterogeneous Substances.

505

not satisfied.

This

relating to the diffusion of the dissolved ion

may be

is

the case with hydrogen and oxygen as ions (or apparent ions)

between electrodes of platinum in some of its foi-ms.

If it be a
(III.) The ion may appear in mass at the electrode.
conductor of electricity, it may be regarded as forming an electrode,
as soon as the deposit has become thick enough to have the properThe case therefore will not be different from
ties of matter in mass.
that

first

When

considered.

the ion

is

a non-conductor, a continuous

would of course prevent the possibility

But the case in which the ion being a non-

thick deposit on the electrode

of an electrical current.

conductor

is

disengaged

not entirely covering

in

by hydrogen appearing

masses contiguous to the electrode but

It may be illustrated

an important one.

it, is

bubbles at a cathode.

in

In case of perfect

equilibrium, independent of passive resistances, the potential of the

may

ion in (687) or (688)

Yet the

be determined in such a mass.

circumstances are quite unfavorable for the establishment of pei'fect

equilibrium, unless the ion

is

to

some extent absorbed by the electrode

is fluid.
For if the ion must pass

or electrolytic fluid, or the electrode

immediately into the non-conducting mass,

into the electrode,

it is

electrolytic current

is

w^hile the electricity passes

evident that the only possible terminus of an

where the electrode, the non-f!onduct-

at the line

ing mass, and the electrolytic fluid meet, so that the electrolytic process

is

necessarily greatly retarded, and an approximate ceasing of the

current cannot be regarded as evidence that a state of approximate

But even

equilibrium has been reached.

a slight degree of solubility

may

of the ion in the electrolytic fluid or in the electrode

greatly

diminish the resistance to the electrolytic process, and help toward

producing that state of complete equilibrium which

And

theorem we are discussing.

liquid electrode

by the

may

act in the

by the

is

supposed

the mobility of the

same way.

When

in the

surface of a

the ion

is

absorbed

comes
under the heads which we have already considered, yet the fact that
the ion is set free in mass is important, since it is in such a mass that
electrode, or

the determination of the

electrolytic fluid, the case of course

value of the potential will generally be

most easily made.

(IV.)

When

the ion

is

the electrolytic fluid, and

not absorbed either by the electrode or

is

not set free in mass,

it

may

still

by
be

deposited on the surface of the electrode.

Although this can take

place only to a limited extent (without forming a body having the

properties of matter in mass), yet the electro-chemical equivalents of

all

substances are so small that a very considerable flux of electricity

J.W.Gibbs

506

may

Eqtiilibriwm of Heterogeneous Substances.

take place before the deposit will have the properties of matter

Even when the

in mass.

ion appears in mass, or

is

absorbed by the

electrode or electrolytic fluid, the non-homogeneous film between the

and the electrode may contain an additional portion

electrolytic fluid

of

Whether the ion is confined to the surface of the electrode

we may regard this as one of the cases in which we have to

it.

or not,

recognize a certain superficial density of substances at surfaces of

which we have already considered.

discontinuity, the general theory of

The

deposit of the ion will

electrode

liquid, or the closely related quantity

if it is

denoted by the same symbol

is solid.

The

effect

o'

(see

which we have

if

the electrode

can of course be best observed in the case of a

V V"

the external electromotive force

is

pages 482-500)

But whether the electrodes

liquid electrode.

combination

the superficial tension of the

afl^ect

varied,

when

it is

too

are liquid or solid,

if

applied to an electrolytic

weak to produce

a lasting current,

and the electrodes are thereby brought into a new state of polarization, in which they make eqiiilibrium with the altered value of the
electromotive force, without change in the nature of the electrodes or
of the electrolytic fluid, then by (508) or (675)

- r; d^l,

d(j'

do"

and by

- r:

dj.ll'

(687),
,/(

F' - V")

=-a^ {dfx: - dij:').

Hence
d{
If

we suppose

trodes

V V") = ^,dff'- ^ da".

(689)

that the state of polarization of only one of the elec-

is aflfected (as

will be the case

when

its

surface

is

very small

compared with that of the other), we have

d(y'=^d{V'V").
The

superficial tension of

one of the electrodes

(690)

is

then a function of

the electromotive force.

This principle has been applied by M. Lippmann to the construc-

which bears his name.* In applying equaand (690) to dilute sulphuric acid between electrodes of
mercury, as in a Lippmann's electrometer, we may suppose that the
tion of the electrometer

tions (689)

* See his memoir

" Relations entre les

Annates de Chimie etde Physique, 5e

serie,

phenom^nes

t. v,

p.

494.

electriques et capillaires,"

W. Gibbs

J.

Equilibrium of Heterogeneous Substances.

hydrogen.

suffix refers to

It will

507

be most convenient to suppose the

dividing surface to be so placed as to make the surface-density of

mercury zero. (See page 397.) The matter which exists in excess or
deficiency at the surface

may

then be expi-essed by the surface-densi-

and of hydrogen. The value of the

According to M. Lipp-

ties of sulphuric acid, of water,

last

may be determined from

mann's determinations,
state

(i.

e.,

is

is

iell's cell,

negative when the surface

the state to which

tive force

V"

it is

equation (690).

applied),

since

increases

a'

mum

V"

the electrode to which

value,

is

V" V.

with

When

equal to nine-tenths of the electromotive force of a Danrelates

and there

This

is

is

remaining

in its natural

the other electrode has a maxi-

state, the tension a' of the surface of

surface.

in its natural

is

tends when no external electromo-

it

no excess or deficiency of hydrogen at that

the condition toward which a surface tends

extended while no flux of electricity takes place.

tricity per unit of

new

The

when

it

flux of elec-

surface formed, which will maintain a surface

in

a constant condition while

in

numerical value, and

its

it

is

extended,

direction,

is

when F^'

represented
is

negative,

by
is

from

the mercury into the acid.

We have so far

supposed,

in

the main, that there are no passive

resistances to change, except such as vanish with the rapidity of the

processes which they

resist.

The

actual condition of things

respect to passive resistances appears to be nearly as follows.

with

There

does not appear to be any passive resistance to the electrolytic process

by which an ion

is

transferred from one electrode to another,

except such as vanishes with the rapidity of the process.

