Theory of Heat - Maxwell PDF

TEXT-BOOKS OF SCIENCE
A D A P T E D F O R T H E U S E OY
ARTISANS AND STUDENTS IN PUBLIC AND SCIF.XCF. SCHOOLS.
THEORY OF HEAT.
IRIS - LILLIAD - Université Lille 1

LONDON t PRINTED BY
1
SPOTTl-SWOOnK AND CO., NEW-STREET SQL A R K
AND PARLIAMENT STREET

T H E O R Y OF HEAT.
EY
J. CLERK MAXWELL, M.A.

LI..D. E D I N . , F.R.SS. L. & E.
Honorary Fellow of Trinity College aud Professor of Experimental Physics
in tlie University of Cambridge.
.KX)J$RTIT EDITION.
LONDON:
LUNliMA tfS, G R E E N , iftrN IV" CO,
i875-

PREFACE.
T H E A I M of this book is to exhibit the scientific

connexion of the various steps by which our know
ledge of the phenomena of heat has been extended.
The first of these steps is the invention of the thermo
meter, by which the registration and comparison
of temperatures is rendered possible. The second
step is the measurement of quantities of heat, or
Calorimetry. The whole science of heat is founded
on Thermometry and Calorimetry, and when these
operations are understood we may proceed to the
third step, which is the investigation of those relations
between the thermal and the mechanical properties of
substances which form the subject of Thermodynamics.
The whole of this part of the subject depends on the
consideration of the Intrinsic Energy of a system of
bodies, as depending on the temperature and physical
state, as well as the form, motion, and relative position
of these bodies. Of this energy, however, only a
part is available for the purpose of producing me
chanical work, and though the energy itself is inde
structible, the available part is liable to diminution by
the action of certain natural processes, such as con
duction and radiation of heat, friction, and viscosity.
These processes, by which energy is rendered unavail
able as a source of work, are classed together under
the name of the Dissipation of Energy, and form the

vi Preface.
subjects of the next division of the book. T h e last

chapter is devoted to the explanation of various
phenomena by means of the hypothesis that bodies
consist of molecules, the motion of which constitutes
the heat of those bodies.
In order to bring- the treatment of these subjects
within the limits of this text-book, it has been found
necessary to omit everything which is not an essential
part of the intellectual process by which the doctrines
of heat have been developed, or which does not
materially assist the student in forming his own judg
ment on these doctrines.
For this reason, no account is given of several very-
important experiments, and many illustrations of the
theory of heat by means of natural phenomena are
omitted. The student, however, will find this part of
the subject treated at greater length in several excel
lent works on the same subject which have lately
appeared.
A full account of the most important experiments
on the effects of heat will be found in Dixon's
'Treatise on H e a t ' (Plodges & Smith, 1849).
Professor Ealfour Stewart's treatise contains all that
is necessary to be known in order to make experi
ments on heat. The student may be also referred to
Deschanel's 'Natural Philosophy,' Part I I . , translated
by Professor Everett, who has added a chapter on
Thermodynamics; to Professor Rankine's work on the
Steam Engine, in which he will find the first systematic
treatise on thermodynamics; to Professor Tait's ' Ther
modynamics/ which contains an historical sketch of
the subject, as well as the mathematical investigations ;
and to Professor Tyndall's work on ' Heat as a Mode
of Motion,' in which the doctrines of the science are
forcibly impressed on the mind by well-chosen illus
trative experiments. The original memoirs of Pro
fessor Clausius, one of the founders of the modern
science of Thermodynamics, have been edited in
English by Professor Hirst,
C O N T E N T S .
CHAPTER I
INTRODUCTION.
PAGE
Meaning of the word Temperature . . . . . . I
The Mercurial Thermometer . . . . . . . 5
Heat as a Quantity . . . . . . . . . 6
Diffusion of Heat by Conduction and Radiation . . . . 10
The three Physical States of Bodies . . . . . . 16
CHAPTER II.
THERMOMETRY, OR THE REGISTRATION OF TEMPERATURE.
Definition of Higher and Lower Temperature . . . . 32

Temperatures of Reference . . . . . . . 34
Different Thermometric Scales . . . . . . . 37
Construction of a Thermometer . . . . . . 40
The Air Thermometer . . . . . . . . 46
Other Methods of Ascertaining Temperatures . . . . 5 1
CHAPTER III.
CALORIMETRY, OR THE MEASUREMENT OF HEAT.
Selection of a Unit of Heat . . . . . . . 54

A l l Heat is of the same Kind . . . . . . . 56
Ice Calorimeters . . . . . . . . . 58
Bunsen's Calorimeter . . . . . . . . 61
Method of Mixture . . . . . . . . . 63
Definitions of Thermal Capacity and Specific lieat . . . 65
Latent Heat of Steam . . . • 69

WE 11 Contents.
C H A P T E R I V .
ELEMENTARY' DYNAMICAL PRINCIPLES.

PAGR
M E A S U R E M E N T O F Q U A N T I T I E S . . . . . . . 74
T H E U N I T S O F L E N G T H , M A S S , A N D T I M E , A N D T H E I R D E R I V E D U N I T S . 76
M E A S U R E M E N T O F F O R C E . . . . . . . . 8 3
W O R K A N D E N E R G Y . . . . . . . . . 87
P R I N C I P L E O F T H E C O N S E R V A T I O N OF E N E R G Y . . . . . 9 2
C H A P T E R V .
MEASUREMENT OF INTERNAL FORCES AND THEIR EFFECTS.
L O N G I T U D I N A L P R E S S U R E A N D T E N S I O N . . . . . . 94
D E F I N I T I O N OF A F L U I D . — H Y D R O S T A T I C P R E S S U R E . . . . 95
W O R K D O N E B Y A P I S T O N O N A F L U I D . . . . . . 1 0 1
W A T T ' S I N D I C A T O R A N D T H E I N D I C A T O R D I A G R A M . . . . 1 0 2
E L A S T I C I T Y OF A F L U I D . . . . . . . . 1 0 7
C H A P T E R V I .
LINES OF EQUAL TEMPERATURE ON THE INDICATOR

DIAGRAM.
R E L A T I O N B E T W E E N V O L U M E , P R E S S U R E , A N D T E M P E R A T U R E . . 1 0 8
I S O T H E R M A L L I N E S OF A G A S . . . . . . 1 RO
I S O T H E R M A L L I N E S O F A V A P O T I R I N C O N T A C T W I T H I T S L I Q U I D . . 1 1 3
S T E A M L I N E A N D W A T E R L I N E . . . . . . . 1 1 7
C O N T I N U I T Y OF T H E L I Q U I D A N D G A S E O U S S T A T E S . — E X P E R I M E N T S O F
C A G N I A R D D C LA T O U R A N D A N D R E W S . . . . . 1 1 8
C H A P T E R V I I .
ADIABATIC LINES.
P R O P E R T I E S OF A S U B S T A N C E W H E N H E A T I S P R E V E N T E D F R O M E N T E R I N G OR
L E A V I N G I T . . . . . . . . . 1 2 7
T H E A D I A B A T I C L I N E S A R E S T E E P E R T H A N T H E I S O T H E N N A L S . . 1 3 0
D I A G R A M S H O W I N G T H E E F F E C T S O F H E A T O N W A T E R . . . . 1 3 4

Contents. ix
CHAPTER VIII.
IIEAT ENGINES.
P A G E
Carnot's Engine , . . . . . , . ,138

Second L a w of Thermodynamics . . . . . . 153
Carnot's Function and Thomson's Absolute Scale of Temperature 155
Maximum Efficiency of a Heat Engine . . . , .158
Thermodynamic Scale of TempcraLure . . . . . 160
Entropy . . . . . . . . . . .162
Fictitious Thermal Lines . . . . . . . .164
CHAPTER IX.
DELATIONS BETWEEN" THE PHYSICAL PROPERTIES

OF A SUBSTANCE.
Four Thermodynamic Relations . . . . . .165

The two Modes of Defining Specific Heat . . . . 169
T h e two Modes of Defining Elasticity . . . . . iji
C H A P T E R X.
LATENT HEAT.
Relation between the Latent Heat and the Alteration of the Volume
of the Substance during a Change of State . . . 173
Lowering of the Freezing Point "by Pressure . . . 176
CHAPTER XI.
THERMODYNAMICS OF GASES.
Cooling by Expansion . . . . . . . .180

Calculation of the Specific Heat of Air . 183
CHAPTER XII.
ON THE INTRINSIC ENERGY OF A SYSTEM OF BODIES.
Intrinsic Energy defined . . . . . . . ,185

Available Energy . . . . . . . . . 187
Dissipation of Energy . . . . . . . . 192
Mechanical and Thermal Analogies . . . . . . 193
Prof. Gibbs' Thermodynamic Model . . . . . 195

x
Contents.
CHAPTER XIII.
ON FREE EXPANSION.
PAGE
Theory of a Fluid rushing through a Porous Plug . . . 209
Determination of the Dynamical Equivalent of Heat . . .211
Determination of the Absolute Scale of Temperature . . .213
CHAPTER XIV.
DETERMINATION OF HEIGHTS BY THE BAROMETER.
Principle of the Barometer . . . . . . ,217

The Barometer in a Diving Bell = 218
Height of the ' Homogeneous Atmosphere' . . . .220
Height of a Mountain found by the Barometer . . . .221
• CHAPTER XV.
ON THE PROPAGATION OF WAVES OF LONGITUDINAL

DISTURBANCE.
Waves of Permanent Type . . . . . . .223

Velocity of Sound 228
CHAPTER XVL
ON RADIATION.
Definition of Radiation . . . . . . . . 230

Interference . . . . . . . . . . 334
Different Kinds of Radiation . . . . . . . 237
Prevost's Theory of Exchanges . . . . . . . 240
Rate of Cooling . . . . . . . . . 246
Effects of Radiation on Thermometers . . . . .248

Contents. XI
CHAPTER XVII.
ON CONVECTION CURRENTS.
PAGE
How they a r e P r o d u c e d . . . . . . . .250
Joule's D e t e r m i n a t i o n o f the P o i n t of M a x i m u m D e n s i t y of W a t e r 252
CHAPTER XVIII.
ON THE DIFFUSION OF HEAT BY CONDUCTION.
Conduction through a Plate . . . . . . .2^3

D i f f e r e n t M e a s u r e s of C o n d u c t i v i t y . . . . . . 255
C o n d u c t i o n in a S o l i d . . . . . . . .255
Sketch of Fourier's T h e o r y . '. . . . . .259
H a r m o n i c Distributions of Temperature . . . . . 263
S t e a d y a n d P e r i o d i c F l o w of H e a t . . . . . 265
D e t e r m i n a t i o n o f the T h e r m a l C o n d u c t i v i t y o f B o d i e s . . 26S
A p p l i c a t i o n s o f the Theory . . . . . . . 272
CHAPTER XIX.
ON THE DIFFUSION OF FLUIDS.
Coefficient of D i f f u s i o n . . . . . . . . 275
R e s e a r c h e s of G r a h a m a n d L o s c h m i d t . . . . . 278
CHAPTER XX.
ON CAPILLARITY.
Superficial E n e r g y and Superficial T e n s i o n . . . . 2S0

R i s e of a L i q u i d in a T u b e . . . . . . . 286
E v a p o r a t i o n , a n d C o n d e n s a t i o n as A f f e c t e d by Capillarity . . Z87
T a b l e of Superficial Tension . . . . . . . 292

Contents.
C H A P T E R XXI.
ON ELASTICITY AND VISCOSITY.

PAGE
D i f f e r e n t K i n d s of Stress and Strain . . . . . . 294.
Coefficient o f V i s c o s i t y . . . . . . . . 297
C H A P T E R XXII.
MOLECULAR THEORY OF THE CONSTITUTION OF BODIES.
Kinetic and Potential E n e r g y . . . . . . . 301

E v i d e n c e that H e a t is the K i n e t i c E n e r g y of the Molecules of a
Body . 303
K i n e t i c T h e o r y of G a s e s . . . . . . . . 307
r
D e d u c t i o n of the L a w s of G a s e s . . . . . - 3 5
Equilibrium of a Vertical C o l u m n . . . . . . 3'9
Diffusion, Viscosity, and Conduction . . . . .321
2
Evaporation and Condensation . . . . . . . 33
2
Electrolysis . . . . . . . . . . 35
2
Radiation 3&
2
L i m i t a t i o n of the S e c o n d L a w of T h e r m o d y n a m i c s . . . 37
T h e P r o p e r t i e s of M o l e c u l e s . . . . . . . 33°

A TREATISE
ON
H E A T .
C H A P T E R I.
I NTRODUCTION.
THE DISTINCTION between hot bodies and cold ones is

familiar to all, and is associated in our minds with the
difference of the sensations which we experience in touching
various substances, according as they are hot or cold. The
intensity of these sensations is susceptible of degrees, so that
we may estimate one body to be hotter or colder than
another by the touch. The words hot, warm, cool, cold,
are associated in our minds with a series of sensations which
we suppose to indicate a corresponding series of states of
an object with respect to heat.
We use these words, therefore, as the names of these
states of the object, or, in scientific language, they are the
names of Temperatures, the word hot indicating a high
temperature, cold a low temperature, and the intermediate
terms intermediate temperatures, while the word temperature
itself is a general term intended to apply to anyone of these
states of the object.
Since the state of a body may vary continuously from
cold to hot, we must admit the existence of an indefinite
number of intermediate states, which we call intermediate
B

2 Introduction.
temperatures. W e may give names to any number of

particular d e g r e e s of temperature, a n d express a n y other
t e m p e r a t u r e b y its relative p l a c e a m o n g these degrees.
T h e t e m p e r a t u r e of a b o d y , therefore, is a q u a n t i t y w h i c h
indicates h o w h o t o r h o w c o l d the b o d y is.
W h e n w e say that the t e m p e r a t u r e o f o n e b o d y is higher
or l o w e r t h a n that o f another, w e m e a n that the first b o d y is
hotter o r c o l d e r than the s e c o n d , b u t w e also i m p l y that w e
refer the state o f b o t h b o d i e s to a c e r t a i n . scale o f tempe
ratures. B y the use, therefore, o f the w o r d t e m p e r a t u r e ,
w e fix in o u r m i n d s the conviction that it is p o s s i b l e , not
o n l y to feel, b u t to m e a s u r e , h o w hot a b o d y is.
Words o f this k i n d , w h i c h express the s a m e things as
the w o r d s o f primitive l a n g u a g e , b u t express them in a w a y
susceptible of accurate numerical statement, are called
1
scientific terms, b e c a u s e they c o n t r i b u t e to the g r o w t h of
science.
We m i g h t s u p p o s e that a p e r s o n w h o has carefully cul
tivated his senses w o u l d b e a b l e b y simply touching an
o b j e c t to assign its p l a c e in a scale of temperatures, b u t it is
f o u n d b y e x p e r i m e n t that the estimate f o r m e d of t e m p e r a t u r e
b y the touch d e p e n d s u p o n a g r e a t variety o f circumstances,
s o m e o f these relating to the texture o r consistency o f the
object, a n d some to the t e m p e r a t u r e o f the h a n d o r the
state o f health of the p e r s o n w h o m a k e s the estimate.
F o r instance, if the temperature o f a p i e c e o f w o o d w e r e
the s a m e as that of a p i e c e of iron, a n d m u c h h i g h e r t h a n
that of the h a n d , w e s h o u l d estimate the iron to b e hotter
than the w o o d , b e c a u s e it parts with its heat m o r e r e a d i l y to
the h a n d , w h e r e a s if their temperatures w e r e e q u a l , a n d
m u c h l o w e r than that o f the h a n d , w e s h o u l d estimate the
iron to b e c o l d e r than the w o o d .
T h e r e is another c o m m o n e x p e r i m e n t , in w h i c h w e p l a c e
o n e h a n d in hot w a t e r a n d the other in c o l d for a sufficient
' ' Scientifick, a d j . P r o d u c i n g d e m o n s t r a t i v e knowledge.'—Johnson's

Diet.

Temperature.
3
time. If we then d i p b o t h h a n d s in the same basin of
l u k e w a r m w a t e r alternately, or e v e n at once, it will a p p e a r
c o l d to the w a r m e d h a n d a n d hot to the c o o l e d h a n d .
I n fact, o u r sensations of every k i n d depend upon so
raany v a r i a b l e conditions, that for all scientific p u r p o s e s w e
prefer to form o u r estimate of the state o f b o d i e s f r o m their
observed action on some a p p a r a t u s w h o s e conditions are
m o r e simple a n d less v a r i a b l e than those o f our o w n senses.
T h e properties o f m o s t substances v a r y w h e n their tem
perature varies. S o m e o f these variations are a b r u p t , a n d
serve to i n d i c a t e particular temperatures as points of re
ference; others are continuous, a n d serve to m e a s u r e o t h e r
temperatures b y c o m p a r i s o n with the temperatures of refer
ence.
F o r instance, the t e m p e r a t u r e at w h i c h ice melts is f o u n d
to be a l w a y s the s a m e u n d e r o r d i n a r y circumstances, t h o u g h ,
as w e shall see, it is slightly altered b y c h a n g e o f pressure.
T h e t e m p e r a t u r e of steam w h i c h issues from b o i l i n g w a t e r
is also constant w h e n the pressure is constant.
T h e s e t w o p h e n o m e n a therefore—the melting of ice a n d
the b o i l i n g o f w a t e r — i n d i c a t e in a visible m a n n e r t w o t e m p e
ratures w h i c h w e m a y use as points of reference, the position
o f w h i c h d e p e n d s o n the properties of w a t e r a n d n o t o n the
conditions of our senses.
O t h e r c h a n g e s o f state w h i c h take p l a c e at temperatures
m o r e or less definite, such as the melting of w a x or of
lead, a n d the b o i l i n g o f l i q u i d s o f definite c o m p o s i t i o n , are
occasionally u s e d to indicate w h e n these temperatures a r e
attained, b u t the m e l t i n g of ice a n d the boiling of pure
w a t e r at a s t a n d a r d pressure r e m a i n the most important
temperatures of reference i n m o d e m science.
These p h e n o m e n a o f c h a n g e o f state serve to indicate
only a certain n u m b e r of particular temperatures. In
o r d e r to m e a s u r e t e m p e r a t u r e s in general, w e m u s t avail
ourselves of some property of a substance which alters
continuously with the temperature.
n 2

4 Introduction.
T h e v o l u m e of m o s t substances increases continuously

as the t e m p e r a t u r e rises, the p r e s s u r e r e m a i n i n g constant.
T h e r e are exceptions to this rule, a n d the dilatations of
different substances are n o t in g e n e r a l in the s a m e p r o p o r
tion ; b u t any substance in w h i c h a n increase of temperature,
h o w e v e r small, p r o d u c e s an increase o f v o l u m e m a y b e u s e d
to indicate c h a n g e s of temperature.
F o r instance, m e r c u r y a n d glass b o t h e x p a n d w h e n heated,
but the dilatation o f m e r c u r y is greater than that of glass.
H e n c e if a c o l d glass vessel b e filled with c o l d m e r c u r y , a n d
if the vessel a n d the m e r c u r y in it are then e q u a l l y heated,
the glass vessel will e x p a n d , b u t the m e r c u r y w i l l expand
m o r e , so that the vessel will n o l o n g e r c o n t a i n the mercury.
I f the vessel b e p r o v i d e d with a l o n g neck, the m e r c u r y
forced out of the vessel will rise in the neck, a n d if the n e c k
is a n a r r o w t u b e finely g r a d u a t e d , the a m o u n t o f m e r c u r y
forced out of the vessel m a y b e accurately m e a s u r e d .
T h i s is the principle of the c o m m o n mercurial thermo
meter, the construction o f w h i c h will b e afterwards m o r e
minutely d e s c r i b e d . A t present w e c o n s i d e r it simply as a s
instrument the indications o f w h i c h v a r y w h e n the tempe
rature varies, b u t are a l w a y s the same w h e n the t e m p e r a t u r e
of the instrument is the same.
T h e dilatation of other liquids, as w e l l as that of solids a n d
of gases, m a y b e u s e d for t h c r m o m e t r i c purposes, a n d the
thermo-electric properties of metals, a n d the variation o f their
electric resistance with temperature, are also e m p l o y e d in
researches o n heat. W e must first, h o w e v e r , study the theory
o f temperature in itself b e f o r e w e e x a m i n e the properties o f
different substances as related to temperature, a n d for this
p u r p o s e w e shall use the particular m e r c u r i a l thermometer
just d e s c r i b e d .

Tlie Thermometer. 5
THE MERCURIAL THERMOMETER.
T h i s t h e r m o m e t e r consists of a glass t u b e terminating in

a b u l b , the b u l b a n d part of the tube being filled with
mercury, a n d the rest of the t u b e b e i n g empty. W e shall
s u p p o s e the t u b e to b e g r a d u a t e d in a n y m a n n e r so that the
h e i g h t of the m e r c u r y in the tube m a y b e o b s e r v e d a n d
recorded. W e shall not, h o w e v e r , a s s u m e either that the
t u b e is o f u n i f o r m section or that the d e g r e e s are o f e q u a l
size, so that the scale of this primitive t h e r m o m e t e r must b e
r e g a r d e d as c o m p l e t e l y arbitrary. B y m e a n s o f our t h e r m o
meter w e c a n ascertain whether o n e temperature is higher or
l o w e r than another, or e q u a l to it, b u t w e c a n n o t assert that
the difference b e t w e e n two temperatures, A a n d B, is greater
or less than the difference b e t w e e n t w o other temperatures,
c a n d D.
W e shall s u p p o s e that in every o b s e r v a t i o n the temperature
o f the m e r c u r y a n d the glass is e q u a l a n d uniform o v e r the
w h o l e thermometer. The r e a d i n g o f the scale will then
d e p e n d o n the temperature o f the thermometer, a n d , since
w e h a v e not yet established a n y m o r e perfect thermometric
scale, w e shall call this r e a d i n g provisionally ' the temperature
b y the arbitrary scale of the thermometer.'
T h e r e a d i n g o f a t h e r m o m e t e r indicates p r i m a r i l y its o w n
temperature, b u t if w e b r i n g the t h e r m o m e t e r into intimate
contact with another substance, as for instance if w e p l u n g e
it into a l i q u i d for a sufficient time, w e find that the r e a d i n g
of the t h e r m o m e t e r b e c o m e s h i g h e r or l o w e r a c c o r d i n g as
the l i q u i d is hotter or c o l d e r than the thermometer, a n d that
if w e leave the t h e r m o m e t e r in contact with the substance for
a sufficient time the r e a d i n g b e c o m e s stationary. L e t us
call this ultimate r e a d i n g ' t h e temperature o f the substance.'
W e shall find as w e g o on that w e h a v e a right to d o so.
L e t us n o w take a vessel o f w a t e r w h i c h w e shall s u p p o s e
to b e at the t e m p e r a t u r e of the air, so that if left to itself it

6 Introduction.
would remain at the same temperature. Take another

smaller vessel o f thin sheet c o p p e r or tin plate, a n d fill it
with water, oil, or a n y other liquid, a n d i m m e r s e it i n the
larger vessel o f w a t e r for a certain time. T h e n , if by means
of our thermometer w e register the temperatures of the
liquids in the t w o v e s s e l s b e f o r e a n d after the i m m e r s i o n of
the c o p p e r vessel, w e find that if they a r c originally at the
s a m e t e m p e r a t u r e the t e m p e r a t u r e of b o t h r e m a i n s the s a m e ,
b u t that i f o n e is at a h i g h e r t e m p e r a t u r e than the other, that
w h i c h has the h i g h e r t e m p e r a t u r e b e c o m e s c o l d e r a n d that
w h i c h has the l o w e r t e m p e r a t u r e b e c o m e s hotter, so that i f
they continue in contact for a sufficient time they arrive at
last at the s a m e temperature, after w h i c h n o c h a n g e o f tem
p e r a t u r e takes place.
T h e loss of t e m p e r a t u r e b y the hot b o d y is not i n g e n e r a l
e q u a l to the g a i n o f temperature b y the c o l d b o d y , b u t it is
manifest that the t w o simultaneous p h e n o m e n a are d u e to
o n e cause, a n d this cause m a y b e d e s c r i b e d as the p a s s a g e
o f H e a t f r o m the hot b o d y to the cold one.
A s this is the first time w e h a v e u s e d the w o r d H e a t , let us
e x a m i n e w h a t w e m e a n b y it.
We find the cooling of a h o t b o d y a n d the h e a t i n g of
a cold b o d y h a p p e n i n g simultaneously as parts of the same
p h e n o m e n o n , a n d w e d e s c r i b e this p h e n o m e n o n as the p a s
sage of h e a t f r o m the hot b o d y to the c o l d one. H e a t , then,
is s o m e t h i n g w h i c h m a y b e transferred from o n e b o d y to
a n o t h e r , so as to d i m i n i s h the quantity o f heat i n the first
and increase that in the second by the same amount.
W h e n h e a t is communicated to a b o d y , the temperature
of the b o d y is generally increased, but sometimes other
effects are p r o d u c e d , such as c h a n g e of state. W h e n heat
leaves a b o d y , there is either a fall o f t e m p e r a t u r e or a
c h a n g e o f state. I f n o heat enters or leaves a body, and
if no changes of state or m e c h a n i c a l actions take place
in the body, the temperature of the body will remain
constant.