For, in any

case of equilibrium, the smallest variation of the externally applied

electromotive force appears to be sufficient to cause a (temporary)

But the case is not the same with respect to

by which the ion passes into new combinations
when it enters into the mass of the electrodes, or sep-

electrolytic current.

the molecular changes

or relations, as

arates itself in mass, or

is

an ion) in the electrolytic

these processes, the

dissolved (no longer with the properties of

In virtue of the passive resistance to

fluid.

external

electromotive force

may

often

vary

within wide limits, without creating any current by which the ion
transferred from one of the masses considered to the other.

words, the value of

V V"

may

obtained from (687) or (688) when

potentials for the ion as in cases

often difier greatly

we determine

I, II,

and

regard these equations as entirely valid,

III.

from that

the values of the

We

when the

is

In other

may, however,

potentials for the

508

J.

W. Gihbs

Equilibrium of Heterogeneous Substances.

ions are determined at the surface of the electrodes with reference to

the ion in the condition in which

by an

it

electrolytic current, without

But

cesses.

complete discussion of the properties of the surface

in a

of an electrode

is brought there or taken away

any attendant irreversible pro-

it

may

be necessary to distinguish (both in respect to

and to potentials) between the substance of the ion

condition and the same substance in other conditions into

surface-densities
in this

which

it

however,

any one of the conditions

when the substance of the ion

electrode by reversible processes from

necessary

is

can pass at the surface of the

The

No

cannot pass (directly) without irreversible processes.

such distinction,

which

in

it

appears to any other.

formulae (687), (688) aiford as

many

equations as there are

These, however, amount to only one independent equation

ions.

additional to those which relate to the independently variable comfluid.

This appears from the consideraany cation may be combined with a flux of any
the same direction so as to involve no electrical current, and

ponents of the electrolytic

tion that a flux of

anion in
that this

may

be regarded as the flux of an independently variable

component of the

electrolytic fluid.

General Properties of a Perfect Electro-chemical Apparatus.

When

an electrical current passes through a galvanic or electro-

lytic cell, the state of the cell is altered.

If

no changes take place

the cell except during the passage of the current, and

all

in

changes

which accompany the current can be reversed by reversing the current, the cell may be called a perfect electro-chemical apparatus.

The electromotive
tions Avhich

to

force of the cell

have just been given.

which such an apparatus

is

may be determined by the equaBut some of the general relations

subject

may

be conveniently stated

in

a form in which the ions are not explicitly mentioned.

In the most general case,

we may regard the cell as

(1) The supply of

external action of four different kinds.

subject to
electricity

and the Avithdrawal of the same quantity at the

or withdrawal of a certain quantity of heat.
(4) The motion of the surfaces enclosing
(3) The action of gravity.
the apparatus, as when its volume is increased by the liberation of
at one electrode
other.

(2)

The supply

gases.

The
which

increase of the energy in the cell

it

receives from external sources.

is

necessarily equal to that

We

may express this by

the

equation

dE

= {V'-

V") de

^dQ + dW^ + d TTp,

(691)

W. Gibhs

J.

ill

Equilihrium of Heterogeneous Substances.

which de denotes the increment of the

intrinsic

energy of the

cell,

V and

V"

de the quantity of electricity which passes through

the electrical potentials in masses

509

it,

same kind of metal con-

of the

dQ the heat received

nected with the anode and cathode respectively,

work done by gravity, and dW^ the

work done by the pressures which act on the external surface of the

dWa

from external bodies,

the

apparatus.

The

conditions under which

we suppose

the processes to take place

are such that the increase of the entropy of the apparatus

the entropy which

it

nal source of entropy

the heat which

is

is

is

equal to

The only

receives from external sources.

exter-

communicated to the

cell

by the surrounding bodies. If we write drj for the increment of

entropy in the cell, and t for the temperature, we have

Eliminating c?,
c?

dii

F") de

we

obtain

F'

-^.

d,i

(692)

^dW^ + d TFp,

(693)

or

It is

worth while to notice that

if

we give up

reversibility of the processes, so that the cell

the condition of the

no longer supposed

is

to be a perfect electro-chemical apparatus, the relation (691) will

subsist.
cell

But,

if

we

still

suppose, for simplicity, that

have the same temperature, which

perfect electro-chemical apparatus,

we

is

all

necessarily the case with a

shall have, instead of (692),

di]^ j^,

and instead of
(

is

cell, will

subjected.

de-^

is

ds +

dr/

+ d Wo + d TFp.
member

(696)

of (694), for

vary with the external influences to which the

cell

If the^cell is enclosed (with the products of electrolysis)

term will vanish.

generally to be neglected.

drawn, the term containing

it is

If

is

The term

no heat

d?/ will vanish.

the electromotive force, which

the equation,

several terms of the second

in a rigid envelop, the last

gravity

(695)

(693), (694)

V" - V)

The values of the

a given

still

parts of the

But

is

relating to

supplied or with-

in the calculation of

the most important application of

generally more convenient to suppose that the tera-

pei'ature remains constant.

510

'J.

The

W. Gihbs

Equilihrimn of Seterogeneoxis Substances.

by the terms containing d Q and di] in

and
(696) are frequently neglected in the consid(691), (693), (694),
eration of cells of which the temperature is supposed to remain constant.
In other words, it is frequently assumed that neither heat nor
cold is produced by the passage of an electrical current through a
quantities expressed

perfect electro-chemical combination (except that heat which

indefinitely diminished

by

tity of electricity passes),

cell,

unless

it

and that only heat can be produced

in

does not appear that this assumption

is

justified

In fact,

force

determined entirely by the term ^-^

it is

electrolysis.

by any

sufficient

easy to find a case in which the electromotive

reason.

dii

is

any

be by processes of a secondary natui-e, which are not

immediately or necessa,rily connected with the process of

It

may be

increasing the time in which a given quan-

terms in the second

member

in (694), all

of the equation vanishing.

the other

This

is

true

of a Grove's gas battery charged with hydrogen and nitrogen.

In

this case, the

hydrogen passes over to the nitrogen,

a process which

cell, when maintained at a constant

The work done by external pressures is evidently
nothing, and that done by gravity is (or may be) nothing. Yet an
The work done (or which may be
electrical current is produced.
done) by the current outside of the cell is the equivalent of the work
(or of a part of the work) which might be gained by allowing the
gases to mix in other ways. This is equal, as has been shown by
Lord Rayleigh,* to the work which may be gained by allowing each

does not alter the energy of the

temperature.

gas separately to expand at constant temperature from

its

initial

volume to the volume occupied by the two gases together. The same
work is equal, as appears from equations (278), (279) on page 217,
(see also page 220,) to the increase of the entropy of the system
multiplied by the temperature.
It is

possible to vary the construction of the cell in such a

that nitrogen or other neutral gas will not be necessary.

consist of a U-shaped tube of sufficient height,

gen

at

Let the

way
cell

and have pure hydro-

each pole under very unequal pressures (as of one and two

atmospheres respectively) which are maintained constant by properly

weighted pistons, sliding

in the

arms of the tube.

The

difference of

the pressures in the gas-masses at the two electrodes must of course

be balanced by the

diff*erence

acidulated water.

It will

in the height of the

two columns of

hardly be doubted that such an apparatus

* Philosophical Magazine,

vol. xlix, p. 311.

W. Glhbs

J.

Eqnilibriura of Heterogeneous Snhatances.

511

would have an electromotive force acting in the direction of a current

which would carry the hydrogen from the denser to the rarer mass.
Certainly the gas could not be carried in the opposite direction by

an external electromotive force without the expenditure of as much

(electromotive) work as is equal to the mechanical Avork necessary to

pump the

gas from the one arm of the

tulie to the other.

And

if

by any
by

modification of the metallic electrodes (which remain unchanged

the passage of electricity)
zero, so that the

we could reduce

the passive resistances to

hydrogen could be carried reversibly from one mass

to the other without finite variation of the electromotive force, the only
j)Ossible

value of the electromotive force would be represented by the

expression

^^

as a

very close a])proximation.

It will

be observed

that, although gravity plays an essential part in a cell of this kind

by maintaining the

difference of pressure in the masses of hydrogen,

the electromotive force cannot possibly be ascribed to gravity, since

the

work done by gravity, when hydrogen passes from the denser

the rarer mass,

Again,

by

it is

is

to

negative.

entirely improbable that the electrical currents caused

diiierences in the concentration of solutions of salts, (as in a cell

containing sulphate of zinc between zinc electrodes, or sulphate of

coj)per

between copper electrodes, the solution of the

salt

being of

unequal strength at the two electrodes,) which have recently been

by MM. Helmholtz and

which the mixture of solutions of
different degrees of concentration will produce heat.
Yet in cases in
which the mixture of more and less concentrated solutions is not

investigated theoretically and experimentally

Moser,* are confined to cases

in

attended with evolution or al)Sorption of heat, the electromotive force

must vanish in a cell of the kind considered, if it is determined

by the diminution of energy in the cell. And when the mixsame rule wouhl make any electromotive force
impossible except in the direction which would tend to increase the
difference of concentration.
Such conclusions as would be quite
irreconcilable with the theory of the phenomena given by Professor
simplj^

ture produces cold, the

Helmholtz.

more striking example of the necessity

of taking account of the

variations of entroj^y in the cell in a priori determinations of electro-

motive force

is

afforded by electrodes of zinc and mercury in a solu-

tion of sulphate of zinc.

Since heat

* Awnalen der Physik und Chemie,

Trans. Coxn. Acad.. Yol.

III.

is

Neue
65

absorbed when zinc

Folge,

Band

iii,

is

dissolved

February, 1878.

June, 1878.

512
in

IV.

tT.

Gihhs

Equilibrium of Heterogeneous

mercury,* the energy of the

to the mercury,

when

cell is

increased

the temperature

is

by

Siibstayices.

a transfer of zinc

maintained constant.

Yet

in this coml)ination, the electromotive force acts in the direction of

the current producing such a transfer.f

The couple presents

anomalies when a considerable quantity of zinc

mercury.
case

The electromotive

lasually cited as

is

motive force

cell,

force changes its direction, so that this

an illustration of the principle that the electro-

i. e.,

which produces or allows those changes which

by evolution of heat when they take place

are accompanied

certain

united with the

the direction of the current which diminishes the

is in

energy of the

is

directly.

whatever may be the cause of the electromotive force which has

been observed acting in the direction from the amalgam through the
Biit

which according to the determinations

electi'olyte to the zinc (a force

of M. Gaugain

only one twenty-fifth part of that which acts in the

is

when pure mercury takes

reverse direction

the place of the amalgam),

these anomalies can hardly affect the general conclusions with which

alone

we

are here concerned.

zinc and an

If

amalgam containing

which the mercury

the electrodes of a cell are pure

zinc not in excess of the

amount

will dissolve at the temperature of the experiment

its fliiidity, and if the only change (other than thermal)

accompanying a current is a transfer of zinc from one electrode to
the other, conditions which may not have been satisfied in all the
experiments recorded, but which it is allowable to suppose in a
theoretical discussion, and which certainly will not be regarded as

without losing

inconsistent with the fact that heat

in

mercury,

it is

is

absorbed when zinc

in the direction of a current transferring zinc

the electrode of pure zinc.

amalgam by
such a

is

dissolved

impossible that the electromotive force should be

from the amalgam to

For, since the zinc eliminated from the

the electrolytic process might be re-dissolved directly,

would involve the pos-

of the electromotive force

dii-ection

sibility of obtaining an indefinite amount of electromotive work, and

therefore of mechanical work, without other expenditure than that of

heat at the constant temperature of the

cell.

None of the cases which we have been considering involve combinations

by

definite proportions, and, except in the case of the cell

with electrodes of mercury and zinc, the electromotive forces are

It may perhaps be thought that with respect to those
quite small.

which combinations take place by definite proportions the

electromotive force may be calculated with substantial accuracy from
cells in

*
j-

J. Regnaiild,

Compks Eendus,

Gaugain, Comptes Eendus,

t. li,

t. xlii,

p. 778.

p.

430.

W. Gibbs

J.

Eqaillbrmni of Heterogoteous

513

iSub{>ta?i,ces.

the diminution of the energy, witliout regarding the variation of

entropy,

liut

the plienoniena of chemical comljination do not in

general seem to indicate any possihility of obtaining from the combination of snlistances
cal

work which

is

by any process whatever an amount of mechani-

equivalent to the heat produced

Ijy

the direct union

of the substances.

A kilogramme of hydrogen, for example, combining by combustion

under the pressure of the atmosphere with eight kilogrammes of oxygen
to form liquid water, yields an amount of heat which may be repre-

We

may suppose that

sented ill round numbers by 84000 calories.*
the gases are taken at the temperature of 0 C, and that the water is
reduced to the same temperature.
at

any temperature

desired.