Heat as a Quantity. 7
H e a t , therefore, m a y pass out o f o n e b o d y into another
just as w a t e r m a y b e p o u r e d f r o m o n e vessel into another,
and it m a y b e r e t a i n e d in a b o d y f o r a n y t i m e , j u s t as w a t e r
m a y b e k e p t i n a v e s s e l . W e h a v e t h e r e f o r e a right t o s p e a k
of heat as o f a measurable quantity, a n d t o t r e a t it m a t h e m a
tically l i k e o t h e r m e a s u r a b l e q u a n t i t i e s s o l o n g as it c o n t i n u e s
t o exist as h e a t . W e shall find, h o w e v e r , t h a t w e h a v e no
right t o t r e a t h e a t as a substance, f o r it m a y b e transformed
into s o m e t h i n g w h i c h is n o t h e a t , a n d is c e r t a i n l y n o t a
s u b s t a n c e a t all, n a m e l y , m e c h a n i c a l w o r k .
W e must r e m e m b e r , therefore, that though w e a d m i t heat
t o t h e title o f a m e a s u r a b l e quantity, w e m u s t n o t g i v e it
rank as a s u b s t a n c e , b u t m u s t h o l d o u r m i n d s i n s u s p e n s e
till w e h a v e further e v i d e n c e as t o t h e n a t u r e o f h e a t .
Such e v i d e n c e is f u r n i s h e d b y e x p e r i m e n t s o n friction, in
which m e c h a n i c a l w o r k , instead o f b e i n g transmitted from
one part of a machine to another, is a p p a r e n t l y l o s t , w h i l e
at t h e s a m e t i m e , a n d i n t h e s a m e p l a c e , h e a t is g e n e r a t e d ,
the amount o f heat being in an exact proportion to the
amount o f w o r k l o s t W e have, therefore, reason to b e l i e v e
that h e a t is o f t h e s a m e n a t u r e as m e c h a n i c a l w o r k , that is,
it is o n e o f t h e f o r m s o f E n e r g y .
In the eighteenth century, when many n e w facts were
being d i s c o v e r e d relating to the action o f h e a t o n bodies,
a n d w h e n at t h e s a m e t i m e g r e a t p r o g r e s s w a s b e i n g made
in t h e k n o w l e d g e o f t h e c h e m i c a l a c t i o n o f s u b s t a n c e s , t h e
w o r d C a l o r i c w a s i n t r o d u c e d t o signify h e a t as a m e a s u r a b l e
quantity. S o l o n g as t h e w o r d d e n o t e d n o t h i n g m o r e t h a n
this, it m i g h t b e usefully e m p l o y e d , b u t t h e f o r m o f t h e w o r d
a c c o m m o d a t e d i t s e l f t o t h e t e n d e n c y o f t h e c h e m i s t s o f that
time to seek for n e w ' i m p o n d e r a b l e substances,' s o that
t h e w o r d c a l o r i c c a m e t o connote^ n o t m e r e l y heat, b u t heat
as an indestructible i m p o n d e r a b l e fluid, i n s i n u a t i n g itself
into the pores o f b o d i e s , dilating a n d d i s s o l v i n g them, a n d
1
' A connotative term is one which denotes a subject and implies an
attribute.'—MilVs Logic, book i. chap. ii. § 5.

8 Introduction.
ultimately v a p o r i s i n g them, c o m b i n i n g w i t h b o d i e s in definite

quantities, a n d so b e c o m i n g latent, a n d r e a p p e a r i n g w h e n
these b o d i e s alter their condition. I n fact, the w o r d caloric,
w h e n once introduced, soon c a m e to i m p l y the r e c o g n i s e d
existence o f s o m e t h i n g material, t h o u g h p r o b a b l y o f a m o r e
subtle nature than the then n e w l y d i s c o v e r e d gases. Caloric
r e s e m b l e d these gases in b e i n g i n v i s i b l e a n d in its p r o p e r t y
of becoming fixed in solid b o d i e s . I t differed from them
because its weight could not b e detected b y the finest
b a l a n c e s , hut there w a s n o d o u b t in the m i n d s o f m a n y
e m i n e n t m e n that caloric w a s a fluid p e r v a d i n g all b o d i e s ,
p r o b a b l y the cause o f all r e p u l s i o n , a n d p o s s i b l y e v e n o f the
e x t e n s i o n o f b o d i e s in space.
Since ideas of this kind have always been connected
w i t h the w o r d caloric, a n d the w o r d itself has b e e n in n o
slight degree the means of embodying and propagating
these ideas, a n d since all these ideas a r e n o w k n o w n to be
false, we shall a v o i d as m u c h a s p o s s i b l e the use of the
w o r d caloric in treating of heat. W e shall find it useful,
however, when we wish to refer to the e r r o n e o u s theory
which supposes heat to be a substance, to call it the
' C a l o r i c T h e o r y of H e a t . '
The word heat, though a primitive word and not a
scientific term, will b e f o u n d sufficiently free from a m b i g u i t y
w h e n w e use it to e x p r e s s a m e a s u r a b l e cpuantity, b e c a u s e it
will b e associated w i t h w o r d s e x p r e s s i v e o f quantity, indi
cating h o w m u c h heat w e a r e s p e a k i n g o f
W e h a v e n o t h i n g to do with the w o r d heat as a n abstract
t e r m signifying the p r o p e r t y o f h o t things, a n d w h e n we
m i g h t say a certain heat, as the heat of n e w m i l k , w e shall
a l w a y s use the m o r e scientific w o r d t e m p e r a t u r e , a n d s p e a k
o f the temperature o f n e w milk.
W e shall n e v e r u s e the w o r d h e a t to d e n o t e the sensation
o f heat. I n fact, it is n e v e r so u s e d in o r d i n a r y l a n g u a g e ,
w h i c h has n o n a m e s for sensations, unless w h e n the sensation
itself is o f m o r e i m p o r t a n c e to us than its p h y s i c a l cause, as

Measurement of Heat. 9
in the case of p a i n , & c . T h e o n l y n a m e w e h a v e for this
sensation is ' the sensation o f heat.'
When we require an a d j e c t i v e to d e n o t e that a phe
nomenon is r e l a t e d to heat we shall call it a thermal
p h e n o m e n o n , as, for instance, w e shall s p e a k of the thermal
conductivity o f a s u b s t a n c e or o f thermal radiation to dis
tinguish the conduction and radiation of heat from the
conduction o f electricity or the radiation o f light. The
science o f heat h a s b e e n called ( b y D r . W h e w e l l a n d others)
T h e r m o t i c s , a n d the theory o f heat as a form of energy is
called T h e r m o d y n a m i c s . I n the s a m e w a y the theory of the
equilibrium of heat might b e called Thermostatics, a n d that
of the m o t i o n of heat T h e r m o k i n e m a t i c s .
T h e instrument by w h i c h the temperature o f b o d i e s is
registered is c a l l e d a T h e r m o m e t e r or m e a s u r e r of w a r m t h ,
a n d the m e t h o d of constructing a n d using thermometers may
b e called T h e r m o m e t r y .
T h e instrument b y w h i c h quantities of heat are m e a s u r e d
is called a C a l o r i m e t e r , p r o b a b l y b e c a u s e it was invented at
a time w h e n heat w a s c a l l e d C a l o r i c . T h e name, however,
is n o w well established, a n d is a convenient one, as its form
is sufficiently distinct f r o m that of the w o r d T h e r m o m e t e r .
T h e m e t h o d of m e a s u r i n g heat m a y b e called Calorimetry.
A certain quantity o f heat, with w h i c h all other quantities
are c o m p a r e d , is c a l l e d a T h e r m a l U n i t . T h i s is the quantity
o f heat r e q u i r e d to p r o d u c e a particular effect, such as to
melt a p o u n d o f ice, or to raise a p o u n d of water from one
defined temperature to another defined temperature. A par
ticular thermal unit has b e e n called b y s o m e authors a Calorie.
We have n o w obtained two of the f u n d a m e n t a l ideas
of the science o f heat—the idea of temperature, or the
property of a b o d y c o n s i d e r e d with reference to its p o w e r of
heating other b o d i e s ; a n d the i d e a o f heat as a m e a s u r a b l e
quantity, w h i c h m a y b e transferred f r o m hotter bodies to
colder ones. W e shall consider the further d e v e l o p m e n t o f
these ideas in the chapters on T h e r m o m e t r y a n d Calorimetry,

10 Introduction.
b u t w e m u s t first d i r e c t o u r a t t e n t i o n t o t h e p r o c e s s b y w h i c h
h e a t is t r a n s f e r r e d f r o m o n e b o d y t o a n o t h e r .
T h i s p r o c e s s is c a l l e d t h e D i f f u s i o n o f H e a t . T h e diffusion
o f h e a t i n v a r i a b l y transfers h e a t f r o m a h o t t e r b o d y t o a c o l d e r
o n e , so as t o c o o l t h e h o t t e r b o d y a n d w a r m t h e c o l d e r b o d y .
T h i s p r o c e s s w o u l d g o o n till a l l b o d i e s w e r e b r o u g h t t o t h e
s a m e t e m p e r a t u r e i f it w e r e n o t f o r c e r t a i n other processes
by which the temperatures o f bodies are changed inde
p e n d e n t l y o f a n y e x c h a n g e c f h e a t w i t h o t h e r b o d i e s , as, f o r
instance, w h e n combustion or any other chemical process
t a k e s p l a c e , o r w h e n a n y c h a n g e o c c u r s i n t h e f o r m , structure,
o r p h y s i c a l state o f the b o d y .
T h e changes o f temperature o f a b o d y arising from other
causes than the transfer o f h e a t f r o m o t h e r bodies will be
c o n s i d e r e d w h e n w e c o m e to describe the different physical
states o f b o d i e s . W e are at p r e s e n t c o n c e r n e d only with
the passage o f heat into the body or out o f it, a n d this
a l w a y s t a k e s p l a c e b y diffusion, a n d is a l w a y s f r o m a h o t t e r
to a c o l d e r b o d y .
T h r e e processes o f diffusion o f heat are c o m m o n l y r e c o g
nised—Conduction, Convection, and Radiation.
C o n d u c t i o n is the flow o f heat through an u n e q u a l l y h e a t e d
b o d y from places o f higher to places o f l o w e r temperature.
C o n v e c t i o n is t h e m o t i o n o f t h e h o t b o d y i t s e l f c a r r y i n g its
h e a t w i t h it. I f b y this m o t i o n it is b r o u g h t n e a r b o d i e s c o l d e r
t h a n i t s e l f it w i l l w a r m t h e m faster than i f it h a d n o t b e e n
m o v e d nearer to them. T h e term c o n v e c t i o n is a p p l i e d to
those processes b y which the diffusion o f h e a t is rendered
more rapid b y the motion o f the hot substance from o n e
p l a c e t o a n o t h e r , t h o u g h t h e u l t i m a t e transfer o f h e a t may
still t a k e p l a c e b y conduction.
I n R a d i a t i o n , the hotter b o d y loses heat, a n d the colder
b o d y r e c e i v e s heat b y m e a n s o f a process occurring in s o m e
i n t e r v e n i n g m e d i u m w h i c h does not itself b e c o m e t h e r e b y hot.
I n each o f these three processes o f diffusion o f heat the
temperatures o f the b o d i e s b e t w e e n w h i c h the process takes

Diffusion of Heat.
place tend to b e c o m e e q u a l . W e shall not at present discuss

the convection o f heat, b e c a u s e it is not a p u r e l y thermal
p h e n o m e n o n , since it d e p e n d s o n a hot substance being
carried from o n e place to another, either b y h u m a n effort,
as w h e n a h o t iron is t a k e n out of the fire a n d put into the
tea-urn, or b y s o m e natural p r o p e r t y o f the h e a t e d substance,
as w h e n water, h e a t e d b y contact with the b o t t o m o f a
kettle p l a c e d on the fire, e x p a n d s as it b e c o m e s w a n n e d ,
a n d forms a n a s c e n d i n g current, m a k i n g w a y for c o l d e r .and
therefore d e n s e r water to d e s c e n d a n d take its place. In
every such case of c o n v e c t i o n the ultimate a n d o n l y direct
transfer of heat is d u e to c o n d u c t i o n , a n d the only effect of
the m o t i o n o f the hot substance is to b r i n g the u n e q u a l l y
heated portions n e a r e r to each other, so as to facilitate the
e x c h a n g e o f heat. W e shall a c c e p t the c o n d u c t i o n o f heat
as a fact, w i t h o u t at present a t t e m p t i n g to form a n y theory
o f the details o f the process b y w h i c h it takes place. We
d o not e v e n assert that in the diffusion of heat b y c o n d u c
tion the transfer of heat is entirely f r o m the hotter to the
colder b o d y . A l l that w e assert is, that the a m o u n t of h e a t
transferred f r o m the hotter to the c o l d e r b o d y is i n v a r i a b l y
greater than the a m o u n t , if any, transferred from the c o l d e r
to the hotter.
ON CONDUCTION.
I n the e x p e r i m e n t s w h i c h w e h a v e d e s c r i b e d , heat passes

from o n e b o d y into a n o t h e r t h r o u g h a n intervening sub
stance, as from a vessel o f w a t e r t h r o u g h the glass b u l b o f a
t h e r m o m e t e r into the m e r c u r y inside the b u l b .
T h i s process, b y w h i c h heat passes from hotter to c o l d e r
parts o f a b o d y , is c a l l e d the c o n d u c t i o n of heat. When
heat is passing t h r o u g h a b o d y b y c o n d u c t i o n , the tem
perature o f t h e b o d y m u s t b e greater in the parts from
which the heat c o m e s than in those to w h i c h it tends,
a n d the quantity of heat w h i c h passes t h r o u g h a n y thin
layer o f the substance d e p e n d s on the difference o f the

12 Introdnttion.
t e m p e r a t u r e s o f the o p p o s i t e sides o f the layer. F o r instance,

if we put a silver s p o o n into a c u p o f hot tea, the part
o f the s p o o n in the tea soon becomes heated, w h i l e the
p a r t just out of the tea is c o m p a r a t i v e l y cool. On ac
count o f this inequality o f temperature, heat immediately
F l G J
- - b e g i n s to flow a l o n g the metal from
/ K ) A to B. T h e heat first w a r m s B a
little, a n d so m a k e s B w a r m e r than
c, a n d then the heat flows o n from
B to C, a n d i n this w a y the very
e n d o f the s p o o n will in course of
time become warm to the touch.
T h e essential requisite to the con-
d u c t i o n o f heat is, that in e v e r y p a r t o f its c o u r s e the h e a t
m u s t p a s s from hotter to c o l d e r parts o f the b o d y . No
heat c a n b e c o n d u c t e d as far as E till A has b e e n made
hotter than B, B than c, c than D, a n d D than E. To do
this requires a certain a m o u n t of heat to be e x p e n d e d in
w a r m i n g in succession all these intermediate parts o f the
s p o o n , so that for s o m e time after the s p o o n is p l a c e d in
the c u p n o alteration of t e m p e r a t u r e c a n b e p e r c e i v e d at
the e n d of the s p o o n .
H e n c e w e m a y define c o n d u c t i o n as the p a s s a g e o f heat
t h r o u g h a b o d y d e p e n d i n g o n i n e q u a l i t y of t e m p e r a t u r e in
a d j a c e n t parts o f the b o d y .
W h e n a n y part of a b o d y is h e a t e d b y c o n d u c t i o n , the
parts o f the b o d y t h r o u g h w h i c h the heat c o m e s to it m u s t
b e hotter than itself, a n d the parts h i g h e r u p the stream of
heat still hotter.
I f w e n o w try the e x p e r i m e n t of the s p o o n in the t e a c u p
with a G e r m a n silver s p o o n a l o n g with the silver one, w e
shall find that the e n d o f the silver s p o o n b e c o m e s hot l o n g
b e f o r e that o f the G e r m a n silver o n e ; a n d if w e also p u t in a
b o n e o r h o r n s p o o n , w e shall not b e a b l e to p e r c e i v e any
w a r m t h at the e n d o f it, h o w e v e r l o n g w e wait.
T h i s shows that silver c o n d u c t s heat q u i c k e r than G e r m a n

Radiation. 13
silver, a n d G e r m a n silver q u i c k e r than b o n e or horn. The

reason w h y the e n d o f t h e s p o o n n e v e r g e t s as h o t as t h e
t e a is, t h a t t h e i n t e r m e d i a t e p a r t s o f t h e s p o o n are c o o l i n g ,
p a r t l y b y g i v i n g t h e i r h e a t t o t h e air i n c o n t a c t w i t h t h e m ,
and partly b y radiation out into space.
T o s h o w t h a t t h e first e f f e c t of heat o n the thermometer
is t o w a r m t h e m a t e r i a l o f w h i c h t h e b u l b is c o m p o s e d , a n d
t h a t t h e heat c a n n o t r e a c h t h e fluid i n s i d e t i l l t h e b u l b has
b e e n w a r m e d , take a t h e r m o m e t e r w i t h a large bulb, w a t c h
t h e fluid in t h e t u b e , a n d dash a little hot water o v e r the
bulb. T h e fluid w i l l fall i n t h e t u b e b e f o r e it b e g i n s to
rise, s h o w i n g t h a t t h e b u l b b e g a n t o e x p a n d b e f o r e t h e fluid
expanded.
ON RADIATION.
O n a c a l m d a y i n w i n t e r w e f e e l t h e sun's r a y s w a r m e v e n
w h e n w a t e r is f r e e z i n g a n d i c e is h a r d a n d d r y .
If w e make use o f a t h e r m o m e t e r , w e find that i f t h e
sun's rays fall o n it, i t i n d i c a t e s a temperature far above
f r e e z i n g , w h i l e t h e air i m m e d i a t e l y s u r r o u n d i n g the b u l b is
at a t e m p e r a t u r e b e l o w f r e e z i n g . T h e heat, t h e r e f o r e , w h i c h
w e f e e l , a n d t o w h i c h t h e t h e r m o m e t e r a l s o r e s p o n d s , is n o t
c o n v e y e d t o it b y c o n d u c t i o n through the air, f o r t h e air
is c o l d , and a c o l d b o d y c a n n o t m a k e a b o d y w a r m e r t h a n
itself b y c o n d u c t i o n . T h e m o d e in w h i c h the heat reaches
t h e b o d y w h i c h it w a r m s , w i t h o u t w a r m i n g t h e air t h r o u g h
which it passes, is called radiation. Substances which
admit of radiation taking place through them are c a l l e d
Diathermanous. T h o s e which do n o t a l l o w heat to pass
through them without b e c o m i n g themselves hot are c a l l e d
Athermanous. That w h i c h passes through the medium
during this process is generally called Radiant Heat,
though as l o n g as it is r a d i a n t it p o s s e s s e s none o f the
properties w h i c h distinguish heat from other forms o f energy,
s i n c e the t e m p e r a t u r e o f t h e b o d y t h r o u g h w h i c h it passes,

14 Introduction.
a n d t h e o t h e r p h y s i c a l p r o p e r t i e s o f the b o d y , a r e in n o w a y
affected b y the passage o f the r a d i a t i o n , p r o v i d e d t h e b o d y
is p e r f e c t l y d i a t h e r m a n o u s . If the b o d y is not perfectly
diathermanous it s t o p s m o r e o r less o f t h e r a d i a t i o n , a n d
becomes heated itself, instead o f transmitting the whole
r a d i a t i o n t o b o d i e s b e y o n d it.
The distinguishing characteristic o f r a d i a n t h e a t is, t h a t
it t r a v e l s i n rays l i k e l i g h t , w h e n c e t h e n a m e r a d i a n t . These
rays h a v e all the physical properties o f rays o f light, a n d are
c a p a b l e o f reflexion, refraction, interference, a n d polarisation.
They m a y b e d i v i d e d into different kinds b y t h e p r i s m , as
l i g h t is d i v i d e d i n t o its c o m p o n e n t c o l o u r s , a n d s o m e o f t h e
heat-rays are identical with the rays o f light, w h i l e other
kinds o f heat-rays make no i m p r e s s i o n On o u r e y e s . For
instance, if w e take a glass c o n v e x lens, a n d p l a c e it i n t h e
sun's r a y s , a b o d y p l a c e d at t h e f o c u s w h e r e a s m a l l i m a g e
o f t h e sun is f o r m e d w i l l b e i n t e n s e l y h e a t e d , w h i l e t h e l e n s
i t s e l f a n d t h e air t h r o u g h w h i c h t h e r a y s p a s s r e m a i n q u i t e
cold. I f w e a l l o w the rays b e f o r e t h e y reach the focus to
fall o n t h e surface o f w a t e r , s o t h a t t h e r a y s m e e t i n a f o c u s
i n t h e i n t e r i o r o f t h e w a t e r , t h e n i f t h e w a t e r is q u i t e c l e a r
a t t h e f o c u s it w i l l r e m a i n t r a n q u i l , b u t i f w e m a k e t h e f o c u s
fall u p o n a m o t e i n t h e w a t e r , t h e r a y s w i l l b e s t o p p e d , the
mote will b e heated and will cause the water n e x t it to
e x p a n d , a n d s o an u p w a r d c u r r e n t w i l l b e p r o d u c e d , a n d the
m o t e will b e g i n t o rise in the water. T h i s s h o w s t h a t it
is o n l y w h e n t h e r a d i a t i o n is stopped t h a t i t has a n y e f f e c t i n
h e a t i n g w h a t it falls o n .
B y m e a n s o f a n y r e g u l a r c o n c a v e p i e c e o f m e t a l , such as
the scale of a balance, pressed when hot against a clear
s h e e t o f i c e , first o n o n e s i d e a n d t h e n o n t h e o t h e r , it is e a s y
t o m a k e a l e n s o f i c e w h i c h m a y b e u s e d o n a s u n n y d a y as
a burning glass ; but this e x p e r i m e n t , w h i c h was f o r m e r l y
i n g r e a t r e p u t e , is far i n f e r i o r i n i n t e r e s t to one invented b y
P r o f e s s o r T y n d a l l , in w h i c h the heat, instead o f b e i n g c o n
c e n t r a t e d byice, is c o n c e n t r a t e d in i c e . T a k e a clear block

Radiation. 15
o f i c e a n d m a k e a flat s u r f a c e o n it, p a r a l l e l t o t h e original
surface o f the lake, or t o the layers of bubbles generally
found in l a r g e b l o c k s ; then let the c o n v e r g i n g rays o f the
sun f r o m an o r d i n a r y b u r n i n g g l a s s fall o n this surface, and
c o m e to a focus within the ice. The ice, not being per
fectly d i a t h e r m a n o u s , w i l l b e w a r m e d b y t h e r a y s , b u t m u c h
m o r e at t h e f o c u s than a n y w h e r e else. Thus the ice will
b e g i n t o m e l t at t h e focus in the interior o f its substance,
a n d , as i t d o e s s o , t h e portions which melt first are regu
larly f o r m e d crystals, a n d so w e see in the path o f the beam
a number o f six-rayed stars, w h i c h a r e h o l l o w s cut out o f
the ice and containing water. This water, however, does
not quite fill them, because the w a t e r is o f less b u l k than
t h e i c e o f w h i c h it w a s m a d e , so t h a t p a r t s o f t h e stars a r e
empty.
Experiments on the h e a t i n g effects of radiation show

that n o t o n l y t h e sun b u t all h o t b o d i e s e m i t r a d i a t i o n . When
the b o d y is h o t e n o u g h , its r a d i a t i o n s b e c o m e v i s i b l e , a n d
the b o d y is s a i d t o b e r e d hot W h e n it is still h o t t e r it
s e n d s forth n o t o n l y r e d rays, b u t rays o f e v e r y colour, and
it is t h e n s a i d t o b e w h i t e h o t . W h e n a b o d y is t o o c o l d
t o s h i n e v i s i b l y , it still shines with invisible heating rays,
which can be perceived' by a sufficiently delicate thermo
meter, and it d o e s n o t a p p e a r that a n y b o d y can be so
c o l d as n o t t o s e n d forth radiations. T h e r e a s o n w h y all
b o d i e s d o n o t a p p e a r t o shine is, that our eyes are sensitive
o n l y to particular k i n d s o f rays, a n d w e o n l y see b y m e a n s
of rays o f these kinds, c o m i n g from some v e r y hot body,
e i t h e r d i r e c t l y o r after r e f l e x i o n or scattering at the surface
of other bodies.
We shall s e e that t h e p h r a s e s r a d i a t i o n o f heat and ra

diant heat are not quite scientifically correct, and must be
used w i t h caution. Heat is certainly communicated from
one body to another by a process which we call ra
diation, which takes place in the region between the
two bodies. W e have n o right, h o w e v e r , t o s p e a k o f this

i6 Introduction.
process of radiation as heat. W e have defined heat

as it exists in hot b o d i e s , a n d w e h a v e seen that all h e a t
is o f the same k i n d . But the radiation b e t w e e n bodies
differs f r o m heat as w e h a v e defined i t — i s t , in n o t making
the b o d y hot t h r o u g h w h i c h it passes ; 2nd, in b e i n g of
m a n y different k i n d s . H e n c e w e shall g e n e r a l l y s p e a k o f
radiation, a n d w h e n w e s p e a k o f radiant heat w e do not
m e a n to i m p l y the existence of a n e w k i n d o f heat, b u t to
consider radiation in its thermal aspect.
ON THE DIFFERENT PHYSICAL STATES OF BODIES.
B o d i e s are f o u n d to b e h a v e in different w a y s u n d e r the

action o f forces. I f w e cause a longitudinal p r e s s u r e to act
o n a b o d y in o n e direction b y m e a n s o f a p a i r o f p i n c e r s o r
a vice, the b o d y b e i n g free to m o v e in all other directions,
w e find that if the b o d y is a piece o f cold iron there is v e r y
little effect p r o d u c e d , unless thè pressure b e v e r y great ; if
the b o d y is a p ie c e of i n d i a - r u b b e r , it is c o m p r e s s e d in the
direction o f its length a n d b u l g e s out at the sides, b u t it
s o o n c o m e s into a state o f e q u i l i b r i u m , in w h i c h it continues
to s u p p o r t the pressure ; b u t if w e substitute w a t e r for the
india-rubber we cannot p e r f o r m the experiment, for the
water flows a w a y laterally, a n d the jaws of the pincers
come together without having exerted any appreciable
pressure.
B o d i e s w h i c h can sustain a longitudinal pressure, h o w e v e r
small that pressure m a y b e , w i t h o u t b e i n g s u p p o r t e d b y a
lateral pressure, are called solid bodies. Those which
c a n n o t d o so are called fluids, W e shall see that in a fluid
at rest the pressure at a n y p o i n t must b e e q u a l in all d i r e c -
tions, a n d this pressure is c a l l e d the pressure o f the fluid.
T h e r e are t w o g r e a t classes o f fluids. I f w e p u t into a
c l o s e d vessel a small quantity o f a fluid o f the first class,
such as water, it will partly fill the vessel, a n d the rest o f the
vessel m a y either b e e m p t y or m a y contain a different fluid.

Solids, Liquids, and Gases. 17
Fluids h a v i n g this p r o p e r t y are c a l l e d liquids. W a t e r is a
liquid, a n d if w e p u t a little w a t e r into a bottle the water
will lie at the b o t t o m o f the bottle, a n d will b e s e p a r a t e d b y
a distinct surface from the air o r the g a s e o u s water-substance
a b o v e it.
If, on the contrary, the fluid w h i c h w e p u t into the c l o s e d
vessel b e one o f the second class, then, h o w e v e r small a
portion w e i n t r o d u c e , it w i l l e x p a n d a n d fill the vessel, or at
least as m u c h o f it as is not o c c u p i e d b y a l i q u i d .
Fluids h a v i n g this p r o p e r t y are called gases. A i r is a
gas, a n d if w e first exhaust the air f r o m a vessel a n d then
introduce the smallest quantity o f air, the air will i m m e d i a t e l y
e x p a n d till it fills the w h o l e vessel so that there is as much
air in a c u b i c i n c h i n o n e part o f the vessel as in another.
Hence a gas cannot, like a l i q u i d , b e k e p t in a n open-
m o u t h e d vessel.
T h e distinction, therefore, b e t w e e n a g a s a n d a l i q u i d is
that, h o w e v e r large the s p a c e m a y b e into w h i c h a portion of
gas is i n t r o d u c e d , t h e g a s will e x p a n d a n d exert pressure on
every part o f its b o u n d a r y , w h e r e a s a l i q u i d will not e x p a n d
m o r e than a v e r y s m a l l fraction o f its b u l k , e v e n w h e n the
pressure is r e d u c e d to zero ; a n d s o m e liquids can even
sustain a hydrostatic tension, or negative pressure, without
their parts b e i n g separated.
T h e three p r i n c i p a l states in w h i c h b o d i e s are f o u n d are,
therefore, the solid, the l i q u i d , a n d the g a s e o u s states.
M o s t substances are c a p a b l e of existing in all these states,
as, for instance, w a t e r exists in the forms o f ice, water, a n d
steam. A few solids, such as c a r b o n , h a v e not yet been
m e l t e d ; a n d a f e w gases, such as o x y g e n , h y d r o g e n , a n d
nitrogen, h a v e n o t yet b e e n liquefied or solidified, b u t these
may be considered as e x c e p t i o n a l cases, arising from the
limited r a n g e o f temperature a n d p r e s s u r e w h i c h we can
c o m m a n d in our experiments.
The o r d i n a r y effects o f heat in m o d i f y i n g the physical
state of b o d i e s m a y b e thus d e s c r i b e d . W e m a y take water
c
i8 Introduction.
as a f a m i l i a r e x a m p l e , a n d e x p l a i n , w h e n it is n e c e s s a r y , the
different p h e n o m e n a o f other bodies.
A t the l o w e s t t e m p e r a t u r e s a t w h i c h it has b e e n o b s e r v e d
w a t e r exists i n t h e solid form as i c e . W h e n h e a t is c o m
municated to v e r y c o l d ice, or t o any other solid b o d y not
at its m e l t i n g t e m p e r a t u r e —
r. T h e t e m p e r a t u r e rises.
2. T h e b o d y g e n e r a l l y e x p a n d s ( t h e o n l y e x c e p t i o n a m o n g
s o l i d b o d i e s , as far as I a m a w a r e , is t h e i o d i d e o f silver,
which has been found by M . Fizeau to contract as the
temperature rises).
3. The rigidity o f t h e b o d y , o r its r e s i s t a n c e t o c h a n g e o f
form, generally diminishes. This phenomenon is more
apparent in s o m e b o d i e s than in others. I t is v e r y con
spicuous in iron, w h i c h w h e n heated but not m e l t e d b e c o m e s
soft a n d e a s i l y f o r g e d . T h e c o n s i s t e n c y o f g l a s s , r e s i n s , fats,
and frozen oils alters v e r y m u c h with c h a n g e o f temperature.
r
O n t h e o t h e r h a n d , it is b e l i e v e d t h a t s t e e l w ire is stiffer at
100° C . t h a n at 0 ° C , and it has b e e n s h o w n b y J o u l e and
Thomson that the longitudinal elasticity of caoutchouc
increases with the temperature between certain limits o f
temperature. W h e n i c e is v e r y n e a r its melting point it
b e c o m e s v e r y soft.
4. A great m a n y solid bodies are constantly in a state o f
evaporation or transformation into the gaseous state at their
f r e e surface. Camphor, iodine, and carbonate o f ammonia
a r e w e l l - k n o w n e x a m p l e s o f this. T h e s e solid bodies, if not
k e p t in s t o p p e r e d bottles, gradually disappear b y evapora
tion, and the vapour which escapes from them may be
r e c o g n i s e d b y its s m e l l a n d by its chemical action. Ice,
t o o , is continually passing into a state o f v a p o u r at its
surface, and in a dry climate during a l o n g frost large
p i e c e s o f i c e b e c o m e s m a l l e r a n d at l a s t d i s a p p e a r .
T h e r e are other solid b o d i e s w h i c h d o n o t s e e m to lose
any o f their substance in this w a y ; at least, w e cannot
detect any loss. I t is p r o b a b l e , h o w e v e r , t h a t t h o s e s o l i d

Fusion. 19
b o d i e s w h i c h can b e d e t e c t e d b y their smell are e v a p o r a t i n g
with extreme slowness. T h u s iron and copper have each a
well-known smell. T h i s , h o w e v e r , m a y arise from chemical
action at the surface, which sets f r e e hydrogen or some
other gas combined with a very small q u a n t i t y - o f . , the
metal.
FUSION.
When the temperature of a solid b o d y T s raised to a

sufficient h e i g h t i t b e g i n s t o m e l t i n t o a l i q u i d . Suppose a
s m a l l p o r t i o n o f t h e s o l i d t o b e m e l t e d , a n d that n o m o r e h e a t
is a p p l i e d till the t e m p e r a t u r e o f t h e r e m a i n i n g s o l i d a n d o f
the l i q u i d has b e c o m e e q u a l i s e d ; i f a l i t t l e m o r e h e a t is t h e n
applied and the temperature again equalised there will be
m o r e l i q u i d m a t t e r a n d less s o l i d matter, b u t since the l i q u i d
a n d the s o l i d a r e at t h e s a m e t e m p e r a t u r e , t h a t temperature
m u s t still b e t h e m e l t i n g t e m p e r a t u r e .
Hence, i f the partly m e l t e d mass b e kept well mixed

t o g e t h e r , so t h a t t h e solid and fluid parts are at the same
temperature, that temperature must b e the m e l t i n g tempera
ture o f t h e s o l i d , a n d n o rise o f t e m p e r a t u r e w i l l f o l l o w f r o m
the a d d i t i o n o f h e a t till t h e w h o l e o f t h e s o l i d has b e e n c o n
verted into liquid.
T h e h e a t w h i c h is r e q u i r e d t o m e l t a c e r t a i n q u a n t i t y o f
a s o l i d at t h e melting point into a liquid at the same
t e m p e r a t u r e is c a l l e d t h e l a t e n t h e a t o f fusion.
I t is called latent heat, because the application o f this
heat t o t h e b o d y d o e s n o t r a i s e its t e m p e r a t u r e o r w a r m t h e
body.
T h o s e , therefore, w h o maintained heat to b e a substance
s u p p o s e d t h a t i t e x i s t e d i n t h e fluid in a c o n c e a l e d o r l a t e n t
state, a n d in this w a y t h e y distinguished it f r o m the heat
w h i c h , w h e n a p p l i e d t o a b o d y , m a k e s i t h o t t e r , o r raises t h e
temperature. T h i s they called sensible h e a t A b o d y , there
fore, w a s s a i d t o p o s s e s s so m u c h h e a t . P a r t o f this h e a t w a s
c a l l e d s e n s i b l e h e a t , a n d t o it w a s a s c r i b e d t h e temperature
c 2
20 Introduction.
of the b o d y . T h e other part was called latent heat, and

t o it w a s a s c r i b e d t h e l i q u i d o r g a s e o u s f o r m o f t h e b o d y .
T h e fact t h a t a c e r t a i n quantity o f heat must b e applied
t o a p o u n d o f m e l t i n g i c e t o c o n v e r t i t i n t o w a t e r is a l l t h a t
we mean in this treatise when w e speak o f this quantity
o f h e a t as the l a t e n t h e a t o f fusion o f a p o u n d o f w a t e r .
W e m a k e no assertion as t o t h e state i n w h i c h t h e heat
exists i n the water. W e do not e v e n assert that t h e heat
c o m m u n i c a t e d t o t h e i c e is still i n e x i s t e n c e as h e a t .
B e s i d e s t h e c h a n g e f r o m s o l i d t o l i q u i d , t h e r e is g e n e r a l l y
a c h a n g e o f v o l u m e in t h e act o f fusion. T h e water formed
f r o m t h e i c e is o f s m a l l e r b u l k t h a n t h e i c e , as is s h o w n b y
ice floating in water, so that the total v o l u m e o f the ice and
w a t e r d i m i n i s h e s as t h e m e l t i n g g o e s o n .
O n the other hand, m a n y substances e x p a n d in the act o f
fusion, s o t h a t t h e s o l i d p a r t s s i n k i n t h e fluid. D u r i n g the
fusion o f t h e m a s s t h e v o l u m e i n t h e s e cases increases.
1
It has been shown by Prof J. Thomson, from the
p r i n c i p l e s o f the d y n a m i c a l t h e o r y o f h e a t , t h a t i f p r e s s u r e is
a p p l i e d t o a m i x t u r e o f i c e a n d w a t e r , it w i l l n o t o n l y c o m p r e s s
both the ice and the water, but some o f the ice will be
m e l t e d at t h e s a m e t i m e , so t h a t t h e total c o m p r e s s i o n will
b e increased b y the c o n t r a c t i o n o f bulk due t o this m e l t i n g .
T h e h e a t r e q u i r e d t o m e l t this i c e b e i n g t a k e n f r o m t h e r e s t
o f t h e mass, t h e t e m p e r a t u r e o f t h e w h o l e w i l l d i m i n i s h .
Hence t h e m e l t i n g p o i n t is l o w e r e d b y pressure in the
case o f ice. T h i s deduction from theory was experimentally
verified b y Sir W . T h o m s o n .
I f the substance had b e e n o n e o f those w h i c h e x p a n d in
melting, the effect o f pressure w o u l d b e to solidify some of
t h e m i x t u r e , a n d t o raise t h e t e m p e r a t u r e o f fusion. Most of
t h e s u b s t a n c e s o f w h i c h the crust o f t h e e a r t h is c o m p o s e d
e x p a n d in the act o f m e l t i n g . H e n c e their m e l t i n g points
w i l l rise u n d e r g r e a t p r e s s u r e . I f the earth w e r e throughout
1
Transactions of the .Royal Society of Edinburgh, 1849.

Fusion. 21
in a state of fusion, w h e n the ext ernal parts b e g a n to solidify

they w o u l d sink in the molten mass, a n d w h e n they h a d
sunk to a great d e p t h they w o u l d r e m a i n solid u n d e r the
enormous pressure e v e n at a t e m p e r a t u r e greatly a b o v e the
point of fusion of the s a m e r o c k at the surface. I t does n o t
follow, therefore, that in the interior o f the earth the matter
is in a liquid state, even if the t e m p e r a t u r e is far a b o v e that
o f the fusion of r o c k s in o u r furnaces.
I t has b e e n s h o w n b y Sir W . T h o m s o n that if the earth, as
a whole, w e r e n o t m o r e rigid t h a n a b a l l of glass of e q u a l size,
the attraction of the m o o n a n d sun w o u l d p u l l it out o f s h a p e ,
and raise tides o n the surface, so that the solid earth w o u l d
rise a n d fall as the sea does, o n l y n o t quite so m u c h . I t is
true that this m o t i o n w o u l d b e so s m o o t h a n d regular that
w e should not b e a b l e to p e r c e i v e it in a direct w a y , b u t its
effect w o u l d b e to diminish the a p p a r e n t rise o f the tides of
the ocean, so as to m a k e them much smaller than they
actually a r e .
I t a p p e a r s , therefore, f r o m w h a t w e k n o w o f the tides of
the ocean, that the earth as a w h o l e is m o r e rigid than glass,
and therefore that n o v e r y l a r g e p o r t i o n o f its interior c a n
b e liquid. The effect o f pressure o n the melting point of
bodies enables us to reconcile this conclusion with the
observed increase of temperature as we d e s c e n d in the
earth's crust, a n d the d e d u c t i o n s as to the interior t e m p e r a
ture f o u n d e d on this fact b y the a i d o f the theory of the
c o n d u c t i o n of heat.
EFFECT OF HEAT ON LIQUIDS.
W h e n heat is a p p l i e d to a l i q u i d its effects a r e —

1. T o w a r m the liquid. T h e quantity o f heat r e q u i r e d to
raise the l i q u i d o n e d e g r e e is g e n e r a l l y greater than that
r e q u i r e d to raise the substance in the solid form o n e d e g r e e ,
a n d in g e n e r a l it requires m o r e heat at high than at low
temperatures to w a r m the l i q u i d o n e d e g r e e .
2. T o alter its volume. M o s t liquids e x p a n d as their

22 Introduction.
temperature rises, but water contracts from o ° C . to 4° C .
and then expands, s l o w l y at first, but afterwards more
rapidly.
3. T o a l t e r its p h y s i c a l state. L i q u i d s , s u c h as o i l , tar,
&c, which are s l u g g i s h in their motion, are said to be
viscous. W h e n they are heated their v i s c o s i t y g e n e r a l l y
diminishes and they b e c o m e m o r e mobile. T h i s is t h e c a s e
e v e n w i t h w a t e r , as a p p e a r s b y t h e e x p e r i m e n t s o f M . O . E .
Meyer.
When s u l p h u r is h e a t e d , t h e m e l t e d sulphur undergoes
several remarkable c h a n g e s as its t e m p e r a t u r e rises, being
m o b i l e w h e n first m e l t e d , then b e c o m i n g r e m a r k a b l y v i s c o u s
at a h i g h e r t e m p e r a t u r e , a n d a g a i n becoming mobile when
still m o r e h e a t e d .
4. T o c o n v e r t the l i q u i d or s o l i d i n t o gas. W h e n a liquid
o r a s o l i d b o d y is p l a c e d in a v e s s e l t h e r e s t o f w h i c h is
e m p t y , it g i v e s o f f p a r t o f its o w n s u b s t a n c e i n t h e f o r m o f
gas. T h i s p r o c e s s is c a l l e d e v a p o r a t i o n , a n d the g a s g i v e n
off is c o m m o n l y c a l l e d the v a p o u r o f the s o l i d o r l i q u i d s u b
stance. T h e p r o c e s s o f e v a p o r a t i o n g o e s o n till t h e d e n s i t y
o f the v a p o u r i n t h e v e s s e l has r e a c h e d a v a l u e w h i c h d e
pends o n l y o n the temperature.
I f in a n y w a y , a s b y t h e m o t i o n o f a p i s t o n , t h e v e s s e l be
m a d e l a r g e r , t h e n m o r e v a p o u r w i l l b e f o r m e d till t h e d e n s i t y
is t h e s a m e as b e f o r e . I f the p i s t o n b e p u s h e d in, a n d the
v e s s e l m a d e s m a l l e r , s o m e o f t h e v a p o u r is c o n d e n s e d into
the l i q u i d state, b u t the density o f the remainder o f the
v a p o u r still r e m a i n s t h e s a m e .
If the remainder o f the vessel, instead of containing
n o t h i n g b u t t h e v a p o u r o f the l i q u i d , c o n t a i n s a n y q u a n t i t y
o f air o r s o m e o t h e r g a s n o t c a p a b l e o f c h e m i c a l a c t i o n on
the liquid, then exactly the same quantity o f v a p o u r will be
formed, but the time required for the vapour to reach the
further parts o f the vessel will be greater, as it has to
diffuse itself through t h e air in t h e v e s s e l b y a kind of
percolation.
T h e s e laws o f evaporation w e r e d i s c o v e r e d by D a l t o n .

Evaporation. 23
The conversion o f the liquid into vapour requires an
amount of ' latent heat' which is g e n e r a l l y m u c h greater
than the l a t e n t h e a t o f f u s i o n o f t h e s a m e s u b s t a n c e .
In all s u b s t a n c e s , t h e density, pressure, and temperature
a r e so c o n n e c t e d that i f w e k n o w a n y t w o o f t h e m t h e v a l u e
o f the third is d e t e r m i n a t e . N o w in t h e c a s e o f v a p o u r s in
contact with their o w n l i q u i d s o r s o l i d s , t h e r e is f o r each
temperature a corresponding d e n s i t y , w h i c h is t h e greatest
density which the vapour can h a v e at that temperature,
without b e i n g c o n d e n s e d into the l i q u i d or solid f o r m .
Hence for each temperature there is a l s o a maximum
pressure w h i c h the v a p o u r can exert.
A v a p o u r w h i c h is a t t h e g r e a t e s t density and pressure
c o r r e s p o n d i n g t o its t e m p e r a t u r e is c a l l e d a saturated vapour.
I t is t h e n j u s t a t t h e p o i n t o f c o n d e n s a t i o n , a n d t h e s l i g h t e s t
increase o f pressure o r decrease of temperature will cause
some o f the vapour to b e condensed. Professor R a n k i n e
restricts t h e use o f t h e w o r d v a p o u r b y i t s e l f t o t h e c a s e o f a
s a t u r a t e d v a p o u r , a n d w h e n t h e v a p o u r is n o t at t h e p o i n t o f
c o n d e n s a t i o n h e calls it superheated v a p o u r , or s i m p l y gas.
BOILING.
When a l i q u i d i n a n o p e n v e s s e l is h e a t e d t o a t e m p e r a
ture s u c h t h a t t h e p r e s s u r e o f its v a p o u r at that t e m p e r a
ture is g r e a t e r t h a n t h e p r e s s u r e at a p o i n t i n t h e interior
of the liquid, the liquid will begin to evaporate at that
point, so that a bubble of vapour will be fonned there.
T h i s process, in w h i c h b u b b l e s of vapour are f o r m e d in
t h e i n t e r i o r o f t h e l i q u i d , is c a l l e d b o i l i n g o r e b u l l i t i o n .
W h e n water is h e a t e d in the ordinary w a y b y applying
h e a t t o t h e b o t t o m o f a v e s s e l , the l o w e s t l a y e r o f t h e w a t e r
b e c o m e s h o t first, a n d b y its e x p a n s i o n it b e c o m e s lighter
than the c o l d e r w a t e r a b o v e , and g r a d u a l l y rises, s o that a
g e n t l e c i r c u l a t i o n o f w a t e r is k e p t up, and the w h o l e water
is g r a d u a l l y w a r m e d , t h o u g h t h e l o w e s t l a y e r is a l w a y s the
hottest. A s the temperature increases, the absorbed air,

24 Introduction.
which is g e n e r a l l y f o u n d i n o r d i n a r y w a t e r , is e x p e l l e d , a n d
rises in small b u b b l e s w i t h o u t noise. A t last t h e w a t e r i n
contact with the heated m e t a l b e c o m e s so h o t that, in spite
of the pressure o f the atmosphere o n the surface o f the
water, the additional pressure due to the water in the
vessel, and the cohesion o f the w a t e r itself, s o m e o f the
w a t e r at t h e b o t t o m is t r a n s f o r m e d into steam, forming a
bubble adhering t o the b o t t o m o f the vessel. A s s o o n as a
b u b b l e is f o r m e d , e v a p o r a t i o n g o e s o n r a p i d l y f r o m t h e w a t e r
a l l r o u n d it, so t h a t it s o o n g r o w s l a r g e , a n d rises f r o m the
bottom. I f the u p p e r part o f the water into which the
bubble rises is still below the b o i l i n g temperature, the
b u b b l e is c o n d e n s e d , and its s i d e s c o m e together with a
sharp rattling noise, c a l l e d simmering. B u t t h e rise o f t h e
bubbles stirs t h e w a t e r a b o u t much m o r e vigorously than
t h e m e r e e x p a n s i o n o f t h e w a t e r , s o t h a t t h e w a t e r is s o o n
heated throughout, and brought to the boil, and then the
bubbles enlarge rapidly during their whole ascent, and
burst into the air, t h r o w i n g t h e w a t e r about, a n d making
t h e w e l l - k n o w n softer and m o r e r o l l i n g n o i s e o f b o i l i n g .
T h e s t e a m , as it b u r s t s o u t o f t h e b u b b l e s , is a n i n v i s i b l e
g a s , b u t w h e n it c o m e s i n t o t h e c o l d e r a i r i t is c o o l e d b e l o w
its c o n d e n s i n g p o i n t , a n d p a r t o f i t is f o r m e d i n t o a c l o u d
consisting o f small drops o f w a t e r w h i c h float i n t h e air.
A s the cloud o f drops disperses itself a n d mixes with dry
air the q u a n t i t y o f w a t e r i n e a c h c u b i c f o o t diminishes as
the v o l u m e o f any part o f the c l o u d increases. T h e little
d r o p s o f w a t e r b e g i n t o e v a p o r a t e as s o o n as t h e r e is suffi
c i e n t r o o m f o r t h e v a p o u r t o b e f o r m e d at t h e temperature
of the atmosphere, a n d so the c l o u d vanishes again into
t h i n air.
T h e temperature t o w h i c h w a t e r m u s t b e h e a t e d b e f o r e it
boils depends, in the first place, on the pressure of the
a t m o s p h e r e , s o that t h e g r e a t e r t h e pressure, the h i g h e r t h e
boiling temperature. But the temperature requires to be
r a i s e d a b o v e that at w h i c h t h e p r e s s u r e o f s t e a m is e q u a l t o

Boiling. 25
that of the a t m o s p h e r e , for in o r d e r to form bubbles the

pressure of the steam has to o v e r c o m e not o n l y the pressure
d u e to the a t m o s p h e r e a n d a certain d e p t h of w a t e r , b u t that
cohesion b e t w e e n the parts of the w a t e r of w h i c h the effects
are visible in the tenacity o f b u b b l e s a n d d r o p s . H e n c e it
is p o s s i b l e to heat w a t e r 20° F . a b o v e its b o i l i n g p o i n t with
out ebullition. I f a small quantity of metal-filings are n o w
t h r o w n into the w a t e r , a little air will b e c a r r i e d d o w n on
the surface of the filings, a n d the p r o c e s s o f e v a p o r a t i o n will
take p l a c e at the interface b e t w e e n this air a n d the hot w a t e r
with such rapidity as to p r o d u c e a violent b o i l i n g , almost
a m o u n t i n g to an e x p l o s i o n .
I f a current of steam f r o m a b o i l e r is p a s s e d into a vessel

of c o l d water, we have first the condensation of steam,
a c c o m p a n i e d with a v e r y l o u d s i m m e r i n g o r rattling noise, a n d
a r a p i d heating of the water. W h e n the w a t e r is sufficiently
h e a t e d , the steam is n o t c o n d e n s e d , b u t escapes in b u b b l e s ,
a n d the w a t e r is n o w b o i l i n g .
A s an instance o f a different k i n d , let us suppose that
the w a t e r is not pure, b u t contains some salt, such as
c o m m o n salt, o r s u l p h a t e o f s o d a , o r a n y other substance
which tends to c o m b i n e w i t h water, a n d f r o m w h i c h the
w a t e r m u s t separate b e f o r e it c a n e v a p o r a t e . Watei con
taining such s u b s t a n c e s in solution r e q u i r e s to b e b r o u g h t
to a temperature h i g h e r t h a n the boiling point of pure
w a t e r b e f o r e it w i l l b o i l . Water, on the other h a n d , con
taining air o r c a r b o n i c a c i d , w i l l b o i l at a l o w e r t e m p e r a t u r e
than p u r e w a t e r till the gas is e x p e l l e d .
I f steam at 100° C . is p a s s e d into a vess'eX'.cdhtaining a
strong solution of one of the salts w e c j i a v e mentioned,
w h i c h h a s a t e n d e n c y to c o m b i n e w j d ^ ' w a t e r , the ^conden
sation of the steam w i l l b e p r o m / ^ d by thisHendency,
a n d will g o o n e v e n after the solutldfi has v"b^erf heated far
a b o v e the o r d i n a r y b o i l i n g p o i n t , scS-that'try passing steam
at i o o ° C. into a s t r o n g solution of nitrate o f s o d a , M r . Peter
1
Spence has h e a t e d it u p to i 2 i ° " i C.
1
Transactions of the British Association, 1869, p. 75-

20 Introduction.
If w a t e r at a temperature b e l o w i o o ° C . b e p l a c e d in a
v e s s e l , a n d i f b y m e a n s o f an air-pump w e reduce the pres
sure o f t h e air o n t h e surface o f the water, e v a p o r a t i o n g o e s
on and the surface o f the water b e c o m e s c o l d e r than the
interior parts. If we go o n w o r k i n g the air-pump, the
p r e s s u r e is r e d u c e d t o t h a t e f v a p o u r o f t h e t e m p e r a t u r e o f t h e
i n t e r i o r o f t h e fluid. T h e water then begins to boil, exactly
as in the ordinary way, and as it b o i l s the temperature
r a p i d l y falls, t h e heat being expended in evaporating the
water.
T h i s experiment m a y b e performed without an air-pump
in the following way : Boil water in a flask over a gas-
f l a m e o r s p i r i t - l a m p , a n d w h i l e i t is b o i l i n g b r i s k l y c o r k t h e
flask, a n d r e m o v e it f r o m the f l a m e . T h e b o i l i n g will soon
cease, b u t i f w e n o w dash a little c o l d w a t e r o v e r the flask,
s o m e o f the s t e a m i n t h e u p p e r p a r t w i l l b e c o n d e n s e d , the
pressure o f the r e m a i n d e r will b e diminished, a n d the water
will begin to boil again. The experiment may be made
more striking by plunging the flask entirely under cold
water. The steam will be condensed as b e f o r e , b u t the
w a t e r , t h o u g h it is c o o l e d m o r e r a p i d l y t h a n w h e n the cold
w a t e r w a s m e r e l y p o u r e d o n ' t h e flask, r e t a i n s its h e a t l o n g e r
than the steam, a n d continues to boil for s o m e time.