Jiut this heat cannot be obtained

very high temperature has the

effect

of pi'eventing to a greater or less extent, the combination of the

elements.

Thus, according to M. Sainte-Claire Deville,f the tempera-

by the combustion of hydrogen and oxygen cannot

C, which im])lies that less than one-half
of the hydrogen and oxygen present combine at that temperature.
ture obtained

much

if

at all exceed 2500

This relates to combustion undei- the pressure of the atmosphere.

According to the determinations of Professor Bunsen]}; in regard

combustion in a confined space, only one-third of a mixture of
hydrogen and oxygen will form a chemical compound at the tem-

to

perature of 2850 C. and a pressure of ten atmospheres, and only a

little

more than one-half when the temperature is reduced by the

C, and the pressure to about three

addition of nitrogen to 2024

atmosijheres exclusive of the part due to the nitrogen.

Now

10 calories at 2500 C. are to be regarded as reversibly con-

vertible into one calorie at 4 C. together with the mechanical

x-epresenting the energy of 9 calories.
ories obtainable

If,

work

therefore, all the 34000 cal-

from the union of hydrogen and oxygen under atmos-

pheric pressure could be obtained at the temperature of 2500

C, and

no higher, we should estimate the electromotive work performed

in

perfect electro-chemical apparatus in which these elements are com-

bined or separated at ordinary temperatures and under atmospheric

pressure as representing nine-tenths of the 34000 calories, and the

heat evolved or absorbed in the apparatus as representing one-tenth

of the 34000 calories.

This, of course,

would give an electromotive

* See RiiUmann's Handhuch der mechanischen Wurmetheo,

ie,

Bd.

ii,

p.

290.

f Comptes Rendus, t. Ivi, p. 199; and t. Ixiv, 67.

X Pogg. Ann., Bd. cxxxi (1867), p. 161.

These numbers are not subject to correction

for the pressure of the atmosphere,

since the 34000 calories relate to combustion under the

same pressure.

514

W. Gibbs

tT.

Equilibrium of Heterogeneous Substances.

force exactly nine-tenths as great as

that

the

all

obtained on the supposition

is

34000 calories are convertible into electromotive

or

mechanical work. But, according to all indications, the estimate

2500 C. (for the temperature at which we may regard all the heat of

combustion as obtainable)

is

far too high,*

and we must regard the

theoretical value of the electromotive force necessary to electrolyze

water as considerably
the supposition that

supply

all

The

than nine-tenths of the value obtained on

less

necessary for the electromotive agent to

is

it

the energy necessary for the process.

case

is

same with respect to the electrolysis of

probably a more typical example of the

essentially the

hydrochloric acid, which

is

The phenomenon

process than the electrolysis of water.

tion

of dissocia-

much lower temperature, more

equally marked, and occurs at a

is

than half of the gas being dissociated at 1400 C.f And the heat
which is obtained by the combination of hydrochloric acid gas with
water, especially with water which already contains a considerable

probably only to be obtained at temperatures

quantity of the acid,

is

comparatively low.

This indicates that the theoretical value of the

electromotive force necessary to electrolyze this acid

(/.

the elec-

e..

ti'omotive force which woiild be necessary in a reversible electro-

chemical ajjparatus), must be very much

less

than that which could

perform in electromotive work the equivalent of

in the

the heat evolved

all

combination of hj^drogen, chlorine and water to form the liquid

submitted to electrolysis.

This presumption, based u^^on the phenom-

ena exhibited

combination of the substances,

rated

by

in the direct

the experiments of M. Favre,

who

tion of heat in the cell in which this acid

is

corrobo-

has observed an absorp-

was

The

electrolyzed.J

* Unless the received ideas concerning the behavior of gases at high temperatures
are quite erroneous,

it

is

possible to indicate the general character of a process

(involving at most only such difficulties as are neglected in theoretical discussions)

which water may be converted

into separate masses of

by

hydrogen and oxygen without

other expenditure than that of an amount of heat equal to the difference of energy of
the matter in the two states and supplied at a temperature far below 2500 C.
essential parts of the process

would be

(1)

vaporizing the water and heating

temperature at which a considerable part will be dissociated,

of the hydrogen and oxygen
until the

vapor they contain

continuous process
filtration

all

by
is

filtration,

condensed.

and

(3)

The
to a

the partial separation

the coohng of both gaseous masses

little

calculation will

the heat ol^tained in the operation of coohng

show
tlie

that in a

products of

could be utiUzed in heating fresh water.

f Sainte-Claire Deville, Comptes Bendus, t. Ixiv, p. G7.

See Memoires des Savants Strangers, Ser. 2, t. xxv, No.
:j:

t.

(2)

it

Ixxiii, p. 97.3.

The

figures obtained

tion with others of the

same nature.

by M. Favre

1, p.

42

or Comptes Bendus,

will be given hereafter, in connec-

W. Gibbs

J.

Jiquilibrhmi of Heterogeneous Substances.

515

electromotive work expended must therefore have been less than the
increase of energj'^ in the

cell.

In both cases of composition in definite proportions which

we have
compound has more entropy than its elements, and
the difl'erence is by no means inconsiderable. This appears to be the
rule rather than the exception with respect to compounds which have
less energy than their elements.
Yet it would be rash to assert that
it is an invai-iable rule.
And when one substance is substituted for
considered, the

another
tions of

in a compound, we may expect great diversity in the

energy and entropy.

In some cases, there

rela-

unit of electricity

a striking correspondence between the elecand the rate of diminution of its energy per
transmitted, the temperature remaining constant.

a notable example of this correspondence.

tromotive force of a
Daniel I's

cell is

is

cell

perhaps be regarded as a very significant case, since of

common

use,

it

all

may

It

cells in

has the most constant electromotive force, and most

nearly approaches the condition of reversibility.

we apply our

If

previous notation [compare (691)] with the substitution of finite for

infinitesimal diiferences to the determinations of

ing energy in calories,

we have

M. Favre,* estimat-

for each equivalent (32.6

kilogrammes)

of zinc dissolved

V" - V) Ae

It will
is

24327"''-,

Ae

=-

JQ= -

25394"-''-,

lOoV""'-.

be observed that the electromotive Avork performed by the

about four per

cent, less

than the diminution of energy in the

cell

cell.f

A Q, which, when negative, represents the heat evolved

when the external resistance of the circuit is very great,
was determined by direct measurement, and does not appear to have
The value

of

in the cell

been corrected

for the resistance of the cell.