Laws of Gases.
ON THE GASEOUS STATE.
The distinguishing property o f g a s e s is t h e i r power of

indefinite expansion. A s the pressure is diminished the
v o l u m e o f the gas n o t o n l y increases, but b e f o r e the pressure
has b e e n r e d u c e d t o z e r o t h e v o l u m e o f t h e g a s h a s b e c o m e
g r e a t e r t h a n t h a t o f a n y v e s s e l w e c a n p u t it i n .
T h i s is t h e p r o p e r t y w i t h o u t which a substance cannot
b e c a l l e d a gas, b u t it is f o u n d tlTat a c t u a l g a s e s fulfil with
g r e a t e r o r less d e g r e e s o f a c c u r a c y c e r t a i n n u m e r i c a l l a w s ,
w h i c h a r e c o m m o n l y r e f e r r e d t o as t h e ' G a s e o u s Laws.'
LAW OF BOYLE.
T h e first o f t h e s e l a w s e x p r e s s e s the relation b e t w e e n the

pressure a n d the density o f a gas, the temperature being
constant, and is usually stated thus : ' T h e volume of a
p o r t i o n o f g a s v a r i e s i n v e r s e l y as t h e p r e s s u r e . '
This law was discovered b y R o b e r t Boyle, and published
b y h i m in 1662, i n an a p p e n d i x t o his ' N e w E x p e r i m e n t s ,
Physico-mechanical, & x . , touching the Spring o f the A i r . '
M a r i o t t e , a b o u t 1676, i n his treatise 'De la N a t u r e d e
l ' A i r , ' e n u n c i a t e d the s a m e l a w , a n d c a r e f u l l y v e r i f i e d it, a n d it
is g e n e r a l l y r e f e r r e d t o b y C o n t i n e n t a l w r i t e r s as Mariotte's
law.
T h i s l a w m a y also b e stated thus :
T h e p r e s s u r e -of a g a s i s p r o p o r t i o n a l t o its d e n s i t y .
A n o t h e r s t a t e m e n t o f t h e s a m e l a w has b e e n p r o p o s e d b y
Professor Rankine, which I think places the l a w in a v e r y
clear light.
I f w e take a c l o s e d and exhausted vessel, a n d introduce
i n t o it o n e g r a i n o f air, this air w i l l , as w e k n o w , e x e r t a
c e r t a i n p r e s s u r e o n e v e r y s q u a r e i n c h o f t h e surface o f t h e
vessel. I f w e n o w i n t r o d u c e a s e c o n d g r a i n o f air, t h e n this
s e c o n d grain will exert e x a c t l y the same pressure on the
s i d e s o f t h e v e s s e l t h a t it w o u l d h a v e e x e r t e d i f t h e first g r a i n

Introduction.
had not b e e n t h e r e b e f o r e it, so t h a t t h e p r e s s u r e w i l l n o w
be doubled. H e n c e we may s t a t e , as the property o f a
p e r f e c t g a s , that a n y p o r t i o n o f it e x e r t s t h e s a m e p r e s s u r e
a g a i n s t t h e sides o f a v e s s e l as i f t h e o t h e r p o r t i o n s h a d n o t
been there.
D a l t o n e x t e n d e d this l a w t o m i x t u r e s o f g a s e s o f d i f f e r e n t
kinds.
W e h a v e a l r e a d } ' seen that if several different portions o f
the s a m e g a s a r e p l a c e d t o g e t h e r i n a v e s s e l , t h e p r e s s u r e o n
any part o f the s i d e s o f f h e v e s s e l is t h e s u m o f t h e pres
sures w h i c h e a c h p o r t i o n w o u l d e x e r t i f p l a c e d b y i t s e l f i n
the v e s s e l .
D a l t o n ' s l a w asserts t h a t t h e s a m e is t r u e f o r p o r t i o n s o f
different gases p l a c e d in the same vessel, and that the
p r e s s u r e o f t h e m i x t u r e is t h e s u m o f t h e p r e s s u r e s d u e t o t h e
several portions o f gas, if introduced separately into the
vessel and b r o u g h t t o the same temperature. •
T h i s l a w o f D a l t o n is s o m e t i m e s s t a t e d as i f p o r t i o n s o f
gas o f different kinds b e h a v e t o e a c h other in a different
manner from portions o f gas o f the same kind, and w e are
told that w h e n gases o f different kinds are p l a c e d in the
s a m e v e s s e l , e a c h a c t s as i f t h e o t h e r w e r e a v a c u u m .
This statement, properly understood, is correct, but it
seems to c o n v e y the impression that i f the gases h a d been
of the s a m e k i n d s o m e o t h e r result would have happened,
w h e r e a s t h e r e is n o d i f f e r e n c e b e t w e e n t h e t w o c a s e s .
A n o t h e r l a w e s t a b l i s h e d b y D a l t o n is t h a t t h e maximum
d e n s i t y o f a v a p o u r i n c o n t a c t w i t h its l i q u i d is n o t a f f e c t e d
by the presence of other gases. It has been shown by
M . R e g n a u l t that w h e n the v a p o u r o f the s u b s t a n c e has a
t e n d e n c y to c o m b i n e with the gas, t h e maximum density
a t t a i n a b l e b y t h e v a p o u r is s o m e w h a t i n c r e a s e d .
B e f o r e t h e t i m e o f D a l t o n it w a s s u p p o s e d that t h e c a u s e
o f e v a p o r a t i o n w a s the t e n d e n c y o f water t o c o m b i n e with
air, a n d that t h e w a t e r w a s d i s s o l v e d i n t h e air j u s t as salt is
d i s s o l v e d in w a t e r .

Gases and Vapours. 29
D a l t o n s h o w e d that the v a p o u r o f w a t e r is a g a s , w h i c h
just at the surface o f the w a t e r has a certain maximum
d e n s i t y , a n d w h i c h w i l l g r a d u a l l y diffuse i t s e l f t h r o u g h the
s p a c e a b o v e , w h e t h e r filled w i t h air o r n o t , t i l l i f t h e s p a c e is
l i m i t e d , t h e d e n s i t y o f t h e v a p o u r is a m a x i m u m throughout,
or, if the s p a c e is l a r g e e n o u g h , till t h e w a t e r is a l l d r i e d up.
T h e p r e s e n c e o f a i r is so far f r o m b e i n g e s s e n t i a l t o this
p r o c e s s that t h e more air t h e r e is, t h e s l o w e r it g o e s o n ,
b e c a u s e the v a p o u r has t o p e n e t r a t e t h r o u g h t h e air b y the
slow process o f diffusion.
T h e p h e n o m e n o n d i s c o v e r e d b y R e g n a u l t that the density
o f v a p o u r is s l i g h t l y i n c r e a s e d b y the presence of a gas
w h i c h has a t e n d e n c y t o c o m b i n e w i t h it, is t h e o n l y instance
in w h i c h t h e r e is a n y t r u t h i n t h e d o c t r i n e o f a l i q u i d b e i n g
h e l d in s o l u t i o n b y a g a s .
T h e l a w o f B o y l e is n o t p e r f e c t l y fulfilled b y a n y actual
gas. I t is v e r y n e a r l y fulfilled b y t h o s e g a s e s w h i c h w e are
n o t a b l e t o c o n d e n s e i n t o l i q u i d s , a n d a m o n g o t h e r gases i t
is m o s t n e a r l y fulfilled w h e n t h e i r t e m p e r a t u r e is m u c h a b o v e
their p o i n t o f c o n d e n s a t i o n .
W h e n a gas is n e a r its p o i n t o f c o n d e n s a t i o n its density
increases more rapidly than the pressure. When it is
actually at the p o i n t o f c o n d e n s a t i o n t h e s l i g h t e s t i n c r e a s e o f
p r e s s u r e c o n d e n s e s t h e w h o l e o f it i n t o a l i q u i d , a n d i n the
liquid form the density increases very slowly with the
pressure.
LAW OF CHARLES.
1
T h e second l a w o f gases was d i s c o v e r e d b y Charles, but
3
is c o m m o n l y r e f e r r e d t o as t h a t o f G a y - L u s s a c o r o f D a l t o n .
I t m a y b e s t a t e d thus :
1
Professor of Physics at the Conservatoire des Arts et Metiers, Pans.
Bom 1746. Died 1823. Celebrated as having first employed hydrogen
in balloons.
2
Dalton, in 1801, first published this law. Gay-Lussac published
it, in 1802, independently of Dalton. In his memoir, however (Ann.

Introduction
T h e volume o f a g a s u n d e r constant pressure expands
w h e n r a i s e d f r o m the freezing to the b o i l i n g temperature b y
the same fraction o f itself, w h a t e v e r b e the nature o f the gas.
It has been found by the careful experiments of M .
R e g n a u l t , M . R u c i b e r g , Prof. B . Stewart, a n d others that the
v o l u m e o f air a t constant pressure e x p a n d s from i to i "3665
between o ° C. a n d ioo° C. Hence 30 c u b i c inches of
air at o ° C . w o u l d e x p a n d to a b o u t 41 cubic inches at
100° C .
I f w e a d m i t the truth of B o y l e ' s l a w at all temperatures,
a n d if the l a w o f C h a r l e s is f o u n d to b e true for a particular
pressure, say that o f the a t m o s p h e r e , then it is e a s y to s h o w
that the l a w o f C h a r l e s must b e true for every other pressure.
F o r if w e call the v o l u m e v a n d the pressure p, then w e
m a y call the p r o d u c t o f the numerical v a l u e of the v o l u m e
a n d pressure v p, a n d Boyle's l a w asserts that this p r o
duct is constant, p r o v i d e d the t e m p e r a t u r e is constant. If
then we are further i n f o r m e d that w h e n p has a given
v a l u e v is i n c r e a s e d f r o m 1 to i'3665 w h e n the temperature
rises f r o m the freezing point to the b o i l i n g point, the p r o d u c t
v p will b e increased in the same p r o p o r t i o n at that particular
pressure. B u t v p w e k n o w b y B o y l e ' s l a w d o e s not d e p e n d o n
the particular pressure, b u t r e m a i n s the s a m e for all pressures
w h e n the t e m p e r a t u r e r e m a i n s the same. H e n c e , whatever
be the pressure, the p r o d u c t v p will b e i n c r e a s e d in the
p r o p o r t i o n o f 1 to i'3665 w h e n the temperature rises from
0° C . to 1 0 « ° C .
T h e l a w o f the equality o f the dilatation o f gases, w h i c h , as
originally stated, a p p l i e d only to the dilatation f r o m o° C .
to r o o ° C . , has b e e n f o u n d to b e true for all other t e m p e r a
tures for w h i c h it h a s hitherto b e e n tested.
de Chimin, xliii. p . 157 [ i S o z ] ) , he states that Citizen Charles had

remarked, fifteen years before the date of his memoir, the equality of
the dilatation of the principal gases ; but, as Charles never published
these results, he had become acquainted with them by mere chance.

T/u Gaseous Siate.
It appears, therefore, that g a s e s are distinguished from

other forms o f matter, not o n l y b y their p o w e r o f indefinite
e x p a n s i o n s o as t o fill a n y v e s s e l , h o w e v e r l a r g e , a n d b y t h e
great effect which heat has in dilating them, but by the
uniformity and simplicity o f the laws which regulate these
changes. In the solid and liquid states the effect of a
g i v e n change o f pressure or o f temperature in changing the
v o l u m e o f t h e b o d y is d i f f e r e n t f o r e v e r y d i f f e r e n t s u b s t a n c e .
On the other hand, i f w e take equal volumes of any two
gases, measured at the same temperature and pressure,
their v o l u m e s will r e m a i n equal if w e afterwards bring them
both to any other temperature and pressure, and this
a l t h o u g h the t w o g a s e s d i f f e r a l t o g e t h e r in c h e m i c a l nature
a n d in d e n s i t y , p r o v i d e d t h e y a r e b o t h in t h e p e r f e c t l y g a s e o u s
condition.
This is only one of many remarkable properties which
p o i n t out the gaseous state o f m a t t e r as t h a t i n w h i c h its
physical properties are least c o m p l i c a t e d .
I n our description o f the physical properties o f b o d i e s as
related to heat w e have b e g u n w i t h s o l i d b o d i e s , as those
which we can most easily handle, and have gone on to
liquids, w h i c h w e can k e e p in o p e n v e s s e l s , a n d have n o w
come to gases, which will escape from open vessels, and
which are generally invisible. This is t h e order which is
m o s t n a t u r a l in o u r first s t u d y o f t h e s e d i f f e r e n t states. But
as s o o n as w e h a v e b e e n m a d e f a m i l i a r w i t h t h e m o s t prominent
features o f these different conditions o f matter, the most
s c i e n t i f i c c o u r s e o f s t u d y is in t h e r e v e r s e order, beginning
with gases, o n a c c o u n t o f the greater simplicity o f their laws,
then advancing to liquids, the m o r e c o m p l e x laws o f which
are much more imporfer.tly known, and concluding with
t h e l i t t l e t h a t has b e e n hitherto discovered about the con
stitution o f solid b o d i e s .

32 Thermometry.
CHAPTER II.
ON THERMOMETRY, OR THE THEORY OF TEMPERATURE.
Definition of T e m p e r a t u r e . — The temperature of a body

is its thermal state considered with reference to its power oj
communicating heat to other bodies.
Definition of H i g h e r a n d L o w e r T e m p e r a t u r e . — I f when
two bodies are placed in thermal communication, one of the
bodies loses heat, and the other gains heat, that body which gives
out heat is said to have a higher te?nperature than t/uzt which
receives heat from it.
C o r . If when two bodies are placed in thermal communica-
tio?i neither of them loses or gains heat, the two bodies are
said to liave equal temperatures or the same temperature. The
two bodies are then said to be in thermal equilibrium. We
have here a means of c o m p a r i n g the t e m p e r a t u r e of any
two bodies, s o as to determine which has the higher
temperature, and a test of the equality of temperature
w h i c h is i n d e p e n d e n t of the nature of the b o d i e s tested.
B u t w e h a v e n o m e a n s of estimating numerically the differ
ence b e t w e e n two temperatures, so as to b e a b l e to assert
that a certain temperature is exactly halfway b e t w e e n two
other temperatures.
L a w of E q u a l T e m p e r a t u r e s . — B o d i e s whose temperature!,
are equal to that of the same body have themselves equal tem
peratures. T h i s l a w is not a truism, b u t expresses the fact
that if a piece of iron w h e n p l u n g e d into a vessel of w a t e r
is in thermal equilibrium with the water, a n d if the same
piece of iron, without altering its temperature, is transferred
to a vessel of oil, a n d is f o u n d to b e also in thermal equi
librium with the oil, then if the oil a n d w a t e r w e r e put
into the s a m e vessel they w o u l d themselves b e in thermal

Comparison of Temperatures. 33
equilibrium, a n d the same w o u l d b e true o f any other three
substances.
T h i s law, therefore, expresses m u c h m o r e than Euclid's
a x i o m . t h a t ' T h i n g s w h i c h are e q u a l t o the s a m e thing are
equal to o n e another,' a n d is t h e f o u n d a t i o n oi the whole
. science o f thermometry. F o r if w e take a thermometer,
s u c h as w e h a v e a l r e a d y described, and bring it i n t o in
timate contact with different b o d i e s , b y plunging it into
liquids, o r inserting it i n t o h o l e s m a d e in solid b o d i e s , w e
find that t h e m e r c u r y i n t h e t u b e rises o r falls t i l l i t has
r e a c h e d a c e r t a i n p o i n t at w h i c h it r e m a i n s s t a t i o n a r y . We
t h e n k n o w that t h e t h e r m o m e t e r is n e i t h e r b e c o m i n g h o t t e r
n o r c o l d e r , b u t is i n t h e r m a l equilibrium with the surround
ing b o d y . It follows from this, b y t h e l a w o f e q u a l tem
peratures, that the t e m p e r a t u r e o f t h e b o d y is t h e s a m e as
that o f the t h e r m o m e t e r , a n d the temperature o f the t h e r m o
m e t e r itself is k n o w n from the h e i g h t at w h i c h the mer
c u r y s t a n d s i n the t u b e .
H e n c e t h e reading, as i t is c a l l e d , o f t h e t h e r m o m e t e r — •
t h a t is, t h e n u m b e r o f d e g r e e s i n d i c a t e d o n t h e s c a l e b y t h e
t o p o f the m e r c u r y in the tube—informs us o f the tem
p e r a t u r e o f t h e s u r r o u n d i n g s u b s t a n c e , as w e l l as o f t h a t o f
the m e r c u r y i n the t h e r m o m e t e r . I n this w a y t h e thermo
meter may b e used to c o m p a r e the temperature of any
two b o d i e s at the same t i m e o r a t d i f f e r e n t t i m e s , so as
to ascertain whether the temperature of one of them is
higher or l o w e r than that of the other. W e may compare
i n this w a y t h e t e m p e r a t u r e s o f t h e air o n different days ;
w e m a y a s c e r t a i n t h a t w a t e r b o i l s at a l o w e r t e m p e r a t u r e at
the t o p o f a m o u n t a i n t h a n i t d o e s at t h e s e a - s h o r e , a n d that
i c e m e l t s a t t h e s a m e t e m p e r a t u r e in a l l p a r t s o f t h e w o r l d .
F o r this p u r p o s e it w o u l d b e n e c e s s a r y t o c a n y t h e s a m e
thermometer to different places, and t o p r e s e r v e it with
g r e a t care, for if it w e r e d e s t r o y e d a n d a n e w o n e made,
w e s h o u l d h a v e n o c e r t a i n t y t h a t t h e s a m e t e m p e r a t u r e is
indicated b y the same reading in the t w o thermometers.
D

$\ Tliermometry.
Thus the observations of temperature recorded during
1
sixteen years b y R i n i e r i at F l o r e n c e lost_ t h e i r scientific
v a l u e after t h e s u p p r e s s i o n o f the A c c a d e m r a del C i m e n t o ,
and the supposed destruction o f the thermometers wkh
w h i c h the observations were made. But when Antinofl in
1829 discovered a number o f the v e r y t h e r m o m e t e r s used_
2
in the ancient observations, L i b r i w a s a b l e t o c o m p a r e t h e m
with Reaumur's s c a l e , a n d thus t o s h o w t h a t t h e c l i m a t e o f
F l o r e n c e has n o t b e e n rendered sensibly colder in winter
b y the c l e a r i n g o f t h e w o o d s o f t h e A p e n n i n e s .
I n t h e c o n s t r u c t i o n o f artificial s t a n d a r d s f o r t h e measure
m e n t o f quantities o f any kind it is d e s i r a b l e t o h a v e the
means o f c o m p a r i n g the standards together, either directly,
or b y means o f s o m e natural o b j e c t or p h e n o m e n o n w h i c h
is e a s i l y a c c e s s i b l e a n d n o t l i a b l e t o c h a n g e . Both methods
are used in the preparation o f thermometers.
We h a v e already n o t i c e d t w o natural p h e n o m e n a which
t a k e p l a c e at d e f i n i t e t e m p e r a t u r e s — t h e m e l t i n g o f i c e a n d
the b o i l i n g o f water. T h e advantage o f e m p l o y i n g these
temperatures to determine t w o points o n the scale o f the
thermometer was pointed out b y Sir I s a a c N e w t o n ( ' S c a l a
Graduum Caloris,' Phil. Trans. 1701).
T h e first o f t h e s e p o i n t s o f r e f e r e n c e is c o m m o n l y c a l l e d
the Freezing Point. T o determine it, t h e thermometer is
p l a c e d i n a v e s s e l filled w i t h p o u n d e d i c e o r s n o w t h o r o u g h l y
moistened with water. I f the atmospheric temperature be
a b o v e the freezing point, the melting o f the ice will ensure
the presence o f water in the vessel. A s l o n g as e v e r y p a r t
o f the vessel contains a mixture o f water and i c e its t e m
perature remains uniform, for i f heat enters the vessel it
can only melt s o m e o f the ice, and i f heat escapes from
the vessel some o f the water will freeze, but the mixture can
b e m a d e n e i t h e r h o t t e r n o r c o l d e r t i l l a l l t h e i c e is m e l t e d
o r all t h e w a t e r f r o z e n .
1
Pupil of Galileo ; died 1647.
1
Annales de Chimie et.de Physique, xlv. (1830).

Temperatures of Reference. 35
T h e t h e r m o m e t e r is c o m p l e t e l y i m m e r s e d i n t h e mixture
o f i c e a n d w a t e r f o r a sufficient t i m e , s o t h a t t h e mercury
has t i m e t o T e S c h its s t a t i o n a r y p o i n t . T h e position o f the
top o f the mercury in the tube is
thtjn r e c o r d e d b ^ m a k i n g a scratch
on the glass tube. We shall call
•this m a r k the Freezing Point It
m a y b e d e t e r m i n e d i n this w a y w i t h
« x t r e m e accuracy, for, as w e shall
see a f t e r w a r d s , the temperature of
m e l t i n g i c e is v e r y n e a r l y t h e s a m e
u n d e r v e r y different pressures.
The other point o f r e f e r e n c e is
called- the B o i l i n g P o i n t . T h e tem
perature at which water boils de
pends o n the pressure o f the atmo
sphere. T h e greater the pressure o f
t h e air o n t h e surface o f the water,
the higher is the temperature to
which the water must be raised
b e f o r e it b e g i n s t o b o i l .
To d e t e r m i n e the B o i l i n g P o i n t , the stem o f t h e t h e r m o
m e t e r is p a s s e d through a h o l e in t h e lid o f a tall vessel,
i n t h e l o w e r p a r t o f w h i c h w a t e r is m a d e t o b o i l b r i s k l y , s o
that t h e w h o l e o f t h e u p p e r p a r t , w h e r e t h e t h e r m o m e t e r is
placed, is f i l l e d with steam. W h e n the thermometer has
acquired the temperature o f the current o f steam the stem
is d r a w n u p t h r o u g h t h e h o l e i n t h e l i d o f t h e v e s s e l till t h e
top o f the c o l u m n o f mercury b e c o m e s visible. A scratch
is t h e n m a d e o n t h e t u b e t o i n d i c a t e t h e b o i l i n g p o i n t .
In careful d e t e r m i n a t i o n s o f t h e b o i l i n g p o i n t n o p a r t o f
the t h e r m o m e t e r is a l l o w e d t o d i p into the boiling water,
b e c a u s e it has b e e n f o u n d b y G a y - L u s s a c t h a t t h e t e m p e r a t u r e
of t h e w a t e r is n o t a l w a y s t h e same, but that it b o i l s at
different t e m p e r a t u r e s in d i f f e r e n t k i n d s o f v e s s e l s . It has
been shown, h o w e v e r , b y R u d b e r g that the temperature of
D 2

36 Tìiermometry
t h e s t e a m w h i c h e s c a p e s f r o m b o i l i n g w a t e r is t h e s a m e in
every kind o f vessel, and depends o n l y on the pressure at
t h e surface o f the water. H e n c e the thermometer is n o t
d i p p e d in the water, but suspended in the issuing steam. To
ensure that the temperature o f the s t e a m shall b e t h e s a m e
w h e n it r e a c h e s t h e t h e r m o m e t e r as w h e n it issues f r o m the
b o i l i n g w a t e r , t h e sides o f t h e v e s s e l a r e s o m e t i m e s p r o t e c t e d
b y w h a t is c a l l e d a s t e a m - j a c k e t . A current o f steam is
m a d e to p l a y o v e r the out-
FIG. 3. side of the sides of the
vessel. T h e v e s s e l is thus
raised to the same t e m p e -
r a t u r e as t h e s t e a m itself, so
that the steam cannot be
cooled d u r i n g its passage
from the boiling water to
the thermometer.
For instance, if w e take
any tall n a r r o w v e s s e l , as
a coffee-pot, and cover its mouth and part o f its sides
with a wider vessel turned upside down, taking care that
t h e r e shall b e p l e n t y o f r o o m for t h e steam to escape, then
if w e b o i l a s m a l l q u a n t i t y o f w a t e r i n t h e c o f f e e - p o t , a t h e r m o -
meter placed in the steam a b o v e will be raised to the
exact temperature o f the boiling point o f water corresponding
t o t h e state o f t h e b a r o m e t e r a t t h e t i m e .
To mark the level o f the mercury on the tube o f the
t h e r m o m e t e r w i t h o u t c o o l i n g it, w e m u s t d r a w i t u p through
a c o r k or a plug o f india-rubber in the steam-jacket through
w h i c h the steam p a s s e s till w e c a n j u s t s e e t h e t o p o f t h e
column o f mercury. A mark must then b e scratched o n the
glass to register the boiling point. This experiment of
e x p o s i n g a t h e r m o m e t e r t o t h e s t e a m o f b o i l i n g w a t e r is an
important o n e , f o r it n o t o n l y s u p p l i e s a means o f gradu-
ating thermometers, and testing t h e m w h e n they h a v e b e e n
g r a d u a t e d , but, s i n c e t h e t e m p e r a t u r e at w h i c h w a t e r b o i l s

Scale of the Thermometer. 37
d e p e n d s o n the pressure o f t h e air, w e m a y d e t e r m i n e the
p r e s s u r e o f t h e air b y b o i l i n g w a t e r w h e n w e a r e n o t a b l e t o
measure it by means o f the appropriate instrument, the
barometer.
W e have n o w obtained two points o f reference marked b y
scratches o n the tube o f the t h e r m o m e t e r — t h e freezing p o i n t
and the b o i l i n g point. W e shall s u p p o s e for the present
that when the boiling point was marked the barometer
happened to indicate the standard pressure of 20/905
inches o f m e r c u r y at 0 ° C . at t h e l e v e l o f t h e sea i n the
latitude of London. In this case the boiling point is
the standard boiling point. I n a n y o t h e r c a s e it m u s t b e
corrected.
Our thermometer will n o w agree with any other properly
c o n s t r u c t e d t h e r m o m e t e r at t h e s e t w o t e m p e r a t u r e s .
I n order to indicate other temperatures, w e must construct
a s c a l e — t h a t is, a series o f m a r k s — e i t h e r o n t h e t u b e i t s e l f or
on a c o n v e n i e n t part o f the apparatus close to the tube a n d
w e l l f a s t e n e d t o it.
F o r this p u r p o s e , h a v i n g s e t t l e d w h a t v a l u e s w e are t o g i v e
t o the freezing and the boiling points, w e d i v i d e the space
b e t w e e n t h o s e p o i n t s i n t o as m a n y e q u a l p a r t s as t h e r e are
d e g r e e s b e t w e e n t h e m , a n d c o n t i n u e t h e series o f e q u a l d i v i
s i o n s u p a n d d o w n t h e s c a l e as far as t h e t u b e o f t h e t h e r m o
meter extends.
T h r e e d i f f e r e n t w a y s o f d o i n g this a r e still i n use, a n d ,
as we often find temperatures stated according to a
different scale from that which w e adopt o u r s e l v e s , i t is
necessary t o k n o w the p r i n c i p l e s o n w h i c h these scales are
formed.
1
T h e C e n t i g r a d e scale was introduced b y Celsius. I n it
the freezing p o i n t is m a r k e d 0° and called zero, and the
b o i l i n g p o i n t is m a r k e d ioo°.
T h e o b v i o u s s i m p l i c i t y o f this m o d e of d i v i d i n g t h e s p a c e
between the points of reference into 100 equal parts and
1
Professor of Astronomy in the University of Upsala.

Thermometry.
c a l l i n g e a c h o f t h e s e a d e g r e e , a n d r e c k o n i n g all temperatutea
in degrees from the freezing point, caused it t o be very
generally adopted, along with the F r e n c h d e c i m a l system o f
m e a s u r e m e n t , b y scientific m e n , e s p e c i a l l y o n the C o n t i n e n t
of Europe. I t is t r u e t h a t the advantage o f the decimal
s y s t e m is n o t so g r e a t i n t h e m e a s u r e m e n t o f t e m p e r a t u r e s as
i n o t h e r c a s e s , as it m e r e l y m a k e s i t e a s i e r t o r e m e m b e r the
freezing and boiling temperatures, but t h e g r a d u a t i o n is n o t
too fine for the roughest purposes, while for accurate
m e a s u r e m e n t s the d e g r e e s m a y b e s u b d i v i d e d into tenths and
hundredths.
T h e other t w o scales are c a l l e d b y the n a m e s o f those w h o

introduced them.
Fahrenheit, of Dantzig, about 1714, first constructed
thermometers comparable with each other. In Fahrenheit's
s c a l e t h e f r e e z i n g p o i n t is m a r k e d 3 2 ° , a n d t h e b o i l i n g p o i n t
212°, t h e s p a c e b e t w e e n b e i n g d i v i d e d i n t o 180 e q u a l parts,
and the g r a d u a t i o n e x t e n d e d a b o v e a n d b e l o w the points o f
reference. A p o i n t 32 d e g r e e s b e l o w t h e freezing point is
called zero, or 0°, a n d temperatures b e l o w this are i n d i c a t e d
b y the number o f degrees b e l o w zero.
This scale is v e r y generally used in English-speaking
c o u n t r i e s f o r p u r p o s e s o f o r d i n a r y l i f e , a n d a l s o for t h o s e o f
science, though the Centigrade scale is c o m i n g i n t o use
a m o n g those w h o w i s h their results t o b e r e a d i l y f o l l o w e d b y
foreigners.
T h e o n l y advantages w h i c h can b e a s c r i b e d to Fahrenheit's
s c a l e , b e s i d e s its e a r l y i n t r o d u c t i o n , its g e n e r a l d i f f u s i o n , a n d
its a c t u a l e m p l o y m e n t b y s o m a n y o f our c o u n t r y m e n , are
that m e r c u r y e x p a n d s a l m o s t e x a c t l y o n e t e n - t h o u s a n d t h o f
its v o l u m e a t 142° F . f o r e v e r y d e g r e e o f F a h r e n h e i t ' s scale,
and that the coldest temperature which w e can get by
mixing snow - and salt is near the zero of Fahrenheit's
scale.
T o c o m p a r e temperatures g i v e n in F a h r e n h e i t ' s scale w i t h
temperatures g i v e n in the C e n t i g r a d e scale w e h a v e o n l y t o

Thermometric Scales. 39
r e m e m b e r t h a t o ° C e n t i g r a d e is 3 2 ° F a h r e n h e i t , a n d t h a t five
d e g r e e s C e n t i g r a d e are equal t o n i n e o f F a h r e n h e i t .
T h e t h i r d t h e r m o m e t r i c s c a l e is t h a t o f R e a u m u r . I n this
scale t h e f r e e z i n g p o i n t is m a r k e d 0 ° a n d t h e b o i l i n g p o i n t
80°. I a m n o t a w a r e o f a n y a d v a n t a g e o f this s c a l e . I t is
used t o s o m e e x t e n t o n the C o n t i n e n t o f E u r o p e for m e d i c a l
and domestic purposes. Four degrees o f Reaumur corre
s p o n d t o five C e n t i g r a d e a n d t o n i n e o f F a h r e n h e i t .
T h e e x i s t e n c e o f these t h r e e t h e r m o m e t r i c scales furnishes
an e x a m p l e o f t h e i n c o n v e n i e n c e o f t h e w a n t o f u n i f o r m i t y i n
systems o f measurement. T h e w h o l e of what w e have said
about the comparison of the different scales might have
b e e n o m i t t e d i f a n y o n e o f these scales h a d b e e n a d o p t e d b y
all w h o use t h e r m o m e t e r s . I n s t e a d o f s p e n d i n g our t i m e in
describing the arbitrary proposals o f different m e n , w e should
have g o n e on to investigate the laws o f heat and the pro
perties o f b o d i e s .
W e shall a f t e r w a r d s h a v e o c c a s i o n t o use a s c a l e d i f f e r i n g
i n its z e r o - p o i n t f r o m a n y o f t h o s e w e h a v e c o n s i d e r e d , b u t
w h e n w e d o s o w e shall b r i n g f o r w a r d r e a s o n s f o r its a d o p t i o n
d e p e n d i n g o n the nature o f things a n d n o t o n the p r e d i l e c
tions of m e n .
I f two thermometers are constructed o f the s a m e k i n d o f
g l a s s , w i t h t u b e s o f u n i f o r m b o r e , a n d a r e filled w i t h t h e s a m e
l i q u i d and then g r a d u a t e d in t h e s a m e w a y , t h e y m a y b e c o n
sidered for ordinary purposes as c o m p a r a b l e instruments;
so that though they m a y never have been actually com
p a r e d together, y e t in ascertaining the temperature o f any
thing there will b e v e r y little difference whether w e use the
o n e t h e r m o m e t e r or the other.
But i f w e desire great accuracy in the measurement of
temperature, so t h a t the observations made by different
observers with different instruments may be strictly c o m
parable, the o n l y satisfactory method is b y agreeing to
c h o o s e o n e t h e r m o m e t e r as a s t a n d a r d a n d c o m p a r i n g a l l t h e
others with i t

4Q Thermometry.
A l l thermometers ought to be made with tubes of as

u n i f o r m b o r e as c a n b e f o u n d ; b u t for a s t a n d a r d t h e r m o m e t e r
t h e b o r e s h o u l d b e c a l i b r a t e d — t h a t is t o say, its size s h o u l d b e
m e a s u r e d at short intervals all a l o n g its l e n g t h .
F o r this p u r p o s e , b e f o r e t h e b u l b is b l o w n , a s m a l l q u a n t i t y
o f m e r c u r y is i n t r o d u c e d i n t o t h e t u b e a n d m o v e d a l o n g t h e
t u b e b y f o r c i n g a i r i n t o t h e t u b e b e h i n d it. T h i s is d o n e b y
s q u e e z i n g t h e air o u t o f a s m a l l i n d i a - r u b b e r b a l l w h i c h is
fastened to the end o f the tube.
I f the length o f the c o l u m n o f mercury remains exactly
t h e s a m e as it passes a l o n g the tube, the b o r e o f the tube
m u s t b e u n i f o r m ; b u t e v e n i n t h e b e s t t u b e s t h e r e is a l w a y s
some want o f uniformity.
But if w e introduce a short c o l u m n o f mercury into the
t u b e , t h e n m a r k b o t h e n d s o f t h e c o l u m n , a n d m o v e it o n its
own l e n g t h , till o n e end comes exactly to the mark where
the other end was originally, then mark the other end, and
m o v e it o n again, w e shall h a v e a series o f m a r k s o n the tube
such that the c a p a c i t y o f the t u b e b e t w e e n a n y t w o consecu
tive marks will be the same, b e i n g equal to that o f the
column o f mercury.
B y this m e t h o d , w h i c h was i n v e n t e d b y Gay-Lussac, a
number of divisions may be marked on the tube, each of
which contains the same volume, and though t h e y will p r o
b a b l y not correspond to degrees w h e n the t u b e is m a d e u p
into a t h e r m o m e t e r , it w i l l b e easy t o c o n v e r t the r e a d i n g o f
this i n s t r u m e n t i n t o d e g r e e s b y m u l t i p l y i n g i t b y a p r o p e r
factor, a n d i n t h e use o f a s t a n d a r d i n s t r u m e n t this t r o u b l e is
r e a d i l y u n d e r t a k e n for the sake o f accuracy.
The tube having been p r e p a r e d i n this w a y , o n e e n d is
h e a t e d till i t is m e l t e d , a n d i t is b l o w n i n t o a b u l b b y f o r c i n g
air in at the other end o f the tube. In order to avoid
i n t r o d u c i n g m o i s t u r e i n t o t h e t u b e , this is d o n e , n o t b y t h e
mouth, but b y means o f a h o l l o w india-rnbber b a l l , w h i c h is
fastened to the e n d o f t h e tube.

Construction of a Tthermometer. 41
The tube o f a t h e r m o m e t e r is g e n e r a l l y s o n a r r o w that
m e r c u r y w i l l n o t e n t e r it, f o r a r e a s o n w h i c h w e shall e x p l a i n
when w e c o m e to the properties o f liquids. Hence the
following m e t h o d is a d o p t e d t o fill t h e t h e r m o m e t e r . By
rolling paper round the o p e n e n d o f
v r
the tube, a n d m a k i n g t h e t u b e thus ' '
formed project a little b e y o n d the
glass tube, a c a v i t y is f o r m e d , into
which a little mercury is poured.
The mercury, h o w e v e r , will n o t run
d o w n the tube o f the thermometer,
partly b e c a u s e t h e b u l b a n d t u b e a r e
already full o f air, a n d p a r t l y b e c a u s e
the m e r c u r y r e q u i r e s a c e r t a i n p r e s
sure f r o m w i t h o u t t o e n t e r s o n a r r o w
a tube. T h e b u l b is t h e r e f o r e g e n t l y
h e a l e d so as t o c a u s e t h e air t o e x
pand, a n d some o f the air escapes
through t h e m e r c u r y . W h e n the bulb
cools, the p r e s s u r e o f t h e air i n the
bulb b e c o m e s less t h a n t h e pressure
o f the air o u t s i d e , a n d t h e difference
of these p r e s s u r e s is sufficient to
make the m e r c u r y enter the tube,
when it runs d o w n a n d p a r t i a l l y fills
the bulb.
I n o r d e r t o g e t rid o f t h e r e m a i n d e r o f t h e air, a n d o f a n y
moisture i n t h e t h e r m o m e t e r , t h e b u l b is g r a d u a l l y heated
till the mercury boils. T h e air and steam escape along
w i t h the v a p o u r o f m e r c u r y , a n d as t h e b o i l i n g c o n t i n u e s the
last r e m a i n s o f air a r e e x p e l l e d t h r o u g h t h e m e r c u r y at the
top of the tube. W h e n t h e b o i l i n g c e a s e s , t h e m e r c u r y runs
back i n t o t h e t u b e , w h i c h is thus p e r f e c t l y filled w i t h m e r c u r y .
W h i l e t h e t h e r m o m e t e r is still h o t t e r t h a n a n y t e m p e r a t u r e
at w h i c h it w i l l a f t e r w a r d s b e u s e d , a n d w h i l e t h e m e r c u r y o r

4 2 Thermometry.
i t s v a p o u r c o m p l e t e l y fills it, a b l o w p i p e flame is m a d e t o
p l a y o n t h e t o p o f t h e t u b e , s o a s t o m e l t it a n d c l o s e t h e e n d
o f the tube. T h e t u b e , t h u s c l o s e d w i t h its o w n s u b s t a n c e ,
1
is s a i d t o b e ' h e r m e t i c a l l y s e a l e d . '
T h e r e is n o w n o t h i n g i n t h e t u b e b u t mercury, and when
t h e m e r c u r y c o n t r a c t s s o as t o l e a v e a s p a c e a b o v e it, t h i s
space is e i t h e r e m p t y o f a l l g r o s s m a t t e r , o r c o n t a i n s only
the vapour o f mercury. If, i n spite o f all our precautions,
t h e r e is still s o m e air i n t h e t u b e , this c a n e a s i l y b e a s c e r t a i n e d
b y inverting the t h e r m o m e t e r a n d letting s o m e o f the mer
cury g l i d e t o w a r d s t h e e n d o f the tube. I f the instrument
is p e r f e c t , it w i l l r e a c h t h e e n d o f t h e t u b e a n d c o m p l e t e l y
fill it. I f t h e r e is a i r i n t h e t u b e t h e a i r w i l l f o r m a n e l a s t i c
cushion, w h i c h will p r e v e n t t h e mercury from r e a c h i n g the
e n d o f the tube, a n d will be seen in the form o f a small
bubble.
W e have next to d e t e r m i n e the freezing and b o i l i n g points,

a s has b e e n a l r e a d y d e s c r i b e d , b u t certain precautions have
still t o b e o b s e r v e d . I n t h e first p l a c e , g l a s s is a s u b s t a n c e
in w h i c h internal changes go on for some t i m e after it
has been strongly heated, or exposed to intense forces.
In fact, glass is in some degree a plastic body. It is
found t h a t after a thermometer has b e e n filled and sealed
the capacity o f the bulb diminishes slightly, and that this
c h a n g e is c o m p a r a t i v e l y r a p i d at first, a n d only gradually
b e c o m e s i n s e n s i b l e as t h e b u l b a p p r o a c h e s its u l t i m a t e c o n
dition. I t c a u s e s t h e f r e e z i n g p o i n t t o r i s e in t h e t u b e to
c , 0 ,
o 3 or o S , and if, a f t e r the displacement o f the zero, the
mercury b e again b o i l e d , the z e r o r e t u r n s t o its o l d p l a c e
a n d g r a d u a l l y rises a g a i n .
This change of the zero-point was discovered by M.
3
Flaugergues. I t m a y b e c o n s i d e r e d c o m p l e t e i n f r o m four t o
1
' F r o m Hermes or Mercury, the imagined inventor of chemistry.'—
J-ohnsori's Diet.
l
' Ann. de Ckimie et de Physique, -xxi. p . 333 (1S22).

Comparison of Thermometers. 43
1
six m o n t h s . I n o r d e r t o a v o i d the error w h i c h it w o u l d
i n t r o d u c e i n t o t h e scare, t h e i n s t r u m e n t s h o u l d , i f p o s s i b l e ,
h a v e its zero determined some months after i t has been
filled, and since e v e n the determination o f the b o i l i n g point
of water produces a slight depression o f the freezing point
( t h a t is, an e x p a n s i o n o f t h e b u l b ) , t h e f r e e z i n g p o i n t s h o u l d
not be determined after the boiling point, but rather
b e f o r e it.
When t h e b o i l i n g p o i n t is d e t e r m i n e d , t h e b a r o m e t e r is
probably not at the standard height. T h e mark made on
the thermometer m u s t , i n g r a d u a t i n g it, b e considered to
represent, n o t the standard boiling point, but the boiling
point corresponding to the o b s e r v e d height o f the baro
meter, w h i c h m a y b e found from the tables.
To construct a t h e r m o m e t e r i n this e l a b o r a t e w a y is b y
n o m e a n s an e a s y task, a n d e v e n w h e n t w o t h e r m o m e t e r s h a v e
been constructed with the utmost c a r e , t h e i r r e a d i n g s at
points distant from the freezing a n d b o i l i n g points m a y not
agree, on a c c o u n t o f differences in the law o f expansion of
the glass o f t h e t w o t h e r m o m e t e r s . T h e s e differences, how
ever, are small, for all t h e r m o m e t e r s are m a d e o f the same
description o f glass.
But since the main object of thermometry is t h a t all
t h e r m o m e t e r s shall b e s t r i c t l y c o m p a r a b l e , a n d s i n c e t h e r m o
meters are easily carried f r o m one place to another, the
best m e t h o d o f o b t a i n i n g t h i s o b j e c t is b y c o m p a r i n g all
thermometers either directly or indirectly with a single
standard thermometer. F o r this p u r p o s e , t h e t h e r m o m e t e r s ,
after b e i n g p r o p e r l y g r a d u a t e d , a r e all p l a c e d a l o n g w i t h the
standard t h e r m o m e t e r in a vessel, the temperature o f which
can be m a i n t a i n e d u n i f o r m for a c o n s i d e r a b l e time. Each
t h e r m o m e t e r is t h e n c o m p a r e d w i t h t h e s t a n d a r d t h e r m o m e t e r .
1
Dr. Joule, however, finds that the rise of the freezing point of a
delicate thermometer has been going on for twenty-six years, though the
changes are now exceedingly minute.—PMl. Soc. Mancliester^ Feb. 22,
1870.

44 Thermometry.
A table of corrections is made for each thermometer

by entering the reading o f that thermometer, a l o n g with
the correction w h i c h must b e applied to that r e a d i n g to
reduce it to the reading of the standard thermometer.
T h i s is c a l l e d t h e proper correction for that reading. If
it is p o s i t i v e i t m u s t b e a d d e d t o t h e r e a d i n g , a n d i f n e g a t i v e
it m u s t b e s u b t r a c t e d f r o m it.
B y b r i n g i n g the vessel t o various temperatures, the cor
rections at these temperatures for each thermometer are
a s c e r t a i n e d , a n d t h e series o f c o r r e c t i o n s b e l o n g i n g t o e a c h
thermometer is m a d e out and preserved along with that
thermometer.
A n y thermometer may be sent to the Observatory at
K e w , a n d w i l l b e r e t u r n e d w i t h a list o f c o r r e c t i o n s , b y t h e
application o f which, observations m a d e with that thermo
m e t e r b e c o m e strictly c o m p a r a b l e with those m a d e b y the
s t a n d a r d t h e r m o m e t e r at K e w , o r w i t h a n y o t h e r t h e r m o m e t e r
similarly corrected. T h e charge for m a k i n g the c o m p a r i s o n
is very small c o m p a r e d with the expense o f making an
original standard thermometer, and the scientific value of
observations m a d e with a t h e r m o m e t e r thus c o m p a r e d is
g r e a t e r than t h a t o f o b s e r v a t i o n s m a d e w i t h t h e m o s t e l a b o
r a t e l y p r e p a r e d t h e r m o m e t e r w h i c h has n o t b e e n c o m p a r e d
with s o m e existing and k n o w n standard instrument.
I h a v e d e s c r i b e d at c o n s i d e r a b l e l e n g t h t h e p r o c e s s e s by
w h i c h t h e t h e r m o m e t r i c s c a l e is c o n s t r u c t e d , a n d those by
which copies o f it are multiplied, because the practical
establishment o f s u c h a s c a l e is a n a d m i r a b l e instance of
the m e t h o d b y w h i c h w e must proceed in the scientific
o b s e r v a t i o n o f a p h e n o m e n o n s u c h as t e m p e r a t u r e , w h i c h , for
t h e p r e s e n t , w e r e g a r d r a t h e r as a quality, capable o f greater
o r less i n t e n s i t y , t h a n as a quantity which m a y b e a d d e d to
or subtracted from other quantities o f the same kind.
A t e m p e r a t u r e , s o far as w e h a v e y e t g o n e i n t h e s c i e n c e
o f h e a t , is n o t considered as capable of being added to
another temperature s o as t o f o r m a t e m p e r a t u r e w h i c h is

Temperature considered as a Quality. 45
the sum o f its c o m p o n e n t s . W h e n w e a r e a b l e t o attach a

distinct m e a n i n g t o such an operation, and determine its
result, our c o n c e p t i o n o f t e m p e r a t u r e w i l l b e raised t o the
rank o f a quantity. F o r t h e p r e s e n t , h o w e v e r , w e must b e
c o n t e n t t o r e g a r d t e m p e r a t u r e as a q u a l i t y o f b o d i e s , a n d be
satisfied t o k n o w t h a t t h e t e m p e r a t u r e s o f a l l b o d i e s c a n b e
referred to their p r o p e r p l a c e s in the same scale.
F o r i n s t a n c e , w e h a v e a right t o s a y t h a t t h e t e m p e r a t u r e s
0
o f f r e e z i n g a n d b o i l i n g differ b y 1 8 0 Fahrenheit; but w e
h a v e as y e t n o right t o say t h a t this d i f f e r e n c e is the s a m e
0
as that b e t w e e n the temperatures 300° and 480 on the
same scale. Still less can w e assert that a temperature o f
244° F . = 32°+2I2°
is e q u a l to t h e sum o f the temperatures o f freezing a n d
boiling. I n the same way, if w e had nothing b y which to
measure t i m e e x c e p t the succession o f our o w n thoughts,
we might b e a b l e t o refer each e v e n t w i t h i n our o w n e x
p e r i e n c e t o its p r o p e r c h r o n o l o g i c a l p l a c e i n a series, b u t
w e should h a v e n o m e a n s o f c o m p a r i n g the interval o f t i m e
b e t w e e n o n e pair o f e v e n t s w i t h that b e t w e e n another pair,
unless it h a p p e n e d that one o f these pairs was included
within the other pair, in w h i c h case the i n t e r v a l b e t w e e n the
first p a i r m u s t b e t h e s m a l l e s t . I t is o n l y b y o b s e r v a t i o n o f
t h e u n i f o r m o r p e r i o d i c m o t i o n s o f b o d i e s , a n d b y ascertain
ing the conditions u n d e r w h i c h certain m o t i o n s are a l w a y s
a c c o m p l i s h e d in the s a m e time, that w e h a v e been enabled
to measure time, first b y days and y e a r s , as i n d i c a t e d b y
the heavenly motions, and then by hours, minutes, and
s e c o n d s , as i n d i c a t e d b y the pendulums o f our c l o c k s , till
w e are n o w a b l e , n o t o n l y t o c a l c u l a t e t h e t i m e o f v i b r a t i o n
o f different kinds o f light, but t o c o m p a r e the time o f vibra
t i o n o f a m o l e c u l e o f h y d r o g e n set i n m o t i o n b y an e l e c t r i c
discharge through a glass tube, with the time o f vibration
o f a n o t h e r m o l e c u l e o f h y d r o g e n i n t h e sun, f o r m i n g p a r t o f
some great eruption o f rosy clouds, a n d with the time of
vibration o f another molecule in Sirius which has not

4 6 Thermometry.
transmitted its vibrations to our earth, but has simply
p r e v e n t e d v i b r a t i o n s a r i s i n g i n t h e b o d y o f t h a t star from
r e a c h i n g us.
In a subsequent chapter w e shall consider the further
p r o g r e s s o f o u r k n o w l e d g e o f T e m p e r a t u r e as a Q u a n t i t y .
ON THE AIR THERMOMETER.
The original thermometer invented b y Galileo was an

air t h e r m o m e t e r . I t consisted o f a glass bulb with a l o n g
neck. T h e air i n t h e b u l b w a s h e a t e d , a n d t h e n the neck
was plunged into a c o l o u r e d liquid. A s t h e air i n t h e b u l b
cooled, the liquid rose in the neck, and the higher the
liquid the lower the temperature o f the air i n t h e bulb.
B y putting the b u l b into the m o u t h o f a patient, and noting
t h e p o i n t t o w h i c h t h e l i q u i d w a s d r i v e n d o w n i n the t u b e , a
physician might estimate whether the a i l m e n t was o f the
nature o f a fever or n o t S u c h a t h e r m o m e t e r has several
obvious merits. It is e a s i l y c o n s t r u c t e d , and gives larger
i n d i c a t i o n s f o r t h e s a m e c h a n g e o f t e m p e r a t u r e than a t h e r m o
meter containing any liquid as the thermometric sub
stance. B e s i d e s this, t h e air r e q u i r e s l e s s h e a t t o w a r m it
than an e q u a l b u l k o f a n y l i q u i d , so t h a t t h e a i r thermo
meter is v e r y r a p i d i n its indications. T h e great incon
venience o f the instrument as a means o f measuring tem
p e r a t u r e is, t h a t t h e h e i g h t o f t h e l i q u i d i n t h e t u b e d e p e n d s
o n the p r e s s u r e o f the atmosphere as w e l l as o n the tem
perature o f the air in the bulb. T h e air t h e r m o m e t e r c a n n o t
t h e r e f o r e o f i t s e l f t e l l us a n y t h i n g a b o u t t e m p e r a t u r e . We
m u s t c o n s u l t t h e b a r o m e t e r at t h e s a m e t i m e , i n order'to
c o r r e c t t h e r e a d i n g o f t h e air t h e r m o m e t e r . H e n c e t h e air
thermometer, to b e o f any scientific value, must b e used
a l o n g w i t h the barometer, and its r e a d i n g s a r e of no use
till after a process o f calculation has b e e n g o n e through.
This p u t s it at a great disadvantage compared with the
m e r c u r i a l t h e r m o m e t e r as a m e a n s o f ascertaining tempera-

The A ir Thermometer. 47
tures. B u t i f the r e s e a r c h e s o n w h i c h w e are e n g a g e d are

o f so i m p o r t a n t a n a t u r e t h a t w e a r e w i l l i n g t o u n d e r g o t h e
labour o f d o u b l e observations and numerous calculations,
then the a d v a n t a g e s o f the air t h e r m o m e t e r m a y again pre
ponderate.
W e h a v e seen that in fixing a scak: o f temperature after
marking on our t h e r m o m e t e r t w o temperatures o f reference
and filling up the i n t e r v a l w i t h e q u a l divisions, two thermo
meters c o n t a i n i n g different liquids w i l l n o t in g e n e r a l agree
e x c e p t at t h e t e m p e r a t u r e s o f reference.
If, o n t h e o t h e r h a n d , w e c o u l d s e c u r e a c o n s t a n t p r e s s u r e
in the air t h e r m o m e t e r , t h e n i f w e e x c h a n g e t h e air f o r a n y
other gas, all the readings w i l l be e x a c t l y the same p r o v i d e d
the r e a d i n g at o n e o f the temperatures o f r e f e r e n c e is t h e
same. I t appears, therefore, that the scale o f temperatures
as i n d i c a t e d b y a n air t h e r m o m e t e r h a s this a d v a n t a g e over
the s c a l e i n d i c a t e d b y m e r c u r y o r a n y o t h e r l i q u i d o r s o l i d ,
that w h e r e a s n o t w o l i q u i d o r s o l i d s u b s t a n c e s c a n b e m a d e t o
agree in their expansion throughout the s c a l e , all t h e gases
agree with one another. In the absence of any better
reasons for choosing a scale, the agreement o f so many
s u b s t a n c e s is a reason w h y the scale o f temperatures fur
n i s h e d b y t h e e x p a n s i o n o f g a s e s s h o u l d b e c o n s i d e r e d as o f
great scientific value. In the course of our study we
shall find t h a t t h e r e a r e s c i e n t i f i c r e a s o n s o f a m u c h h i g h e r
order w h i c h enable us to fix on a scale o f temperature,
b a s e d n o t o n a p r o b a b i l i t y o f t h i s k i n d , b u t o n a m o r e inti
mate k n o w l e d g e o f the properties o f heat. T h i s s c a l e , so
far as it has b e e n i n v e s t i g a t e d , is f o u n d t o a g r e e v e r y c l o s e l y
w i t h that o f t h e a i r t h e r m o m e t e r .
T h e r e is a n o t h e r r e a s o n , o f a p r a c t i c a l k i n d , in f a v o u r o f
the use o f air as a t h e r m o m e t r i c s u b s t a n c e , n a m e l y , that air
remains in the gaseous s t a t e at t h e l o w e s t as w e l l as the
highest temperatures w h i c h .we can p r o d u c e , a n d there are
n o i n d i c a t i o n s i n e i t h e r c a s e o f its a p p r o a c h i n g t o a c h a n g e
o f state. H e n c e air, o r o n e o f t h e p e r m a n e n t g a s e s , is o f

4 8 Thermometry.
the greatest use in estimating temperatures l y i n g far o u t s i d e
o f the temperatures o f r e f e r e n c e , such, f o r i n s t a n c e , as the
freezing p o i n t o f mercury or the m e l t i n g p o i n t o f silver.
W e shall c o n s i d e r t h e p r a c t i c a l m e t h o d of using air as a
thermomecric substance w h e n w e c o m e to G a s o m e t r y . In
the meantime l e t us consider the air thermometer in its
s i m p l e s t f o r m , t h a t o f a l o n g t u b e o f u n i f o r m b o r e c l o s e d at
one end, and containing air or some other gas which is
s e p a r a t e d f r o m t h e o u t e r air b y a s h o r t column o f mercury,
F I G . 5.
oil, or s o m e o t h e r l i q u i d w h i c h is
AIR THKKMOMHTKK. capable o f m o v i n g freely along the
T i n melts
1
t u b e , w h i l e a t the s a m e t i m e it p r e
233 45
vents all c o m m u n i c a t i o n b e t w e e n the
confined air and the atmosphere.
W e shall a l s o s u p p o s e that t h e p r e s
ö sure a c t i n g o n t h e c o n f i n e d air is in
some w a y maintained constant dur
212° Boiling
ing the course o f the experiments
w e are g o i n g to describe.
The air t h e r m o m e t e r is first sur

0
3 2 Free zing.
rounded with ice and ice-cold water.
L e t us s u p p o s e t h a t t h e u p p e r s u r f a c e
l
~~ 37°' JoMf e rth e air n o i v s t a n d s at t h e point
cury freezes-
marked' Freezing.' T h e thermometer
is t h e n s u r r o u n d e d with the steam
Natterer's lowest
observed temperature.
rising from water boiling under an
a t m o s p h e r i c p r e s s u r e o f 29 '905 i n c h e s
o f mercury. L e t t h e surface o f the
e n c l o s e d air n o w s t a n d a t t h e point
marked 'Boiling.' I n this w a y , the
t w o temperatures o f reference are to
-460 0
b e m a r k e d o n the tube.
To complete the scale of the
t h e r m o m e t e r w e must d i v i d e the distance b e t w e e n b o i l i n g and
freezing into a selected number of equal parts, a n d carry
this g r a d u a t i o n up a n d d o w n the tube b e y o n d the freezing
and boiling points with degrees o f the s a m e length.