This correction would

A ^, and increase that of

was obtained 'by subtracting AQ from As.
diminish the value of

It

V" V)

Ae, which

appears that under certain conditions neither heat nor cold

is

For M. Favre has found that with

dif-

ferent degrees of concentration of the nitric acid sometimes heat

and

produced

in a Grove's cell.

sometimes cold

is

produced.^

* See Mem. Savants Strang.,

When

loc. cit., p.

90

neither

is

produced, of course

or Comptes Rendus, vol. Ixix, p. 35, where

the numbers are slightly different.

|-

comparison of the experiments of different physicists has in some cases given

much

ii,

1117, 1118.
\ Mem. Sa rants

Ixxiii, p.

closer correspondence.

893.

Etrang., loc.

See Wiedemann's Galvanismus,

cit.,

p. 9.^

or Comptes Rendus,

etc.,

t.

2''^

Ixix,

Auflage, Bd.

p.

37,

and

t.

516

W. Glbbs

tT.

Ecimlibriutti of HetevKxjeneous Substances.

the electromotive force of the cell

is

exactly equal to

far less significant than the fact that

is

With

observed.

its

dimiinition

But such a coincidence

of energy per unit of electricity transmitted.

an absorption of heat has been

acid containing about seven equivalents of water

(HNOg + mO), M.

Favre has found

(J^"_ F') Z/e=

Z/

46V81''"-,

= -41824^^'-, J^ = 4957^"'-;
(HNOg+HO),
^ = -2867'^''^

and with acid containing about one equivalent of water

(

X^" F')Z/e= 49847

In the

first

example,

will

it

Jf=: 52714

"',

z/

be observed that the quantity of heat

in the cell is not small,

absorbed

^"',

and that the electromotive force

nearly one-eighth greater than can be accounted for

tion of energy in the

cell.

This absorption of heat in the

in

is

by the diminu-

cell

he has observed in other cases,

which the chemical processes are much more simple.

For electrodes of cadmium and platinum in hydrochloric acid

his

experiments give*
(

-p"_

9256
A TFp = 290'-,
V')

Ae

In this case the electromotive force

8258^"'-,

AQz=^

1288^'"-.

Z/6 z=

'-''',

is

nearly one-sixth greater than

can be accounted for by the diminution of energy in the

Avork done against the pressure of the atmosphere.

For electrodes of

zinc

and platinum

cell

same acid one

in the

with the

sei'ies

of

experiments givesf

(F" V) Ae=:

A= -

16950'^'-,

AWp = -290'^\
and a

16189

'^^',

J^z=1051'-;

later series,J

(V"- V)

Ae=i

Ae=16738'''';

17702'^'"-,

J^ = -674''''-.

J Wp = -290'-,

In the electrolysis of hydrochloric acid in a cell with a porous partition,

he has found

* Comptes Bendus,
(inchidiug the cell)

t.

Ixviii, p.

when

all

V'' V)

is

Ae

AQ, also by

The

Ae + A Wp.

obtained by adding AQ, and that of

whole

total heat obtained in the

work

is

[See (691).]

Ae by

adding

is

evidently represented

The value

of

A Wp, which

F"
is

mated, being determined by the evolution of one kilogramme of hydrogen,

f Ibid.
X

Mem. Savants

Ibid,

p. 142.

Etrang.. loc.

cit., p.

145.

circuit

turned into heat, was ascer-

This quantity, 79G8 calories,

tained by direct experiment.

(

1305.

the electromotive

F'

by
Ae

easily esti-

W. Gihhs

J.

Equllihriuni of Heterogeneous

V V") Ae 34825

Suhstancei^.

AQIW?,

'-

517

"'',

whence

Z/f-JTFp = 36938.

We

cannot assign a precise value to

rine

which was evolved

zJ

value of

TFp

must

in the

lie

W^, since the quantity of chlo-

form of gas

between

and

290*"'-

is

Hut the

not stated.

580'-,

probably nearer

to the former.

The great

difference in the results of the

two

series of

experiments

relating to electrodes of zinc and platinum in hydrochloric acid

most naturally explained by supposing some difference

in

is

the condi-

tions of the experiment, as in the concentration of the acid, or in the

extent to which the substitution of zinc for hydrogen took place.*

That which

it is

important for us to observe in

there are conditions under which heat

is

all

these cases

absorbed

in

is

that

a galvanic or

electrolytic cell, so that the galvanic cell has a greater electromotive

force than can be accounted for

by the diminution

of its energy, and

the operation of electrolysis requii'es a less electromotive force than

would be calculated from the increase of energy in the cell, especially when the work done against the pressure of the atmosphei'e is
taken into account.
It

should be noticed that

in all these

experiments the quantity rep-

by A Q (which is the critical quantity with respect to the

point at issue) was determined by direct measurement of the heat
absorbed or evolved by the cell when placed alone in a calorimeter.
The resistance of the circuit was made so great by a rheostat placed
outside of the calorimeter that the resistance of the cell was regarded
resented

as insignificant in comparison,

made

in

due to

any case for

this circumstance,

absorbed

and no correction appears to have been

this resistance.

which would

With exception
in all cases

of the error

diminish the heat

heat evolved), the probable error

in the cell (or increase the

AQ

must be very small in comparison with that of ( F'' V") Ae,

or with that of As, which were in general determined by the comparoi

* It should perhaps be stated that in his extended memoir published in 1877 in the

Memoires des Savants Strangers, in which he has presumably collected those results
of his experiments

which he regards as most important and most accurate, M. Favre

does not mention the absorption of heat in a

which cadmium takes the place of

preference for the later experiments which

the ground of this preference
of the absorption of heat,

ments.

may have

cell of this kind,

This

zinc.

t.

or iu the similar cell in

be taken to indicate a decided

showed an evolution

been,

which was a matter

See Comptes Rendus,

may

Ixviii, p. ISO.'S.

it

of heat.

Whatever

can hardly destroy the significance

of direct observation in repeated experi-

518

Gihbs

VT.

-T.

Eqiiilihrmm of Heterogeneous Substances.

ison of difFereut calorimetrical measurements, involving very miicli

greater quantities of heat.

we

In considering the numbers which liave been cited,

remember

when hydrogen

that

general very lar from reversible.

same changes

tus, the

tus, the diiference

It often

much

less

be much greater than

amount.