A bsolute Zero. 49
O f course, i f w e c a r r y the g r a d u a t i o n far e n o u g h down
the tube, w e shall at last c o m e t o t h e b o t t o m o f t h e tube.
W h a t w i l l b e t h e r e a d i n g at t h a t p o i n t 1 a n d w h a t is m e a n l
b y It?
T o d e t e r m i n e t h e r e a d i n g at t h e b o t t o m o f t h e t u b e is a
very simple matter. W e k n o w that the d i s t a n c e o f the
f r e e z i n g p o i n t f r o m t h e b o t t o m o f t h e t u b e is t o t h e d i s t a n c e
o f the b o i l i n g p o i n t f r o m t h e b o t t o m in t h e p r o p o r t i o n o f
i t o i'3665, s i n c e this is t h e d i l a t a t i o n o f air b e t w e e n the
freezing a n d the b o i l i n g t e m p e r a t u r e s . H e n c e it f o l l o w s , b y
an easy a r i t h m e t i c a l c a l c u l a t i o n , t h a t if, as in Fahrenheit's
0
scale, t h e freezing point is m a r k e d 32 , and the boiling
0
point 212 , the bottom o f the tube must be marked
— I
459°' 3' If, as i n t h e C e n t i g r a d e scale, t h e f r e e z i n g p o i n t
is m a r k e d o ° , a n d t h e b o i l i n g p o i n t r o o ° , the b o t t o m o f the
tube w i l l b e m a r k e d — 2"]2°-&e . T h i s , then, is t h e r e a d i n g at
l
the b o t t o m o f the s c a l e .
The other question, W h a t is meant b y this reading ?

requires a m o r e careful c o n s i d e r a t i o n . W e have begun by
denning the measure o f the temperature as the reading
o f the s c a l e o f o u r t h e r m o m e t e r w h e n it is e x p o s e d t o that
temperature. N o w i f t h e r e a d i n g c o u l d b e o b s e r v e d at t h e
b o t t o m o f t h e t u b e , it w o u l d i m p l y t h a t t h e v o l u m e o f the
air h a d b e e n r e d u c e d t o n o t h i n g . I t is h a r d l y n e c e s s a r y t o
say that w e h a v e n o e x p e c t a t i o n o f e v e r o b s e r v i n g such a
reading. I f it w e r e p o s s i b l e t o a b s t r a c t f r o m a s u b s t a n c e all
the heat it contains, it would probably still r e m a i n an
extended substance, a n d w o u l d o c c u p y a certain v o l u m e .
S u c h an a b s t r a c t i o n o f a l l its h e a t f r o m a b o d y has never
been effected, so that w e k n o w nothing about the tem
p e r a t u r e w h i c h w o u l d b e i n d i c a t e d b y an air thermometer
placed in c o n t a c t with a b o d y absolutely d e v o i d o f heat.
T h i s m u c h w e are sure of, h o w e v e r , that the r e a d i n g w o u l d
b e a b o v e — -4.S9°"i3 F .
I t is e x c e e d i n g l y c o n v e n i e n t , e s p e c i a l l y in dealing with
questions relating to gases, t o r e c k o n temperatures, n o t from
E
Thermometry.
the freezing point, or from Fahrenheit's zero, but from the

b o t t o m o f the tube o f the air t h e r m o m e t e r .
T h i s p o i n t is t h e n called the absolute zero of the air
thermometer, and temperatures r e c k o n e d from it a r e c a l l e d
absolute temperatures. I t is p r o b a b l e t h a t t h e d i l a t a t i o n o f
a p e r f e c t g a s is a l i t t l e l e s s t h a n 1 3 6 6 5 . I f w e suppose it
i\366, then absolute zero will b e —460° on Fahrenheit's
s c a l e , o r —273°^- C e n t i g r a d e .
I f we add 4 6 0 ° to the ordinary reading on Fahrenheit's
scale, w e shall obtain the absolute temperature in Fahren
heit's degrees.
I f w e a d d 273°^ t o t h e C e n t i g r a d e r e a d i n g , w e shall obtain
the absolute temperature in C e n t i g r a d e degrees.
We shall often have occasion to speak of absolute
t e m p e r a t u r e b y the air t h e r m o m e t e r . W h e n w e d o so w e
m e a n n o t h i n g m o r e than w h a t w e h a v e just s a i d — n a m e l y ,
t e m p e r a t u r e r e c k o n e d f r o m the b o t t o m o f the t u b e o f the air
thermometer. W e assert n o t h i n g as t o t h e s t a t e o f a body
d e p r i v e d o f a l l its h e a t , a b o u t w h i c h w e h a v e n o e x p e r i m e n t a l
knowledge.
O n e o f the most important applications o f the c o n c e p t i o n '
o f a b s o l u t e t e m p e r a t u r e is t o s i m p l i f y t h e e x p r e s s i o n o f t h e
t w o laws discovered respectively b y B o y l e and b y Charles.
The laws m a y be combined into the statement that the
product of the volume and pressure of any gas is proportional
to the absolute temperature.
F o r instance, if w e h a v e t o measure quantities o f a gas b y
their v o l u m e s under v a r i o u s c o n d i t i o n s as t o temperature
and pressure, w e can reduce these v o l u m e s t o w h a t they
w o u l d b e at s o m e standard temperature a n d pressure.
T h u s i f v , p, T b e t h e a c t u a l v o l u m e , p r e s s u r e , a n d absolute-
temperature, and v 0 t h e v o l u m e at the s t a n d a r d p r e s s u r e p 0 >
a n d t h e s t a n d a r d t e m p e r a t u r e T„, t h e n

Absolute Temperatures. 51
I f w e have only to c o m p a r e the relative quantities o f the

gag in different m e a s u r e m e n t s i n t h e s a m e s e r i e s o f e x p e r i
ments, w e m a y s u p p o s e P a n d T 0 0 b o t h unity, a n d use the
quantity without always m u l t i p l y i n g it b y — ° , w h i c h is

T p 0
1
a constant q u a n t i t y .
T h e great scientific i m p o r t a n c e o f the scale o f t e m p e r a t u r e
as d e t e r m i n e d b y m e a n s o f t h e a i r o r g a s t h e r m o m e t e r a r i s e s
from the fact, e s t a b l i s h e d b y t h e e x p e r i m e n t s o f J o u l e and
T h o m s o n , that t h e scale o f temperature derived from the
e x p a n s i o n o f t h e m o r e p e r m a n e n t g a s e s is a l m o s t e x a c t l y t h e
same as that f o u n d e d u p o n p u r e l y t h e r m o d y n a m i c c o n s i d e r a
tions, w h i c h a r e i n d e p e n d e n t o f t h e p e c u l i a r p r o p e r t i e s o f t h e
t h e r m o m e t r i c b o d y . T h i s a g r e e m e n t has b e e n e x p e r i m e n t a l l y
verified o n l y w i t h i n a r a n g e o f t e m p e r a t u r e b e t w e e n 0 ° C.
and i o o ° C. If, however, w e a c c e p t the m o l e c u l a r theory o f
gases, the v o l u m e o f a p e r f e c t g a s o u g h t t o b e e x a c t l y p r o
p o r t i o n a l t o the a b s o l u t e t e m p e r a t u r e o n t h e t h e r m o d y n a m i c
scale, a n d it is p r o b a b l e that as t h e temperature rises the
properties o f real gases a p p r o x i m a t e t o t h o s e o f the t h e o
retically perfect gas.
A l l the t h e r m o m e t e r s w h i c h w e h a v e c o n s i d e r e d h a v e
been constructed on the principle o f measuring the expansion
o f a s u b s t a n c e as t h e t e m p e r a t u r e rises. I n c e r t a i n c a s e s it is
convenient to estimate the temperature o f a substance b y the
heat w h i c h it g i v e s o u t as i t c o o l s t o a s t a n d a r d t e m p e r a t u r e .
T h u s i f a p i e c e o f p l a t i n u m h e a t e d i n a f u r n a c e is d r o p p e d
into water, w e m a y f o r m a n e s t i m a t e o f t h e t e m p e r a t u r e o f
the furnace b y t h e a m o u n t o f heat c o m m u n i c a t e d to the
water. S o m e ^ h a v e s u p p o s e d t h a t this m e t h o d o f e s t i m a t i n g
t e m p e r a t u r e s is m o r e s c i e n t i f i c t h a n t h a t f o u n d e d o n e x p a n
sion. It would b e so if the same quantity o f heat always
caused t h e s a m e rise o f t e m p e r a t u r e , w h a t e v e r t h e o r i g i n a l
1
For a full account of the methods of measuring gases the student is
referred to Bunsen's Gasometry, translated by Roscoe.
E2
Thermometry.
temperature o f the b o d y . But the specific heat of most

substances i n c r e a s e s as the t e m p e r a t u r e rises, a n d it in
creases in different d e g r e e s f o r d i f f e r e n t s u b s t a n c e s , s o that
this m e t h o d c a n n o t furnish a n a b s o l u t e s c a l e o f t e m p e r a t u r e .
I t is o n l y i n t h e c a s e o f g a s e s t h a t t h e s p e c i f i c h e a t o f a g i v e n
m a s s o f t h e s u b s t a n c e r e m a i n s t h e s a m e at a l l t e m p e r a t u r e s .
T h e r e are t w o methods o f estimating temperature which
are founded on the electrical properties o f bodies. We
cannot, within the limits o f this treatise, enter into the
t h e o r y o f t h e s e m e t h o d s , b u t m u s t refer t h e s t u d e n t t o w o r k s
on electricity. O n e o f these m e t h o d s d e p e n d s o n the fact
that i n a c o n d u c t i n g c i r c u i t f o r m e d o f t w o different metals,
if o n e o f t h e j u n c t i o n s b e w a r m e r t h a n t h e o t h e r , t h e r e w i l l
b e an e l e c t r o m o t i v e force w h i c h w i l l p r o d u c e a current o f
electricity in the circuit, and this m a y b e measured by
m e a n s o f a g a l v a n o m e t e r . I n this w a y v e r y m i n u t e d i f f e r e n c e s
o f temperature b e t w e e n the ends o f a p i e c e o f m e t a l m a y b e
detected. T h u s i f a p i e c e o f i r o n w i r e is s o l d e r e d at both
e n d s t o a c o p p e r w i r e , a n d i f o n e o f t h e j u n c t i o n s is at a p l a c e
where w e cannot introduce an ordinary thermometer, w e m a y
a s c e r t a i n its t e m p e r a t u r e b y p l a c i n g t h e o t h e r j u n c t i o n in a
vessel o f water and adjusting the temperature o f the water
till n o c u r r e n t p a s s e s . T h e temperature o f the water will
then b e equal t o that o f the inaccessible j u n c t i o n .
E l e c t r i c currents excited b y differences o f temperature in

different parts o f a m e t a l l i c circuit are c a l l e d t h e r m o - e l e c t r i c
currents. A n a r r a n g e m e n t b y w h i c h the e l e c t r o m o t i v e forces
arising from a n u m b e r o f j u n c t i o n s m a y b e a d d e d together
is c a l l e d a t h e r m o p i l e , a n d is u s e d in e x p e r i m e n t s o n the
h e a t i n g effect o f r a d i a t i o n , b e c a u s e it is m o r e s e n s i t i v e t o
changes o f temperature caused b y small quantities o f heat
than a n y o t h e r i n s t r u m e n t .
1
Professor T a i t has found that if t l and / 2 denote the
temperatures o f the hot and cold junction o f t w o metals,
1
Proceedings of the Royal Society of Edinburgh

Electrical Tkermometric Methods. 53
the e l e c t r o m o t i v e f o r c e o f t h e c i r c u i t f o r m e d b y t h e s e t w o
m e t a l s is
A _ ) [T -
T J (t, + /,)].
w h e r e A is a c o n s t a n t d e p e n d i n g o n t h e n a t u r e o f t h e m e t a l s ,
and T is a temperature also depending on the metals,
such that w h e n o n e j u n c t i o n is as m u c h h o t t e r than T as the
o t h e r is c o l d e r , n o c u r r e n t is p r o d u c e d , T m a y b e called the
neutral t e m p e r a t u r e for the t w o m e t a l s . F o r copper and
i r o n it is a b o u t 284° C .
T h e other m e t h o d o f estimating the temperature of a place
at w h i c h w e c a n n o t set a t h e r m o m e t e r is f o u n d e d o n the
i n c r e a s e o f t h e e l e c t r i c r e s i s t a n c e o f m e t a l s as t h e t e m p e
rature rises. T h i s m e t h o d h a s b e e n successfully e m p l o y e d
1
by M r . Siemens. T w o c o i l s o f t h e s a m e k i n d o f fine p l a t i n u m
w i r e are p r e p a r e d s o as t o h a v e e q u a l resistance. Their
e n d s are c o n n e c t e d w i t h l o n g t h i c k c o p p e r w i r e s , so t h a t t h e
coils m a y b e p l a c e d i f necessary a l o n g w a y from the g a l v a
nometer. T h e s e c o p p e r t e r m i n a l s a r e a l s o a d j u s t e d so as t o
b e o f the s a m e r e s i s t a n c e for b o t h c o i l s . T h e resistance o f
the t e r m i n a l s s h o u l d b e s m a l l as c o m p a r e d w i t h that o f t h e
coils. O n e o f t h e c o i l s is t h e n sunk, s a y t o t h e b o t t o m o f
the sea, a n d t h e o t h e r is p l a c e d i n a v e s s e l o f w a t e r , the
t e m p e r a t u r e o f w h i c h is a d j u s t e d till t h e r e s i s t a n c e of both
coils is t h e s a m e . By ascertaining with a thermometer the
r
t e m p e r a t u r e o f t h e v e s s e l o f w a t e r , t h a t o f t h e b o t t o m o f the
sea m a y b e d e d u c e d .
M r . Siemens has found that the resistance o f the metals
may b e expressed b y a formula o f the form
/
R = a v T+ /3T+y,
w h e r e R is t h e r e s i s t a n c e , T t h e a b s o l u t e t e m p e r a t u r e , and
a ft y c o e f f i c i e n t s . O f these a is t h e largest, a n d t h e r e
sistance d e p e n d i n g o n i t i n c r e a s e s as t h e s q u a r e r o o t o f t h e
absolute temperature, so that the resistance increases m o r e
s l o w l y as t h e t e m p e r a t u r e rises. T h e s e c o n d t e r m , (S T, is
1
Proceedings of the Royal Society, April 27, 1871.

54 Calorimetry.
proportional to the temperature and m a y b e attributed to

the e x p a n s i o n o f the substance. T h e third t e r m is , c o n -
stant
C H A P T E R III.
CALORIMETRY.
HAVING e x p l a i n e d t h e p r i n c i p l e s o f T h e r m o m e t r y , o r the
m e t h o d o f ascertaining temperatures, w e are a b l e t o under
stand what we may call C a l o r i m e t r y , or the m e t h o d o f
measuring quantities o f heat.
When h e a t is a p p l i e d t o a body it p r o d u c e s effects o f
various kinds. I n m o s t c a s e s it raises t h e t e m p e r a t u r e o f
t h e b o d y ; i t g e n e r a l l y a l t e r s its v o l u m e o r its pressure, a n d i n
c e r t a i n c a s e s i t c h a n g e s t h e state o f t h e b o d y f r o m s o l i d t o
liquid or from liquid to gaseous.
A n y effect o f h e a t m a y b e u s e d as a m e a n s o f m e a s u r i n g
quantities o f heat b y a p p l y i n g the principle that w h e n t w o
e q u a l p o r t i o n s o f t h e s a m e s u b s t a n c e i n t h e s a m e state a r e
acted o n b y heat in the same w a y so as to produce the
s a m e effect, t h e n t h e q u a n t i t i e s o f h e a t a r e e q u a l .
W e b e g i n b y choosing a standard b o d y , and defining the
s t a n d a r d effect o f h e a t upon it. Thus w e may choose a
p o u n d o f i c e at t h e f r e e z i n g p o i n t as t h e s t a n d a r d b o d y , a n d
w e m a y d e f i n e as t h e u n i t o f h e a t t h a t q u a n t i t y o f h e a t w h i c h
m u s t b e a p p l i e d t o this p o u n d o f i c e t o c o n v e r t i t i n t o a
pound o f water still at t h e freezing point. This is an
e x a m p l e o f a c e r t a i n c h a n g e o f state b e i n g u s e d t o define
w h a t is m e a n t b y a q u a n t i t y o f h e a t . T h i s unit o f heat w a s
brought into actual use in the e x p e r i m e n t s o f L a v o i s i e r and
Laplace.
In this system a quantity o f heat is m e a s u r e d b y the
number o f pounds ( o r o f g r a m m e s ) o f i c e at t h e freezing

The Unit of Heat. 55
p o i n t w h i c h that q u a n t i t y o f h e a t w o u l d c o n v e r t i n t o w a t e r
at the f r e e z i n g p o i n t .
W e might also e m p l o y a different system o f measurement
b y d e n n i n g a q u a n t i t y o f h e a t as m e a s u r e d b y t h e n u m b e r o f
p o u n d s o f w a t e r at t h e b o i l i n g p o i n t w h i c h it w o u l d c o n v e r t
i n t o s t e a m at t h e s a m e t e m p e r a t u r e .
T h i s m e t h o d is f r e q u e n t l y u s e d i n d e t e r m i n i n g t h e a m o u n t
o f heat g e n e r a t e d b y t h e c o m b u s t i o n o f fuel.
N e i t h e r o f these m e t h o d s requires the use o f the thermo
meter.
A n o t h e r m e t h o d , d e p e n d i n g on the use o f the thermo
m e t e r , is t o d e f i n e as t h e unit o f h e a t that q u a n t i t y o f heat
which if a p p l i e d to unit o f mass ( o n e p o u n d o r o n e g r a m m e )
o f w a t e r at s o m e standard temperature (that o f greatest
density, 39° F . o r 4 ° C , o r o c c a s i o n a l l y s o m e temperature
m o r e c o n v e n i e n t f o r l a b o r a t o r y w o r k , s u c h as 62° F . o r 15° C ) ,
will raise that water o n e d e g r e e (Fahrenheit or Centigrade)
in t e m p e r a t u r e .
A c c o r d i n g t o this m e t h o d a q u a n t i t y o f h e a t i s m e a s u r e d
b y the q u a n t i t y o f w a t e r at a s t a n d a r d t e m p e r a t u r e w h i c h that
quantity o f heat w o u l d raise o n e d e g r e e .
A l l t h a t is a s s u m e d i n t h e s e m e t h o d s o f m e a s u r i n g heat is
that if it t a k e s a c e r t a i n q u a n t i t y o f h e a t t o p r o d u c e a c e r t a i n
effect o n o n e p o u n d o f w a t e r i n a c e r t a i n state, t h e n t o p r o d u c e
the same effect on another similar p o u n d o f water will
r e q u i r e as m u c h h e a t , s o t h a t t w i c e t h e q u a n t i t y o f heat
is r e q u i r e d f o r t w o p o u n d s , t h r e e t i m e s f o r t h r e e p o u n d s ,
and so on.
W e h a v e n o right t o assume that b e c a u s e a unit o f heat
0
raises a p o u n d o f w a t e r at 3 9 F. o n e degree, therefore two
units o f h e a t w i l l r a i s e t h e s a m e p o u n d t w o d e g r e e s ; for the
0
q u a n t i t y o f h e a t r e q u i r e d t o r a i s e the w a t e r f r o m 40° t o 4 1
0 0
may b e different from t h a t w h i c h r a i s e d it f r o m 3 9 t o 40 .
I n d e e d , it has b e e n f o u n d b y e x p e r i m e n t that m o r e heat
is r e q u i r e d t o r a i s e a p o u n d o f w a t e r o n e d e g r e e at h i g h
t e m p e r a t u r e s t h a n at l o w o n e s .

56 Calorimetry.
But i f w e measure heat according to either o f the m e t h o d s

already described, cither b y the quantity o f a particular kind
o f m a t t e r w h i c h i t c a n c h a n g e f r o m o n e e a s i l y o b s e r v e d state
to another without altering its temperature, or by the
q u a n t i t y o f a p a r t i c u l a r k i n d o f m a t t e r w h i c h i t c a n raise
from one g i v e n temperature to another given temperature,
w e m a y t r e a t - q u a n t i t i e s o f h e a t as m a t h e m a t i c a l q u a n t i t i e s ,
a n d a d d o r s u b t r a c t t h e m as w e p l e a s e .
W e h a v e , h o w e v e r , i n t h e first p l a c e t o e s t a b l i s h that the
heat w h i c h b y e n t e r i n g o r l e a v i n g a b o d y in a n y manner
p r o d u c e s a g i v e n c h a n g e i n i t is a q u a n t i t y s t r i c t l y c o m
p a r a b l e w i t h that w h i c h m e l t s a pound o f ice, and differs
f r o m it o n l y b y b e i n g s o m a n y t i m e s g r e a t e r o r l e s s .
I n other words, w e h a v e to show that heat o f all kinds,
w h e t h e r c o m i n g from the hand, or h o t water, o r steam, or red-
h o t i r o n , o r a flame, o r t h e sun, or f r o m a n y o t h e r s o u r c e , c a n
b e m e a s u r e d i n t h e s a m e w a y , a n d t h a t the q u a n t i t y o f e a c h
r e q u i r e d t o effect a n y g i v e n c h a n g e , t o m e l t a p o u n d o f i c e ,
to b o i l away a p o u n d o f water, or to w a r m the water from o n e
t e m p e r a t u r e t o a n o t h e r , is t h e s a m e f r o m w h a t e v e r s o u r c e the
hea^t c o n i e s .
T o find w h e t h e r t h e s e effects d e p e n d o n a n y t h i n g e x c e p t
the quantity o f heat r e c e i v e d — f o r instance, if t h e y d e p e n d in
any w a y o n t h e temperature o f the source o f heat—suppose
t w o e x p e r i m e n t s tried. I n t h e first a c e r t a i n q u a n t i t y o f h e a t
( s a y t h e h e a t e m i t t e d b y a c a n d l e w h i l e a n i n c h o f c a n d l e is
c o n s u m e d ) is a p p l i e d d i r e c t l y t o m e l t i c e . I n the s e c o n d the
s a m e q u a n t i t y o f h e a t is a p p l i e d t o a p i e c e o f i r o n at t h e
f r e e z i n g p o i n t so as t o w a r m it, a n d t h e n t h e h e a t e d i r o n is
p l a c e d i n i c e s o as t o m e l t a c e r t a i n q u a n t i t y o f i c e , w h i l e t h e
i r o n i t s e l f is c o o l e d t o its o r i g i n a l t e m p e r a t u r e .
I f the quantity o f ice melted depends o n the temperature
o f the source from w h e n c e the heat proceeds, o r o n any
other circumstance than the quantity o f the heat, the quan
t i t y m e l t e d will differ i n t h e s e t w o c a s e s ; f o r i n t h e first t h e
heat c o m e s d i r e c t l y , f r o m an e x c e e d i n g l y h o t flame, a n d in

All Heat is of the same kind. 57
the s e c o n d t h e s a m e q u a n t i t y o f h e a t c o m e s from compara
tively cool iron.
I t is f o u n d b y e x p e r i m e n t t h a t n o s u c h d i f f e r e n c e exists,
a n d t h e r e f o r e h e a t , c o n s i d e r e d w i t h r e s p e c t t o its p o w e r o f
r
w a r m i n g t h i n g s a n d c h a n g i n g t h e i r state, is a q u a n t i t y s t r i c t l y
capable o f measurement, a n d n o t subject to a n y variations
in quality or in kind.
A n o t h e r principle, the truth o f w h i c h is e s t a b l i s h e d b y
c a l o r i m e t r i c a l e x p e r i m e n t s , is, t h a t i f a b o d y i n a g i v e n state
is first h e a t e d so as t o m a k e i t p a s s t h r o u g h a s e r i e s o f states
defined- b y the temperature and the v o l u m e o f the body
in each state, a n d i f it is t h e n a l l o w e d t o c o o l s o as to
pass i n r e v e r s e o r d e r t h r o u g h e x a c t l y the same series o f
states, t h e n t h e q u a n t i t y o f h e a t w h i c h e n t e r e d it d u r i n g t h e
heating p r o c e s s is e q u a l t o t h a t w h i c h left it during the
cooling process. B y t h o s e w h o r e g a r d e d heat as a sub
stance, a n d c a l l e d i t C a l o r i c , this p r i n c i p l e w a s r e g a r d e d
as s e l f - e v i d e n t , a n d w a s g e n e r a l l y t a c i t l y a s s u m e d . W e shall
s h o w , h o w e v e r , that t h o u g h i t is t r u e as w e h a v e s t a t e d it,
yet, i f t h e s e r i e s o f states d u r i n g t h e p r o c e s s o f h e a t i n g is
different f r o m t h a t d u r i n g t h e p r o c e s s o f c o o l i n g , t h e quan
tities o f h e a t absorbed a n d e m i t t e d m a y b e different. In
fact heat may be generated or d e s t r o y e d b y certain p r o
cesses, a n d this s h o w s t h a t h e a t is n o t a substance, v B y
finding w h a t i t is p r o d u c e d f r o m , a n d w h a t i t is r e d u c e d t o ,
w e m a y h o p e t o d e t e r m i n e the nature o f heat.
I n most o f the cases in w h i c h w e measure quantities of

h e a t , t h e h e a t w h i c h w e m e a s u r e is p a s s i n g o u t o f o n e b o d y
into another, o n e o f these bodies b e i n g the calorimeter
itself. W e assume that the quantity o f heat which leaves
the one body is e q u a l t o t h a t w h i c h t h e o t h e r receives,
p r o v i d e d , ist, that neither b o d y receives or parts w i t h heat
to any third b o d y ; a n d , 2ndly, t h a t n o a c t i o n t a k e s p l a c e
a m o n g the b o d i e s e x c e p t the g i v i n g a n d r e c e i v i n g o f heat.
The truth o f this a s s u m p t i o n m a y b e established ex
perimentally by taking a number of bodies at different

58 Calorimetry.
temperatures, and d e t e r m i n i n g first t h e q u a n t i t y o f h e a t r e

quired to b e g i v e n to or taken from each separately to bring
it t o a c e r t a i n standard temperature. I f the bodies are
n o w b r o u g h t to their original temperatures, and a l l o w e d t o
e x c h a n g e h e a t a m o n g t h e m s e l v e s in a n y w a y , t h e n t h e t o t a l
quantity o f heat required to b e given to the system to bring
it t o t h e s t a n d a r d t e m p e r a t u r e w i l l b e f o u n d t o b e t h e s a m e
as t h a t w h i c h w o u l d b e d e d u c e d f r o m t h e results i n t h e first
case.
W e n o w proceed to describe the e x p e r i m e n t a l methods
b y w h i c h these results m a y b e verified, a n d b y w h i c h quanti
ties o f heat in g e n e r a l m a y b e measured.
I n s o m e o f the earlier experiments o f B l a c k o n the heat
required t o melt ice and to boil water, the heat was applied
b y m e a n s o f a flame, a n d as t h e s u p p l y o f h e a t w a s a s s u m e d
to b e uniform, the quantities o f heat supplied w e r e inferred
to be proportional to the time during w h i c h the supply
continued. A method o f this k i n d is o b v i o u s l y v e r y i m
p e r f e c t , a n d in o r d e r t o m a k e it at all a c c u r a t e w o u l d n e e d
numerous precautions and auxiliary investigations with
respect to the laws o f the p r o d u c t i o n o f heat b y the flame
a n d its a p p l i c a t i o n t o t h e b o d y w h i c h is h e a t e d . Another
m e t h o d , a l s o d e p e n d i n g o n t h e o b s e r v a t i o n o f t i m e , is m o r e
worthy of confidence. W e shall d e s c r i b e it u n d e r t h e n a m e
of the M e t h o d o f C o o l i n g .
ICE CALORIMETERS.
W i l c k e , a S w e d e , w a s t h e first w h o e m p l o y e d t h e m e l t i n g
o f s n o w t o measure the heat g i v e n off b y b o d i e s in c o o l i n g .
T h e p r i n c i p a l difficulty i n this m e t h o d is t o e n s u r e t h a t a l l
the heat g i v e n off b y the b o d y is e m p l o y e d i n m e l t i n g the
ice, and that n o other heat reaches t h e i c e s o as t o m e l t it,
o r e s c a p e s f r o m t h e w a t e r so as t o f r e e z e it. This condition
was first fulfilled b y the calorimeter o f Laplace and La
v o i s i e r , o f w h i c h t h e d e s c r i p t i o n is g i v e n i n t h e M e m o i r s o f

The Ice Calorimeter. 59
the F r e n c h A c a d e m y o f Sciences for 1780. T h e instrument
itself is p r e s e r v e d in the C o n s e r v a t o i r e des A r t s et Me'tiers
at Paris.
This apparatus, which
afterwards received the
n a m e o f C a l o r i m e t e r , con
sists of three vessels, one
within another.
The first or innermost
vessel, w h i c h w e m a y call
the receiver, is i n t e n d e d to
hold the b o d y f r o m w h i c h
the heat to be measured
escapes. It is, made of
thin sheet c o p p e r , s o that '
the heat m a y r e a d i l y pass 1TZ
=:
into the s e c o n d vessel. T h e i^—
s e c o n d vessel, o r calorimeter p r o p e r , entirely s u r r o u n d s the
first. T h e l o w e r p a r t o f the space b e t w e e n the t w o vessels is
filled with b r o k e n ice at the freezing ( o r melting) point, a n d
the first vessel is then c o v e r e d b y m e a n s o f a lid, w h i c h is
itself a vessel full o f b r o k e n ice. W h e n the ice melts in this
vessel, w h e t h e r in the l o w e r part or in the c o v e r o f the first
vessel, the w a t e r trickles d o w n a n d passes t h r o u g h a d r a i n e r ,
w h i c h prevents any ice f r o m escaping, a n d so runs out into a
bottle set to catch it. T h e third vessel, w h i c h w e m a y call
the ice jacket, entirely s u r r o u n d s the s e c o n d , a n d is furnished,
like the s e c o n d , w i t h a n u p p e r lid to c o v e r the second. Both
the vessel a n d the lid are full of b r o k e n ice at the freezing
point, b u t the w a t e r f o r m e d b y the melting of this ice is
carried off to a vessel distinct from that w h i c h contains the
water from the calorimeter p r o p e r .
N o w , s u p p o s e that there is n o t h i n g in the receiver, a n d

that the temperature o f the s u r r o u n d i n g air is a b o v e the
freezing point. A n y heat which enters the outer vessel
will melt s o m e o f the ice in the jacket, a n d will n o t pass o n ,

6o Calorimetry.
a n d n o ice will b e m e l t e d in the calorimeter. A s long as

t h e r e is i c e i n t h e j a c k e t and in the c a l o r i m e t e r the tem
p e r a t u r e o f b o t h w i l l b e t h e s a m e , t h a t is, t h e f r e e z i n g p o i n t ,
and therefore, b y the law o f equilibrium o f heat, n o heat
will pass through the second vessel either outwards or
inwards. H e n c e , i f a n y i c e is m e l t e d i n the calorimeter,
t h e h e a t w h i c h m e l t s it m u s t c o m e f r o m t h e r e c e i v e r .
L e t us n e x t s u p p o s e t h e r e c e i v e r at t h e f r e e z i n g t e m p e r a
ture ; let the t w o lids b e carefully lifted off for an instant, a n d
a b o d y at s o m e h i g h e r t e m p e r a t u r e i n t r o d u c e d i n t o t h e r e
ceiver ; then let the lids b e quickly r e p l a c e d . H e a t will pass
from the b o d y through the sides o f the r e c e i v e r into the
calorimeter, ice will be melted, and the b o d y will b e cooled,
and this p r o c e s s will g o o n till the b o d y is c o o l e d t o the
freezing point, after which there will be no more ice
melted.
I f w e measure the water p r o d u c e d b y the m e l t i n g o f the
ice, w e m a y estimate the quantity o f heat w h i c h escapes
f r o m t h e b o d y w h i l e it c o o l s f r o m its o r i g i n a l t e m p e r a t u r e t o
the freezing point. T h e r e c e i v e r is at t h e f r e e z i n g p o i n t at
t h e b e g i n n i n g a n d at the e n d o f the operation, so that the
heating and subsequent cooling o f the receiver does not
i n f l u e n c e t h e result.
N o t h i n g can b e m o r e p e r f e c t than the theory and design
o f this a p p a r a t u s . I t is w o r t h y o f L a p l a c e a n d o f L a v o i s i e r ,
a n d i n t h e i r h a n d s i t f u r n i s h e d g o o d results.
T h e c h i e f i n c o n v e n i e n c e i n u s i n g it arises from the fact
that the w a t e r adheres t o the b r o k e n i c e instead o f draining
a w a y f r o m it c o m p l e t e l y , so t h a t it is i m p o s s i b l e t o e s t i m a t e
a c c u r a t e l y h o w m u c h i c e has r e a l l y b e e n m e l t e d .
To a v o i d this source o f uncertainty, Sir J o h n Herschel
p r o p o s e d t o fill t h e i n t e r s t i c e s o f t h e i c e w i t h w a t e r at the
freezing point, and to estimate the quantity o f i c e m e l t e d b y
the contraction w h i c h the v o l u m e o f the w h o l e undergoes,
since, as w e shall a f t e r w a r d s s e e , t h e v o l u m e o f t h e w a t e r is
less t h a n t h a t o f t h e i c e f r o m w h i c h it w a s f o r m e d . I am

Bunsen's Calorimeter. 61
n o t a w a r e that this s u g g e s t i o n w a s e v e r d e v e l o p e d i n t o an
experimental method.
1
Bunsen, independently, devised a calorimeter founded on
the same principle, but in the use o f w h i c h the sources
o f error a r e e l i m i n a t e d , a n d the physical constants deter
mined with a degree o f precision s e l d o m before attained
i n r e s e a r c h e s o f this k i n d .
B u n s e n ' s c a l o r i m e t e r , as d e v i s e d b y its a u t h o r , is a s m a l l
instrument. T h e b o d y w h i c h is t o F l G 7
g i v e off the heat which is t o be

measured is h e a t e d in a test-tube
placed in a current of steam of
known temperature. It is then
d r o p p e d , as q u i c k l y as m a y b e , i n t o
the test-tube T o f t h e calorimeter,
which contains water at o ° C . The
b o d y sinks t o the b o t t o m a n d gives
off heat to the water. T h e h e a t e d w a t e r d o e s n o t rise in t h e
tube, for the effect o f h e a t o n w a t e r b e t w e e n o ° C . a n d 4" C.
is t o i n c r e a s e its d e n s i t y . I t therefore remains surrounding
the b o d y at t h e b o t t o m o f t h e t u b e , a n d its h e a t c a n escape
only by conduction either upwards through the water, or
through the sides o f t h e tube, which, b e i n g thin, afford a
better channel. T h e t u b e is s u r r o u n d e d b y i c e at 0 ° C . in
t h e c a l o r i m e t e r , c, s o that as s o o n as a n y p a r t o f t h e w a t e r
i n the t u b e is r a i s e d t o a h i g h e r t e m p e r a t u r e , conduction
takes p l a c e through t h e s i d e s , a n d p a r t o f t h e i c e is m e l t e d .
T h i s will go on till e v e r y t h i n g w i t h i n the t u b e is again
reduced to 0° C , and the w h o l e quantity o f ice m e l t e d by
heat from within is an a c c u r a t e m e a s u r e o f t h e h e a t w h i c h
t h e h e a t e d b o d y g i v e s o u t as it c o o l s t o 0 ° C .
T o p r e v e n t any e x c h a n g e o f heat b e t w e e n the calorimeter
c a n d s u r r o u n d i n g b o d i e s , it is p l a c e d i n a v e s s e l s f i l l e d w i t h
s n o w g a t h e r e d w h e n n e w f a l l e n a n d free f r o m s m o k e . This
1 A
Fogg- »"- Sept. 1870, and Phil. Mag. 1871.

62. Calorimetry,
s u b s t a n c e , u n l e s s the t e m p e r a t u r e o f t h e r o o m is b e l o w o" C ,
s o o n acquires and l o n g maintains the temperature o f o ° C .
I n p r e p a r i n g t h e c a l o r i m e t e r , it is f i l l e d w i t h d i s t i l l e d w a t e r ,
f r o m w h i c h e v e r y t r a c e o f air m u s t b e e x p e l l e d b y a careful
process o f boiling. I f t h e r e is air in t h e w a t e r , t h e p r o c e s s
o f f r e e z i n g e x p e l s i t a n d p r o d u c e s b u b b l e s o f air, t h e v o l u m e
of which introduces an error o f measurement. T h e lower
part o f the calorimeter contains mercury, and communicates
with a bent tube also containing mercury. T h e upper part
o f this t u b e is b e n t horizontally, and is c a r e f u l l y calibrated
and graduated. A s the m e r c u r y a n d the vessel are a l w a y s
at d i e t e m p e r a t u r e o° C , they are o f constant v o l u m e , and
any changes in the position o f the mercury in the graduated
tube are due t o the m e l t i n g o f i c e in the calorimeter, a n d
the c o n s e q u e n t diminution o f v o l u m e o f the mass o f i c e a n d
w a t e r i n it.
T h e m o t i o n s o f the extremity o f the column of mercury
b e i n g proportional to the quantities of heat emitted from
the test-tube i n t o the c a l o r i m e t e r , it is easy to see how
quantities o f heat may be compared. I n fact, B u n s e n has
m a d e s a t i s f a c t o r y d e t e r m i n a t i o n s o f the s p e c i f i c h e a t o f t h o s e
r a r e m e t a l s , such as i n d i u m , o f w h i c h o n l y a f e w g r a m m e s
have been obtained.
To prepare the c a l o r i m e t e r f o r use, i c e m u s t b e f o r m e d
in the c a l o r i m e t e r r o u n d the test-tube. F o r this purpose,
B u n s e n c a u s e s a c u r r e n t o f a l c o h o l , c o o l e d b e l o w o ° C. b y a
f r e e z i n g m i x t u r e , t o flow t o t h e b o t t o m o f t h e t e s t - t u b e a n d
u p a l o n g its s i d e s . I n this w a y t h e g r e a t e r p a r t o f t h e w a t e r
in t h e c a l o r i m e t e r is s o o n f r o z e n . W h e n t h e a p p a r a t u s has
b e e n l e f t f o r a sufficient t i m e in t h e v e s s e l c o n t a i n i n g snow,
t h e t e m p e r a t u r e o f this i c e rises t o o° C , a n d the apparatus
is r e a d y f o r u s e . A great many experiments may b e made
1
after o n e f r e e z i n g o f t h e w a t e r .
1
See Pogg. Ann, Sept. 1870, or Phil. Meg. 1871.

Experiments for the Student. 63
METHOD OF MIXTURE.
The second calorimetric method is u s u a l l y called the

Method o f Mixture. T h i s n a m e is g i v e n t o a l l t h e p r o c e s s e s
in which the quantity o f h e a t w h i c h escapes from one body
is m e a s u r e d b y t h e i n c r e a s e o f t e m p e r a t u r e it p r o d u c e s in
another body into which it escapes. T h e most perfect
m e t h o d o f ensuring that all the heat which escapes from d i e
o n e b o d y p a s s e s i n t o t h e o t h e r is t o m i x t h e m , b u t i n m a n y
cases t o w h i c h t h e m e t h o d is n o w a p p l i e d this cannot be
done.
We shall illustrate this m e t h o d by a few experiments,
which can b e p e r f o r m e d b y the student w i t h o u t a n y special
apparatus. A f e w e x p e r i m e n t s o f this kind actually per
formed b y h i m s e l f will g i v e the student a m o r e intelligent
interest i n t h e s u b j e c t , a n d w i l l g i v e h i m a m o r e l i v e l y faith
in the exactness and uniformity o f nature, a n d in t h e i n a c
curacy and uncertainty o f our observations, than any reading
of b o o k s , or e v e n witnessing elaborate experiments p e r f o r m e d
by professed m e n o f science.
I shall s u p p o s e the student t o h a v e a thermometer, the
bulb o f which he can immerse in the liquids o f which the
temperature is t o be measured, and I shall suppose the
g r a d u a t i o n o f t h e t h e r m o m e t e r t o b e that o f F a h r e n h e i t , as
it is t h e m o s t c o m m o n i n this c o u n t r y .
T o c o m p a r e t h e effects o f h e a t o n w a t e r a n d on l e a d , t a k e
a strip o f s h e e t l e a d , w e i g h i n g , say, o n e p o u n d , a n d r o l l it
i n t o the f o r m o f a l o o s e spiral, s o t h a t w h e n i t is d r o p p e d
i n t o w a t e r t h e w a t e r m a y p l a y r o u n d e v e r y p a r t o f it f r e e l y .
T a k e a v e s s e l o f a c o n v e n i e n t s h a p e , such t h a t t h e r o l l o f
l e a d w h e n p l a c e d in the vessel will b e w e l l c o v e r e d with a
p o u n d o f water.
H a n g u p t h e l e a d b y a fine string a n d d i p it i n a s a u c e p a n
o f b o i l i n g w a t e r , a n d c o n t i n u e t o b o i l it till it is t h o r o u g h l y
heated. W h i l e this is g o i n g o n w e i g h out a p o u n d o f c o l d

6 4
Calorimetry.
water in your vessel, a n d ascertain its temperature with

the thermometer. Then lift the roll o f l e a d out o f the
b o i l i n g water, h o l d it in the steam t i l l t h e w a t e r is drained
off, a n d i m m e r s e i t as q u i c k l y as p o s s i b l e i n t h e c o l d water
i n t h e v e s s e l . B y m e a n s o f t h e s t r i n g y o u m a y stir it a b o u t i n
t h e w a t e r so as t o b r i n g i t i n c o n t a c t w i t h n e w p o r t i o n s o f t h e
w a t e r , a n d t o p r e v e n t it f r o m g i v i n g its h e a t d i r e c t l y t o the
sides o f the vessel.
F r o m t i m e t o t i m e o b s e r v e the temperature o f the water
as i n d i c a t e d b y t h e t h e r m o m e t e r . In a few minutes the
temperature o f t h e w a t e r w i l l c e a s e t o rise, a n d the experi
m e n t m a y then b e s t o p p e d and the calculation begun.
I shall s u p p o s e ( f o r t h e s a k e o f fixing o u r i d e a s ) t h a t the
t e m p e r a t u r e o f t h e w a t e r b e f o r e t h e h o t l e a d w a s p u t in w a s
57° F . , a n d t h a t t h e final t e m p e r a t u r e , w h e n t h e l e a d c e a s e d
to impart h e a t t o the water, w a s 62° F , I f w e t a k e as our
unit o f heat that quantity o f heat w h i c h w o u l d raise a p o u n d
o f w a t e r at 6 o ° F . o n e d e g r e e , w e h a v e h e r e five units o f h e a t
i m p a r t e d t o the w a t e r b y the lead.
S i n c e the l e a d was for s o m e t i m e in b o i l i n g w a t e r , and
w a s a f t e r w a r d s h e l d i n t h e s t e a m , w e m a y a s s u m e its o r i g i n a l
t e m p e r a t u r e t o b e 2 1 2 ° (this, h o w e v e r , s h o u l d b e t e s t e d b y t h e
t h e r m o m e t e r ) . D u r i n g the e x p e r i m e n t the l e a d c o o l e d 150°—
f r o m 212° t o 6 2 ° — a n d g a v e o u t , as w e h a v e s e e n , five u n i t s
o f heat to the water. H e n c e the difference o f the heat o f a
0
p o u n d o f l e a d at 2 1 2 a n d at 6 2 ° is five units ; o r t h e same
q u a n t i t y o f h e a t w h i c h w i l l h e a t a p o u n d o f w a t e r five d e g r e e s
0 0
from 57 to 62 will heat a pound o f lead 150 degrees from
0
62 to 2T2°. I f w e assume, what is n e a r l y though not
e x a c t l y true, that the quantity o f h e a t r e q u i r e d to heat the
l e a d is t h e s a m e for e a c h d e g r e e o f rise o f t e m p e r a t u r e , t h e n
w e might say that t o raise a pound of lead five degrees
requires o n l y o n e thirtieth part o f the heat r e q u i r e d to raise
a p o u n d o f w a t e r five d e g r e e s .
W e h a v e thus m a d e a c o m p a r i s o n o f t h e effects o f h e a t o n
lead and o n water. W e h a v e found that the s a m e quantity

TJiermal Capacity of a Body. 65
of heat w o u l d raise a p o u n d o f lead t h r o u g h thirty times as
m a n y d e g r e e s as it w o u l d r a i s e a p o u n d o f water, a n d we
have inferred that, t o produce any moderate change of
temperature o n a p o u n d o f l e a d requires one-thirtieth o f the
heat r e q u i r e d t o p r o d u c e t h e s a m e c h a n g e o n a n e q u a l w e i g h t
o f water.
This comparison is e x p r e s s e d in scientific language by
saying that t h e c a p a c i t y o f l e a d f o r h e a t is o n e - t h i r t i e t h of
that o f an e q u a l w e i g h t o f w a t e r .
W a t e r is g e n e r a l l y t a k e n as a standard substance with
which other substances are c o m p a r e d , a n d t h e fact w h i c h w e
h a v e stated a b o v e is e x p r e s s e d i n a still m o r e c o n c i s e m a n n e r
b y saying t h a t t h e s p e c i f i c h e a t o f l e a d is
T h e fact t h a t w h e n e q u a l w e i g h t s o f q u i c k s i l v e r a n d w a t e r
are m i x e d t o g e t h e r the r e s u l t i n g t e m p e r a t u r e is n o t t h e m e a n o f
the t e m p e r a t u r e s o f the ingredients was k n o w n to B o e r h a a v e
and Fahrenheit. D r . B l a c k , h o w e v e r , w a s t h e first t o e x p l a i n
this p h e n o m e n o n a n d m a n y o t h e r s b y t h e d o c t r i n e w h i c h h e
established, t h a t t h e e f f e c t o f t h e s a m e q u a n t i t y o f h e a t i n
raising the t e m p e r a t u r e o f t h e b o d y d e p e n d s n o t o n l y o n t h e
amount o f m a t t e r in the b o d y , but o n the k i n d o f m a t t e r o f
w h i c h it is f o r m e d . D r . I r v i n e , B l a c k ' s p u p i l a n d assistant,
g a v e t o this p r o p e r t y o f b o d i e s t h e name o f C a p a c i t y for
Heat. T h e expression Specific H e a t was afterwards intro
d u c e d b y G a d o l i n , o f A b o , in 1784.
I t h i n k w e shall s e c u r e a c c u r a c y , a l o n g w i t h t h e greatest
conformity to established custom, b y defining these terms
thus:
DEFINITION OF T H E C A P A C I T Y OF A BODY.
The capacity of a body for heat is the number of units of

heat required to raise that body one degree of temperature.
We m a y speak o f the capacity for heat of a particular
t h i n g , s u c h as a c o p p e r v e s s e l , i n w h i c h c a s e t h e capacity
depends o n t h e w e i g h t as w e l l as o n the k i n d o f matter,
F

66 Calorimetry.
T h e capacity of a particular thing is often expressed by

stating the quantity of water which has the same capacity.
W e may also speak o f the capacity for heat o f a substance,
such as copper, in which case w e refer to unit o f mass of the
substance.
DEFINITION OF SPECIFIC HEAT.
The Specific Heat of a body is the ratio of the quantity of

heat required to raise that body one degree to the quantity
required to raise an equal weight of water one degree.
T h e specific heat therefore is a ratio of two quantities of
the same kind, and is expressed by the same number, what
ever b e the units employed by the observer, and whatever
themlometric scale he adopts.
I t is very important to bear in mind that these phrases
mean neither more nor less than what is stated in these defi
nitions.
Irvine, wtio contributed greatly to establish the fact that
the quantity of heat which enters or leaves a b o d y depends
on its capacity for heat multiplied b y the number o f degrees
through which its temperature rises or falls, went on to
assume that the whole quantity o f heat in a body is equal to
its capacity multiplied by the total temperature o f the body,
reckoned from a point which he called the absolute zero.
This is equivalent to the assumption that the capacity o f the
body remains the same from the given temperature down
wards to this absolute zero. T h e truth o f such an assump
tion could never be proved b y experiment, and its falsehood
is easily established by showing that the specific heat of
most liquid and solid substances is different at different
temperatures.
T h e results which Irvine, and others long after him,
deduced b y calculations founded on this assumption are not
only o f no value, but are shown to be so by their incon
sistency with each other.
W e shall now return to the consideration of the experiment

Spécifie Heat of a Substance. 67
with the l e a d a n d water, in o r d e r t o s h o w h o w it can be
made m o r e accurate b y attending to all the circumstances o f
the case. I h a v e p u r p o s e l y a v o i d e d d o i n g so at first, as m y
o b j e c t w a s t o illustrate t h e m e a n i n g o f ' S p e c i f i c H e a t . '
In the former description of the experiment it was
assumed, n o t o n l y t h a t a l l t h e h e a t w h i c h e s c a p e s f r o m t h e
lead enters t h e w a t e r i n t h e v e s s e l , b u t that it remains in
the w a t e r till t h e c o n c l u s i o n o f t h e experiment, when the
t e m p e r a t u r e s o f the l e a d a n d w a t e r h a v e b e c o m e e q u a l i s e d .
T h e l a t t e r p a r t o f this a s s u m p t i o n cannot b e quite true,
for the w a t e r m u s t b e c o n t a i n e d i n a v e s s e l o f s o m e kind,
and must c o m m u n i c a t e s o m e o f its h e a t t o this v e s s e l , a n d
also must l o s e h e a t at its u p p e r surface b y e v a p o r a t i o n , & c .
I f w e could form the vessel o f a perfect non-conductor o f
heat, this l o s s o f h e a t f r o m t h e w a t e r w o u l d n o t o c c u r ; but
n o substance o f w h i c h a v e s s e l c a n be formed can be con
sidered e v e n a p p r o x i m a t e l y a n o n - c o n d u c t o r o f h e a t ; a n d i f
w e use a v e s s e l w h i c h is m e r e l y a s l o w c o n d u c t o r o f h e a t , i t is
very difficult, e v e n b y t h e most elaborate calculations, to
determine how much h e a t is t a k e n u p b y t h e v e s s e l i t s e l f
during the e x p e r i m e n t .
A better plan is t o use a v e s s e l w h i c h is a v e r y g o o d
conductor of heat, but o f w h i c h the capacity for h e a t is
small, such as a t h i n c o p p e r o r s i l v e r v e s s e l , a n d t o p r e v e n t
this v e s s e l f r o m p a r t i n g r a p i d l y w i t h its h e a t b y p o l i s h i n g
its o u t e r surface, and not a l l o w i n g it to touch any large
mass o f m e t a l , but r a t h e r g i v i n g it s l e n d e r supports and
p l a c i n g it w i t h i n a m e t a l v e s s e l h a v i n g its inner surface
polished.
I n this w a y w e shall e n s u r e t h a t t h e h e a t shall b e q u i c k l y
distributed b e t w e e n the w a t e r and the vessel, a n d m a y c o n
sider their t e m p e r a t u r e s at a l l t i m e s n e a r l y e q u a l , w h i l e t h e
loss o f h e a t f r o m t h e v e s s e l w i l l t a k e p l a c e s l o w l y a n d at a
rate w h i c h m a y b e c a l c u l a t e d w h e n w e k n o w t h e temperature
o f the v e s s e l a n d o f t h e air o u t s i d e .
F o r this p u r p o s e , i f w e i n t e n d e d t o m a k e a v e r y e l a b o r a t e
f2