In either case,

in the imperfect appara-

being measured perhaps by thousands of calories.*

occurs in a galvanic or electrolytic cell that an ion which

one of the electrodes appears

set free at

is

in

would yield a much greater amount

in the cell

A Q would

is

In a perfect electrochemical appara-

of electromotive work, or absorb a

the value oi

should,

evolved as gas the process

is

by the

part absorbed

electrolytic fluid,

and

and

in pai't as gas,
in

is in

part absorbed by the

In such cases, a slight variation in the circumstances,

electrode.

which would not sensibly affect the electromotive force, would cause
all of the ion to be disposed of in one of the three ways mentioned, if
the current were sufficiently weak. This would make a considerable
* Except in the case of the Grove's
the absorption of heat

is

cell, in

marked

nfost

which the reactions are quite complicated,

in the electrolysis of hydrochloric acid.

(See page 514.)

the behavior of the substances in other circumstances.

to the circumstances

heat, the following,

The
tlie

electrolysis

The

experiments confirm the presumption afforded by

latter case is interesting, since the

In addition

mentioned above tending to diminish the observed absorption of

which are peculiar to

was performed

this case, should be noticed.

in a cell

with a porous

partition, in order to prevent

chlorine and hydrogen dissolved in the liquid from coming in contact with each

other.

It

had appeared

loc. cit., p. 1.31

in a previous series

or Comptes Eendus,

t.

Sarants Mrang.,

of experiments {Mem.

Ixvi, p. 1231,) that

a very considerable

heat might be produced by the chemical union of the gases in solution.

amount of
In a cell

without partition, instead of an absorption, an evolution of heat took place, which

sometimes exceeded 5000

form

its office, this

calories.

If,

therefore, the partition did not perfectly per-

could only cause a diminution in the value of

A Q.

large part at least of the chlorine appears to have been absorbed

A.

lytic fluid.

ment

It is

by the

electro-

probable that a slight difference in the circumstances of the experi-

a diminution of pressure, for example, might have caused the greater

part of

the chlorine to be evolved as gas, without essentially affecting the electromotive force.

The

solution of chlorine in water presents

complex reactions, but

tion of heat.

it

some anomalies, and may be attended with

appears to be always attended with a very considerable evolu-

(See Berthelot, Comptes Rendus,

t.

Ixxvi, p. 1514.)

form of gas as the normal process, we

absorption of heat in the

cell

was greatly

dimini.shed

we regard the evolumay suppose that the

If

tion of the chlorine in the

by the retention of the chlorine

in solution.

Under

certain circumstances,

chloric acid.

It

experiments which
regard

it

oxygen

is

evolved in the electrolysis of dilute hydro-

does not appear that this took place to any considerable extent in the

we

are considering.

But so far as

as a case of the electrolysis of water.

absorption of heat

is

not thereby affected.

it

may have

occurred,

we may

Tlie significance of the fact of the

W. Gibbs

J.

Equilibrium of Heterogeneous Substances.

519

and the electromotive

difference in the variation of energy in the cell,

force cannot certainly be calculated from the variation of enei'gy

alone in

all

The

these cases.

correction due to the

against the pressure of the atmosphere Avhen the ion

will not help us in reconciling these differences.

work performed
is

set free as

gas

appear on

It will

consideration that this correction will in general increase the discord-

ance in the values of the electromotive force.

appear which of these cases

is

Nor does

distinctly

it

to be regarded as normal

and which

are to be rejected as involving secondary processes.*

any case secondary processes are excluded, we should expect

when the ion is identical in substance with the electrode upon
which it is deposited, or from which it passes into the electrolyte.
But even in this case we do not escape the difficulty of the different
forms in which the substance may appear. If the temperature of the
experiment is at the melting point of a metal which forms the ion
and the electrode, a slight variation of temperature will cause the
ion to be deposited in the solid or in the liquid state, or, if the current
is in the opposite direction, to be taken up from a solid or from a
If in

it

to be

liquid body.

Since this will

variation of energy,
force

we

make

a considerable difference in the

obtain different values for the electromotive

above and below the melting point of the metal, unless we

Experiment does

also take account of the variations of entropy.

not indicate the existence of any such difference,! and

account of variations of entropy, as

in

equation (694),

that there ought not to be any, the terms -j and

*

It will

make any

between primary and secondary processes.

to the generality of these

and
\

it is

apparent

being both

we do

be observed that in using the formulae (694) and (696)

disthiction

when we take

not have to

The only

limitation

formulae depends upon the recersibilUy of the processes,

this limitation does not apply to (696).

M. Raoult has experimented with a galvanic element having an electrode of

muth

(See Comptes Rendus,

calories per

t.

Ixviii,

p.

kilogramme or 885

643.)

Since this metal absorbs

calories per equivalent

yields about 24000 calories of electromotive

liquid state of the

force
tion.

cell.

But

was manifested
In

fact,

above to about

(TO''''),

work per equivalent

in melting 12.64

while a Daniell's

cell

of metal, the solid or

bismuth ought to make a difference of electromotive force repre-

sented by .037 of a Daniell's

energy of the

bis-

with phosphoric acid containing phosphate of bismuth in solution.

in contact

in

at the

cell, if

the electromotive force depended simply upon the

M. Raoult's experiments no sudden change of electromotive

moment when

the bismuth changed

its

state of aggrega-

a change of temperature in the electrode from about fifteen degrees

fifteen

degrees below the temperature of fusion only occasioned a

variation of electromotive force equal to .002 of a Daniell's

Experiments upon lead and

Tbans. Conn. Acad., Vol.

tin

gave similar

III.

cell.

results.

66

July, 1878.

520

Gihhs

J. iPT

affected

Equilibrium^ of Heterogeneous /Substances.

by the same

difference, viz., the heat of fusion of an electro-

chemical equivalent of the metal.

it

would be easy

by

In fact,

such a difference existed,

if

arrangements by which the heat yielded

to devise

a metal in passing from the liquid to the solid state could be

transformed into electromotive work (and therefore into mechanical

work) without other expenditure.

The foregoing examples

be

will

sufficient, it is believed, to

the necessity of regarding other considerations

electromotive force of a galvanic or electrolytic
of

its

energy alone (when

temperature

its

cell

show

determining the

in

than the variation

supposed to remain con-

is

work which may be done by external

But the relations expressed l)y (693), (694),

stant), or corrected only for the

pressures or

by

gravity.

and (696) may be put in a briefer form.

If we set, as on page 144,
i/^=

we

t //,

have, for any constant temperature,

df

td i}\

=. de

and for any perfect electrochemical apparatus, the temperature of

which is maintained constant,

y_y,^_d^

dW^

dW^

de

de

de

any cell whatever, when the temperature

form and constant,

and

for

In a

cell

V"

V) de^ dip +

tZ

TTg

of any ordinary dimensions, the

f?

is

maintained uni-

TFp

(698)

work done by

gravity, as

well as the inequalities of pressure in different parts of the cell

be neglected.

If the pressure as well

we

tained uniform and constant, and

C=
where p denotes the pressure

in

if

//

the

cluding the products of electrolysis),

d'Q^:^

and

de

as the temperature

set, as

is

may
main-

on page 147,

+ jo w,
and

cell,

its

total

volume

(in-

we have

dif -\-

p dv,

for a perfect electro-chemical apparatus,

F'-F'=-f,
or for any

cell,
(

V"

V) de ^

(699)

dl.

(700)

SYNOPSIS OF SUBJECTS TREATED.

Page

PREr.iMiNARY

REMARK on

the role of energy and entropy in

thermodynamic systems

the

theory of
108

.-

CRITERIA OF EQUILIBRIUM AND STABILITY.

Criteria enunciated,

100

Meaning

110

of the term possible variations,

Passive resistances.
Validity of the criteria,

HI
112

THE CONDITIONS OF EQUILIBRIUM FOR HETEROGENEOUS MASSES IN CONTACT, WHEN

UNINFLUENCED BY GRAVITY, ELECTRICITY, DISTORTION OF THE SOLID MASSES,
OR CAPILLARY TENSIONS.
115

Statement of the problem,

Conditions relating to equilibrium between the initially existing homogeneous
parts of the system,
Meaning of the term homogeneous,
Variation of the energy of a homogeneous mass,
Actual and possible
(Jhoice of substances to be regarded as components.
components,
Deduction of the particular conditions of equilibrium when all parts of the
system have the same components,
Definition of the potentials for the component substanogs in the various
homogeneous masses,
Case in which certain substances are only possible components in a part of
-the system,
Form of the particular conditions of equilibrium when there are relations of
convertibility between the substances which are regarded as the components of the different masses,
Conditions relating to the possible formation of masses unlike any previously

existing,..

116
118
119

120

121

124

--

..-

Very small masses cannot be treated by the same method as those

116
116
116

of con-

129

siderable size,

Sense in which formula (52)

may

be regarded as expressing the condition

129
but not always necessary, 131
A mass in which this condition is not satisfied, is at least practically unstable, 133
See p. 156).
(Tills condition is farther discussed under the head of Stability.
134
Effect of solidity of any part of the system
137
Effect of additional equations of condition,
equilibrium of osmotic forces,
138
Effect of a diaphragm,
sought,

Condition (53)

is

always

sufficient for equilibrium,

FUNDAMENTAL EQUATIONS.
140
Definition and properties,
Concerning the quantities ip, Xi C -144
Expression of the criterion of equilibrium by means of the quantity i/a
145
Expression of the criterion of equilibrium in certain cases by means of the
quantity

...

C,

147

POTENTIALS.

The value

of a potential for a substance in a given mass is not dependent on the

other substances which may be chosen to represent the composition of the
mass,
148
Potentials defined so as to render this property evident,
149

522

J.

W. Gihhs

Equilihrium, of Heterogeneous Substances.

Page

In the same homogeneous mass we may distinguish the potentials for an indefinite
number of substances, each of which has a perfectly determined value. Between
the potentials for different substances in the same homogeneous mass the same
equations will subsist as between the units of these substances
149
The values of potentials depend upon the arViitrary constants involved in the definition of the energy and entropy of each elementary substance
151

COEXISTENT PHASES.

Definition of phages
of coexistent phases,
152
Number of the independent variations which are possible in a system of coexistent
phases,
152
Case of w + 1 coexistent phases, ..
153
Cases of a less number of coexistent phases,
155

INTERNAL

STABILITY

OF

HOMOGENEOUS FLUIDS AS INDICATED

BY

FUNDAMENTAL

EQUATIONS.

156
160
162
169

Greneral condition of absolute stability, .Other forms of the condition,

Stability in respect to continuous changes of phase,
Conditions which characterize the limits of stability in this respect,

GEOMETRICAL ILLUSTRATIONS.
Surfaces in which the composition of the body represented is constant,
172
Surfaces and curves in which the composition of the body represented is variable
pressure
are
constant,
and its temperature and
:
176

CRITICAL PHASES.
188

Definition,

Number

of independent variations which are possible for a critical phase while

188
remaining such,
Analytical expression of the conditions which characterize critical phases. Situ189
ation of critical phases with respect to the limits of stability,
Variations which are possible under different circumstances in the condition of a

mass

191

initially in a critical phase,

ON THE VALUES OF THE POTENTIALS WHEN

COMPONENTS IS VERY SMALL,

THE QUANTITY OF ONE OF THE

194

ON CERTAIN POINTS RELATING TO THE MOLECULAR CONSTITUTION OF

BODIES.

Proximate and ultimate components,

Phases of dissipated energy,
Cataly.sis.

catalytic agent,
perfect
equation for phases of

-.

197
200
201

dissipated energy may be formed from the

201
more general form of the fundamental equation,
The phases of dissipated energy may sometimes be the only phases the existence
201
of which can be experimentally verified,

A fundamental

THE CONDITIONS OF EQUILIBRIUM FOR HETEROGENEOUS MASSES UNDER THE INFLUENCE OF GRAVITY.
The problem is treated by two different methods
203
The elements of volume are regarded as variable,
.- 207
The elements of volume are regarded as fixed,

FUNDAMENTAL EQUATIONS OF IDEAL GASES AND GAS-MIXTURES.

Ideal gas,
Ideal gas-mixture

Dalton's Law,

...
Inferences in regard to potentials in liquids and solids,
Considerations relating to the increase of entropy due to the mixture of gases by

^27

diffusion,

of dissipated energy of an ideal gas-mixture with

are chemically related,

The phases

210
215
225

components which
230

J.

W. Gibhs

Equilibriwn of Heterogeneous Substances.

523
Page

Gas-mixtures with convertible components,

Case of peroxide of nitrogen,
Fundamental equations for the phases of equilibrium,

234
237
245

SOLIDS.

The conditions

of internal and external equilibrium for solids in contact with fluids

with regard to all possible states of strain,
._
343
Strains expressed by nine differential coefficients,
344
Variation of energy in an element of a solid,
..
344
Deduction of the conditions of equilibrium,
346
Discussion of the condition which relates to the dissolving of the solid,
352
Fundamental equations for solids.
361

Concerning solids which absorb

375

fluids,

THEORY OF CAPILLARITY.
SURFACES OF DtSCONTINUITY BETWEEN FLUID MASSES.
Preliminary notions. Surfaces of discontinuity.
Dividing surface,
The particular conditions of equilibrium for contiguDiscussion of the problem.
ous masses relating to temperature and the potentials which have already been
obtained are not invalidated l\v the influence of the surface of discontinuity.
Superficial energy and entropy.
Superficial densities of the component subGeneral expression for the variation of the superficial energy. Constances.
dition of equilibrium relating to the pressures in the contiguous masses,
Fundamental equations for surfaces of discontinuity between fluid masses,
Experimental determination of the same,
Fundamental equations for plane surfaces,

Stability of surfaces of discontinuity

(1 ) with respect to changes in the nature of the surface,
(2) with respect to changes in which the form of the surface is varied,
On the possibility of the formation of a fluid of different phase within any

geneous

On

380

400
405

homo-

"_

fluid,

380
391
394
395

42g

the possible formation at the surface where two different homogeneous fluids

meet of a fluid of different phase from either,

422
Substitution of pressures for potentials in fundamental equations for surfaces,
429
Thermal and mechanical relations pertaining to the extension of surfaces of discontinuity,

Impermeable

434
44Q

films,

The conditions

of internal equilibrium for a system of heterogeneous fluid masses

without neglect of the influence of the surfaces of discontinuity or of gravity,. 442
Conditions of stability,
[
45 j
On the possibility of the formation of a new surface of discontinuity where several surfaces of discontinuity meet,

The conditions of stability for fluids relating to the formation

line in which three surfaces of discontinuity meet,
The conditions of stability for fluids relating to the formation
point where the vertices of four different masses meet,
Liquid

453
of a

new phase

at a

of a

new phase

at a

455

"

films,

Definition of an element of the film,

454
4gij
^g-j

Each element may generally be regarded as in a state of equilibrium. Properties of an element in such a state and sufficiently thick for its interior to
have the properties of matter in mass. Conditions under which an exten-

sion of the film will not cause an increase of tension.

When the film has
more than one component which does not belong to the contiguous masses
extension will in general cause an increase of tension.
Value of the elasticity of the film deduced from the fundamental equations of the surfaces
and masses. Elasticity manifest to observation,
4gg
The elasticity of a film does not vanish at the limit at which its interior
ceases to have the properties of matter in mass, but a certain kind
of
instability is developed,
aijo
Application of the conditions of equilibrium already deduced for a system
under the influence of gravity (pages 447, 448) to the case of a liquid film,
473
Concerning the formation of liquid films and the processes which lead to
their destruction.
Black spots in films of soap-water,
_
475

524

J.

W. Gihhs

Equilihriimi of Heterogeneous Substances.

SURFACES OF DISCONTINUITY BETWEEN SOLIDS AND FLUIDS.

Page

Preliminary notions,
Conditions of equilibrium for isotropic solids,

'

--

Effect of gravity,

Conditions of equilibrium in the case of crystals,

Effect of gravity,
Limitations,
Conditions of equilibrium for a line at

which

which three

different

masses meet, one of

495

_-

is solid,

482
485
488
489
492
493

General relations,

49'7

Another method and notation,

49t

ELECTROMOTIVE FORCE.
Modification of the conditions of equilibrium by electromotive force,
Equation of fluxes. Ions. Pllectro-chemical equivalents,
Conditions of equilibrium,

501
501
502
503

Four cases,
Lippmann's electrometer,
Limitations due to passive resistances,
General properties of a perfect electro-chemical apparatus,
Reversibility the test of perfection,

506
507
508
508

Determination of the electromotive force from the changes which take place
Modification of the formula for the case of an imperfect
in the cell.

apparatus,
When the temperature of tlie cell is regarded as constant, it is not allowable
This
to neglect the variation of entropy due to heat absorbed or evolved.
is shown by a Grove's gas battery charged with hydrogen and nitrogen,
by the currents caused by differences in the concentration of the electrolyte,
and by electrodes of zinc and mercury in a solution of sulphate of zinc,
That the same is true when the chemical processes take place by definite
proportions is shown by a priori considerations based on the phenomena
exhibited in the direct combination of tlie elements of water or of hydro,

509

510
51

511

513

chloric acid,

and by the absorption of heat which M. Favre has in many cases observed
516
in a galvanic or electrolytic cell,
different physical states in which the ion is deposited do not affect the
Experiments
value of the electromotive force, if the phases are coexistent.

The

of M. Raoult,

Other formulae for the electromotive force,

518
520

ERRATA TO VOL.

Hagerman, read Hagenman.

Page

1,

line 13, for

Page

5,

line 30, for Yetumnus, read Yertumnus.

Page

9,

last line, for 1873,

Page

11, line 31, for virttcillata,

Page

13, line 34, for cappilare,

read capillare.

Paga

23, line 4, for Smythella,

read Samythella.

Page

28, line 19, for

Page

35, line 3, for

read 1874.
read

verticillata

Caridon, read Caridion.

Scapellum, read Scalpellum.
read branchlets.

Page

58, line 14, for branches,

Page
Page

60, line 12, for Plate

167, formula (168), for

m,, read

Page

167, formula (169), for

m,,

Page

239, formula (333), for

read

Page

295, note

Ueber de Gliedmassen, read Ueber das Skelett der Glied-

X, read IX.

z^,.

mn_i, read

1st line, for

/'n-i-

a.it

f,

fj-,,

massen.

Page

304. note, for prominal, read proximal.

Page 356,

last line but two, for crystalline solid, read solid of continuous crystalline

structure.

Page 385, line 13, for M', read M.

Pages 391, 394, 395, 400, in headings, after Discontinuity^ add between Fluid Masses.
Page 403, line 16, after any other film, add of the same components.
add case.

Page 405,

line 29, after this,

Page 432,

line 15 of foot-note, for

In figure 40, plate XVI, there

points.

is

11,

read H,.

a series of ovals around one-half of the real double

There should be added to the curve, as represented,

ovals around each of the remaining real double points.

a like

series of

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