68 Calorimetry.
experiment, we should in the first place determine the

capacity for heat of the vessel by a separate experiment, and
then we should put into the vessel about a pound of warm
water and determine its temperature from minute to minute,
while at the same time we observe with another thermometer
the temperature of the air in the room. I n this way we should
obtain a set o f observations from which we might deduce the
rate of cooling for different temperatures, and compute the
rate of cooling when the vessel is one, two, three, & c ,
degrees hotter than the air - and then, knowing the tempe
rature of the vessel at various stages o f the experiment for
finding the specific heat of lead, we should be able to calcu
late the loss o f heat from the vessel due to the cooling during
the continuance o f the experiment.
But a much simpler method of getting rid o f these diffi
culties is by the method of making two experiments—the first
with the lead which w e have described, and the second with
hot water, in which w e endeavour to make the circumstances
which cause the loss o f heat as similar as we can to those in
the case of the lead.
F o r instance, if we suppose that the specific gravity of lead
is about eleven times that o f water, if instead o f a pound of
lead we use one-eleventh of a pound of water, the bulk of the
water will be the same as that of the lead, and the depth of
the water in the vessel* will be equally increased by the lead
and the water.
I f we also suppose that the specific heat of lead is one-
thirtieth o f that of water, then the heat given out by a pound
o f lead in cooling 150° will be equal to the heat given out
by one-eleventh of a pound o f water in cooling 5 5 ° .
H e n c e , if we take one-eleventh of a pound of water at 55
0
above 6 2 ° , that is at n 7 , and pour it into the vessel wirlitf
0
the water as before at 5 7 , we may expect that the level of
the water will rise as much as when the hot lead was put in,
and that the temperature will also rise to about the same
degree. T h e only difference between the experiments, a s

Method of Double Experiments. 69
far as t h e l o s s o f h e a t is c o n c e r n e d , is, t h a t t h e w a r m w a t e r
w i l l raise the temperature of the cold water in a much
shorter t i m e t h a n t h e h o t l e a d d i d , s o t h a t i f w e o b s e r v e t h e
temperature at t h e same t i m e after the mixture in both
cases, t h e l o s s b y c o o l i n g w i l l b e g r e a t e r w i t h t h e w a r m w a t e r
than with the hot lead.
I n this w a y w e m a y g e t rid o f t h e c h i e f p a r t o f t h e diffi-
culty of many experiments o f comparison. Instead of
m a k i n g o n e e x p e r i m e n t , i n w h i c h t h e c o o l i n g o f t h e l e a d is
compared with the heating o f the water and the vessel,
including an u n k n o w n loss o f heat f r o m the outside o f the
vessel, w e make t w o experiments, in which the heating
o f the v e s s e l a n d t h e t o t a l l o s s o f h e a t shall b e as n e a r l y ail
p o s s i b l e t h e s a m e , b u t i n w h i c h t h e h e a t is f u r n i s h e d i n t h e
one case by hot lead, and in t h e other b y w a r m water.
T h e student m a y c o m p a r e this m e t h o d w i t h the m e t h o d of
double w e i g h i n g i n v e n t e d by Père A m i o t , but commonly
k n o w n as Borda's. m e t h o d , in which first the b o d y to be
w e i g h e d , a n d then the weights, are p l a c e d in t h e same scale,
and w e i g h e d against the s a m e counterpoise.
W e shall illustrate this m e t h o d b y f i n d i n g t h e effect o f s t e a m

in h e a t i n g w a t e r , a n d comparing it w i t h that o f hot water.
T a k e a kettle, and m a k e the lid tight w i t h a little flour and
water, a n d a d a p t a short i n d i a - r u b b e r t u b e t o the spout, a n d
a tin o r g l a s s n o z z l e t o t h e t u b e . M a k e the w a t e r in the kettle
boil, and w h e n the steam c o m e s freely through the nozzle
d i p it i n cold water, a n d y o u will satisfy y o u r s e l f t h a t the^
steam is r a p i d l y c o n d e n s e d , every bubble o f steam as it
issues c o l l a p s i n g w i t h a s h a r p r a t t l i n g n o i s e .
H a v i n g m a d e yourself familiar with the general nature o f
ithe experiment of the condensation o f steam, you may
p r o c e e d to measure the heat g i v e n out to the water. For
this p u r p o s e , p u t s o m e c o l d w a t e r in y o u r vessel, say about
three-quarters o f a pound. Weigh the vessel and water
carefully, a n d o b s e r v e t h e temperature o f the water ; then,
w h i l e the s t e a m flows f r e e l y f r o m t h e n o z z l e , c o n d e n s e steam

7° Calorimetry.
in the water for a short t i m e , a n d r e m o v e the n o z z l e ; o b s e r v e

the temperature and weigh the w a t e r in its v e s s e l a g a i n ,
taking note o f the time o f the experiment.
L e t us suppose the original weight . . S,ooo grains

"Weight after the condensation of steam . 5 , 1 0 0 grains
Hence the weight of steam condensed is . 1 0 0 grains
Temperature of water at first . . . 55° F .
Temperature at the end of experiment . 77° F .
Rise of temperature . . . . . 22°
Let us n o w m a k e a second e x p e r i m e n t , as l i k e t h e first

as w e c a n , o n l y d i f f e r i n g f r o m i t b y t h e use of hot water
i n s t e a d o f s t e a m t o p r o d u c e t h e rise o f t e m p e r a t u r e .
I t is i m p o s s i b l e i n p r a c t i c e t o e n s u r e t h a t e v e r y t h i n g shall
be e x a c t l y the same, but after a f e w trials w e m a y s e l e c t a
m e t h o d w h i c h w i l l n e a r l y , i f n o t q u i t e , fulfil t h e c o n d i t i o n s .
T h u s i t is e a s y t o b r i n g t h e v e s s e l a n d c o l d water to the
s a m e w e i g h t as b e f o r e , n a m e l y , 5,000 g r a i n s \ b u t w e shall
suppose the temperature n o w to be 5 6 ° F . i n s t e a d o f 55°.
W e n o w p o u r in w a t e r a t 176° F . g r a d u a l l y , so as t o m a k e this
e x p e r i m e n t last a b o u t as l o n g as t h e first, a n d w e find t h a t
the temperature is n o w 76°, a n d the weight 6,000 g r a i n s .
Hence 1,000 grains o f water c o o l i n g i o o ° raise the vessel
a n d its c o n t e n t s 22°.
A s s u m i n g that the specific heat o f w a t e r is the s a m e at
all temperatures, which is n e a r l y , though by no means
e x a c t l y , true, t h e q u a n t i t y of- h e a t given out b y the water
in the second e x p e r i m e n t is equal to what would raise
100,000 g r a i n s o f w a t e r o n e d e g r e e .
I n the e x p e r i m e n t with the steam the temperatures w e r e
n e a r l y t h o u g h n o t e x a c t l y e q u a l , b u t t h e rise o f temperature
w a s g r e a t e r i n t h e p r o p o r t i o n o f 22 t o 20. Hence we may
c o n c l u d e that t h e quantity of heat which produced this
h e a t i n g effect i n t h e e x p e r i m e n t w i t h s t e a m w a s g r e a t e r t h a n
in t h e e x p e r i m e n t w i t h w a t e r 121 t h e s a m e p r o p o r t i o n . This
m a k e s the heat g i v e n out b y the steam equal to that w h i c h
w o u l d r a i s e r 10,000 g r a i n s o f w a t e r o n e d e g r e e .

Latent Heat of Steam. 71
This was done by the condensation and subsequent
cooling of 1 0 0 grains o f steam. L e t us b e g i n w i t h t h e h e a t
0
g i v e n out b y the 1 0 0 g r a i n s o f w a t e r at 212 F., into which
0
the s t e a m is c o n d e n s e d . I t is c o o l e d f r o m 212 to 7 7 ° or
135°, and gives out therefore an amount o f heat which
w o u l d raise 13,500 grains o f water one degree. But the
w h o l e effect was 110,000, so that there is a n amount of
heat w h i c h w o u l d r a i s e 9 0 , 5 0 0 grains o f water o n e degree,
which must be g i v e n out during the condensation o f the
steam, a n d b e f o r e the cooling begins. Hence each grain
of steam in c o n d e n s i n g g i v e s o u t as m u c h heat as w o u l d
raise 9 6 5 g r a i n s o f w a t e r 1 ° F. or 5 3 6 grains 1 ° Centi
grade.
T h e fact that s t e a m a t t h e b o i l i n g p o i n t g i v e s o u t a l a r g e
q u a n t i t y o f h e a t w h e n i t is c o n d e n s e d i n t o w a t e r w h i c h is
still a t t h e s a m e t e m p e r a t u r e , a n d the c o n v e r s e f a c t t h a t i n
o r d e r t o c o n v e r t w a t e r at t h e b o i l i n g t e m p e r a t u r e i n t o s t e a m
of the same temperature a large quantity o f heat must
be communicated t o it, w a s first clearly established by
Black in 1757.
H e expressed it b y saying that the latent heat o f steam
0
is 9 6 5 F., and this form o f e x p r e s s i o n is still in use, and
w e should take it t o m e a n neither m o r e n o r less than w h a t
we h a v e just stated.
B l a c k , h o w e v e r , a n d m a n y o f his f o l l o w e r s , s u p p o s e d heat
to b e a substance w h i c h w h e n it m a k e s a thing hot is
sensible, but w h i c h w h e n i t is n o t p e r c e i v e d b y t h e hand
or t h e t h e r m o m e t e r still e x i s t s i n t h e b o d y i n a l a t e n t o r
c o n c e a l e d state. B l a c k s u p p o s e d that t h e d i f f e r e n c e b e t w e e n
b o i l i n g w a t e r a n d s t e a m is, t h a t s t e a m contains a great deal
m o r e c a l o r i c t h a n t h e h o t w a t e r , s o t h a t it m a y be con
sidered a c o m p o u n d o f water and c a l o r i c ; but, s i n c e this
additional caloric produces no effect on the temperature,
b u t l u r k s c o n c e a l e d i n t h e s t e a m r e a d y t o a p p e a r w h e n i t is
c o n d e n s e d , he c a l l e d this part o f the heat latent heat.
I n c o n s i d e r i n g the scientific v a l u e o f Black's d i s c o v e r y o f

72 Calorimetry.
latent heat, and o f his m o d e o f expressing it, w e should

r e c o l l e c t t h a t B l a c k h i m s e l f i n 1754 w a s t h e d i s c o v e r e r o f t h e
f a c t t h a t t h e b u b b l e s f o r m e d w h e n m a r b l e is p u t i n t o a n a c i d
c o n s i s t o f a r e a l s u b s t a n c e d i f f e r e n t f r o m air, w h i c h , w h e n free,
is s i m i l a r t o air i n a p p e a r a n c e , b u t w h e n f i x e d m a y e x i s t in
liquids and in solids. T h i s substance, w h i c h w e n o w call
carbonic acid, Black called fixed air, a n d this w a s t h e first
g a s e o u s b o d y d i s t i n c t l y r e c o g n i s e d as such. O t h e r airs o r
gases w e r e afterwards d i s c o v e r e d , a n d the impulse g i v e n to
chemistry was so great, on account o f the extension o f the
science to these attenuated bodies, that m o s t philosophers
o f t h e t i m e w e r e o f o p i n i o n that h e a t , l i g h t , e l e c t r i c i t y , and
m a g n e t i s m , i f n o t t h e v i t a l f o r c e itself, w o u l d s o o n e r o r l a t e r
be added t o t h e list. O b s e r v i n g , h o w e v e r , that the gases
c o u l d b e w e i g h e d , w h i l e the presence o f these other agents
c o u l d n o t b e d e t e c t e d b y the balance, those w h o admitted
them to the rank o f substances called t h e m i m p o n d e r a b l e
substances, and sometimes, on account o f their mobility,
imponderable fluids.
T h e a n a l o g y b e t w e e n the free and fixed states o f c a r b o n i c

acid and the sensible and latent states o f h e a t encouraged
t h e g r o w t h o f m a t e r i a l i s t i c p h r a s e s as a p p l i e d t o h e a t ; and
it is e v i d e n t t h a t t h e s a m e w a y o f t h i n k i n g l e d e l e c t r i c i a n s t o
the notion o f disguised or dissimulated electricity, a notion
w h i c h s u r v i v e s e v e n y e t , a n d w h i c h is n o t s o e a s i l y s t r i p p e d
o f its e r r o n e o u s c o n n o t a t i o n as t h e p h r a s e ' l a t e n t h e a t . '
I t is w o r t h y o f r e m a r k t h a t C a v e n d i s h , t h o u g h o n e o f t h e
g r e a t e s t c h e m i c a l d i s c o v e r e r s o f his t i m e , w o u l d n o t accept
the phrase ' latent heat.' He prefers to speak of the
generation of heat when steam is c o n d e n s e d , a phrase
inconsistent with the notion that heat is matter, and
objects to Black's term as relating ' to an hypothesis
depending on the supposition that the heat o f b o d i e s is
owing t o their containing more or less of a substance
c a l l e d t h e m a t t e r o f h e a t ; a n d , as I t h i n k S i r I s a a c N e w t o n ' s
opinion that heat consists in the internal motion of the

Latent Heat. 73
particles of bodies much the most probable, I chose to use

1
the expression, "heat is generated." '
W e shall not now be in danger of any error if w e use
latent heat as an expression meaning neither more nor less
than this :
DEFINITION.—Latent heat is the quantity of heat which
must be communicated to a body in a given state in order
to convert it into another state without changing its tempera
ture.
W e here recognise the fact that heat when applied to a
body may act in two ways—by changing its state, or by
raising its temperature—and that in certain cases it may act
by changing the state without increasing the temperature.
T h e most important cases in which heat is thus employed
are—
1. T h e conversion of solids into liquids. This is called
melting or fusion. I n the reverse process o f freezing or
solidification heat must be allowed to escape from the body
to an equal amount.
2 . T h e conversion of liquids (or solids) into the gaseous
state. This is called evaporation, and its reverse condensa
tion.
3. When a gas expands, in order to maintain the tem
perature constant, heat must be communicated to it, and
this, when properly defined, may b e called the latent heat o f
expansion.
4. There are many chemical changes during which heat is
generated or disappears.
In all these cases the quantity of heat which enters or
leaves the body may be measured, and in order to express
the result of this measurement in a convenient form, we
may call it the latent heat required for a given change in the
substance.
W e must carefully remember that all that we know about
"heat is what occurs when it passes from one body to another,
1
Phil. Trans. 1783, quoted by Forbes. Dissertation V I . Encyc. Bt\t.

74 Elementary Dynamical Principles.
and t h a t w e m u s t n o t a s s u m e t h a t after h e a t has entered

a substance it exists in the form of heat within that
substance. That we have no right to make such an
assumption will b e a b u n d a n t l y s h o w n b y the demonstration
that heat m a y b e transformed into and may be produced
f r o m s o m e t h i n g w h i c h is n o t h e a t .
Regnault's method of passing large quantities o f the
substance through the calorimeter will be described in
treating o f the properties o f gases, a n d the Method ol
C o o l i n g will b e c o n s i d e r e d in the chapter o n R a d i a t i o n .
CHAPTER IV.
ELEMENTARY DYNAMICAL PRINCIPLES.
I N t h e first p a r t o f this t r e a t i s e w e h a v e c o n f i n e d o u r s e l v e s
t o the explanation o f the m e t h o d o f ascertaining the tem
perature o f b o d i e s , w h i c h w e call t h e r m o m e t r y , and the
m e t h o d of measuring the quantity o f heat w h i c h enters or
l e a v e s a b o d y , a n d this w e c a l l c a l o r i m e t r y . B o t h o f these
a r e r e q u i r e d i n o r d e r t o s t u d y t h e effects o f h e a t u p o n b o d i e s ;
b u t w e c a n n o t c o m p l e t e this s t u d y w i t h o u t m a k i n g m e a s u r e
ments of a mechanical kind, because heat and mechanical
force may act on the same body, and the actual result
d e p e n d s on both actions. I propose, therefore, to recall to
the student's m e m o r y s o m e o f those d y n a m i c a l principles
which he ought t o bring with h i m to the study o f heat, and
which are necessary w h e n h e passes from purely thermal
p h e n o m e n a , such as w e h a v e c o n s i d e r e d , t o p h e n o m e n a i n
v o l v i n g pressure, expansion, & c , a n d w h i c h w i l l e n a b l e h i m
afterwards to proceed to the study of thermodynamics
p r o p e r , in w h i c h the relations o f thermal p h e n o m e n a among
t h e m s e l v e s are d e d u c e d f r o m p u r e l y d y n a m i c a l p r i n c i p l e s .
The most important slep in the progress of every

Measurement of Quantities. 75
science is the measurement of quantities. T h o s e whose
curiosity is satisfied with observing what happens have
occasionally done service b y directing the attention of others
to the phenomena they have seen ; but it is to those who
endeavour to find out how much there is of anything that
we owe all the great advances in our knowledge.
Thus every science has some instrument o f precision,
which may be taken as a material type of that science which
it has advanced, by enabling observers to express their
results as measured quantities. I n astronomy we have
the divided circle, in chemistry the balance, in heat the
thermometer, while the whole system of civilised life may
be fitly symbolised by a foot rule, a set o f weights, and a
clock. I shall, therefore, make a few remarks on the
measurement of quantities.
Every quantity is expressed by a phrase consisting o f two
components, one of these being the name of a number, and
the other the name of a thing of the same kind as the
quantity to be expressed, but of a certain magnitude agreed
on among men as a standard or unit
Thus we speak of two days, of forty-eight hours.
Each of these expressions has a numerical part and a
denominational part, the numerical part being a number,
whole or fractional, and the denominational part being the
name of the thing, which is to be taken as many times as is
indicated by the number.
I f the numerical part is the number one, then the quantity
is the standard quantity itself, as when we say one pound,
or one inch, or one day. A quantity of which the numerical
part is unity is called a unit. W h e n the numerical part is
some other number, the quantity is still said to be referred to,
or to be expressed in terms of that quantity which would be
denoted if the number were one, and which is called the unit
I n all cases the unit is a quantity of the same kind as the
quantity which is expressed by means of it.
I n many cases several units of the same kind are in use,

as m i l e s , y a r d s , f e e t , a n d i n c h e s , as m e a s u r e s o f l e n g t h ; c u b i c
yards, gallons, and fluid o u n c e s , as m e a s u r e s of capacity;
b e s i d e s t h e endless v a r i e t y o f units w h i c h h a v e b e e n a d o p t e d
b y different nations, a n d b y different districts a n d different
t r a d e s in the s a m e n a t i o n .
W h e n a quantity g i v e n in t e r m s o f o n e unit has to b e ex
pressed in terms o f another, w e find the number o f times
t h e s e c o n d u n i t is c o n t a i n e d in the first, and m u l t i p l y this
b y the given number.
H e n c e the numerical part o f the expression o f the same
q u a n t i t y v a r i e s i n v e r s e l y as t h e u n i t i n w h i c h it is t o b e e x
p r e s s e d , as i n t h e e x a m p l e , t w o d a y s a n d forty-eight hours,
w h i c h m e a n the same thing.
T h e r e are m a n y quantities w h i c h can b e d e f i n e d in terms
of standard quantities o f a different k i n d . I n this c a s e w e
make use o f d e r i v e d units. F o r instance, as s o o n as we
have fixed on a measure o f length, w e m a y define by means
o f it n o t o n l y a l l l e n g t h s , b u t a l s o t h e a r e a o f a n y surface,
and the content o f any space. F o r this p u r p o s e , i f t h e f o o t
is t h e u n i t o f l e n g t h , w e c o n s t r u c t , b y E u c l i d I . 4G, a s q u a r e
w h o s e s i d e is a f o o t , a n d express all areas in t e r m s o f this
square foot, and by constructing a cube whose e d g e is
a f o o t w e h a v e d e f i n e d a c u b i c f o o t as a unit o f capacity.
W e a l s o e x p r e s s v e l o c i t i e s i n m i l e s a n h o u r , or f e e t i n a
second, & c .
I n fact, a l l q u a n t i t i e s w i t h w h i c h w e h a v e t o d o in d y n a m i c s
m a y b e e x p r e s s e d i n terms o f units d e r i v e d b y definition from
the three fundamental u n i t s — o f L e n g t h , M a s s , and Time.
STANDARD OF LENGTH.
I t is s o i m p o r t a n t t o m a n k i n d that these units should be

w e l l d e f i n e d that i n all c i v i l i s e d nations t h e y are defined by
the State with r e f e r e n c e to material standards, w h i c h are pre
served with the utmost care. F o r i n s t a n c e , i n this c o u n t r y
1
it was enacted'by Parliament 'that the straight line or
' 18 & 19 Vict. c. 72, July 30, 1855.

Units of Length. 77
distance between the centres o f the transverse lines in the

two gold plugs in the bronze bar deposited in the office
of the Exchequer shall be the genuine standard yard
0
at 6 2 F., and if lost it shall be replaced by means of its
copies.'
T h e authorised copies here referred to are those which are
preserved at the R o y a l M i n t , the R o y a l Society o f London,
the Royal Observatory at Greenwich, and the N e w Palace
at Westminster. Other copies have been made with great
care, and with these all measures of length must be com-
pared.
T h e length o f the Parliamentary standard was chosen so
as to be as nearly as possible equal to that of the best
standard yards formerly used in England. T h e State, there-
fore, endeavoured to maintain the standard o f its ancient
magnitude, and by its authority it has defined the actual
magnitude o f this standard with all the precision of which
modern science is capable.
T h e mètre derives its authority as a standard from a law
of the French Republic i » 1795.
I t is defined to be the distance between the ends of a rod
1
of platinum made b y Borda, the rod being at the tempera-
ture of melting ice. This distance was chosen without
reference to any former measures used in France. I t was
intended to be a universal and not a national measure, and
was derived from Delambre and Mechain's measurement o f
the size o f the earth. T h e distance measured along the
earth's surface from the pole to the equator is nearly ten
million of mètres. If, however, in the progress of geodesy, a
different result should be obtained from that of Delambre,
the mètre will not be altered, but the new result will be
expressed in the old mètres. T h e authorised standard of
length is therefore not the terrestrial globe, but Borda's
1
Mètre conforme à la. loi du 18 Germinal, an I I I . Présenté le
4 Messidor, a n V I I .

p l a t i n u m r o d , w h i c h is m u c h m o r e likely to b e accurately
measured.
The value of the French system o f measures does not
d e p e n d so m u c h o n t h e a b s o l u t e v a l u e s o f t h e u n i t s a d o p t e d
as on the fact that all t h e units of the same kind are
connected together b y a decimal system o f multiplication
a n d division, so that the w h o l e system, u n d e r the n a m e of
the metrical system, is r a p i d l y gaining ground even in
countries w h e r e the old national system has b e e n carefully
defined.
The m è t r e is 3 9 " 3 7 o 4 3 B r i t i s h i n c h e s .
STANDARD OF MASS.
B y the A c t a b o v e cited a weight o f platinum marked

' P . S. 1844, 1 l b . , ' d e p o s i t e d in t h e office o f t h e E x c h e q u e r ,
' shall b e t h e l e g a l a n d g e n u i n e s t a n d a r d m e a s u r e o f w e i g h t ,
and shall b e a n d be denominated the Imperial Standard
P o u n d Avoirdupois, and shall b e d e e m e d to b e the o n l y
standard measure o f w e i g h t from w h i c h all other weights and
o t h e r m e a s u r e s h a v i n g r e f e r e n c e t o w e i g h t shall b e d e r i v e d ,
computed, and ascertained, and o n e equal seven-thousandth
part o f such p o u n d a v o i r d u p o i s shall b e a g r a i n , a n d five
t h o u s a n d s e v e n h u n d r e d a n d sixty such grains shall b e and
be d e e m e d to b e a p o u n d troy. I f at a n y t i m e h e r e a f t e r the
said I m p e r i a l S t a n d a r d P o u n d A v o i r d u p o i s b e lost o r in a n y
manner destroyed, defaced, or otherwise injured, the Com-
missioners o f H e r Majesty's T r e a s u r y m a y cause t h e same to
b e restored b y reference to or adoption o f any o f the copies
1
aforesaid, o r s u c h o f t h e m as m a y r e m a i n a v a i l a b l e f o r t h a t
purpose.'
The construction o f this standard w a s entrusted to P r o -
fessor W . H. Miller, w h o has given an account of the
2
m e t h o d s e m p l o y e d in a paper, which m a y b e here referred
t o as a m o d e l o f s c i e n t i f i c a c c u r a c y .
1
In the same places as the Standards of Length.
* Phil Trans. 1856, p . 753.

Units of Mass.
79
The French standard o f mass is t h e Kilogramme des
Archives, made o f platinum b y B o r d a , a n d is i n t e n d e d to
represent the mass o f a cubic d é c i m è t r e o f distilled water
at the t e m p e r a t u r e 4° C .
The actual d e t e r m i n a t i o n o f t h e d e n s i t y o f w a t e r is an
operation which requires great care, and the differences
b e t w e e n t h e results o b t a i n e d b y t h e m o s t skilful o b s e r v e r s ,
t h o u g h s m a l l , a r e a t h o u s a n d t i m e s g r e a t e r t h a n the differ-
ences o f t h e results o f a c o m p a r i s o n o f s t a n d a r d s b y w e i g h i n g
them. T h e differences o f the values o f the density of water
as f o u n d b y careful o b s e r v e r s are as m u c h as a thousandth
part o f t h e w h o l e , w h e r e a s t h e m e t h o d of weighing admits
o f an a c c u r a c y o f w i t h i n o n e p a r t i n five m i l l i o n s .
Hence the French standards, though originally formed
to represent certain natural quantities, must b e n o w c o n -
s i d e r e d as arbitrary standards, o f w h i c h c o p i e s are to be
taken b y d i r e c t c o m p a r i s o n . T h e French or metric system
has t h e a d v a n t a g e o f a u n i f o r m a p p l i c a t i o n o f t h e decimal
m e t h o d , a n d i t is a l s o in m a n y c a s e s c o n v e n i e n t t o r e m e m b e r
that a c u b i c m e t r e o f w a t e r is a t o n n e , a c u b i c d é c i m è t r e a
kilogramme, a cubic centimètre a gramme, and a cubic
m i l l i m è t r e a m i l l i g r a m m e , t h e w a t e r b e i n g at its m a x i m u m
d e n s i t y o r at a b o u t 4 ° C .
In 1826 the British standard o f mass was defined by
0
saying that a cubic inch o f water at 6 2 F . c o n t a i n s 252'458
grains, a n d t h o u g h this is n o l o n g e r a l e g a l d e f i n i t i o n , w e
m a y t a k e it as a r o u g h s t a t e m e n t o f a fact, t h a t a c u b i c i n c h
o f w a t e r w e i g h s about 252'$ g r a i n s , a c u b i c f o o t about 1,000
o u n c e s a v o i r d u p o i s , a n d a c u b i c y a r d about three-quarters o f
a ton. O f these estimates t h e s e c o n d is t h e furthest from
the truth.
Professor M i l l e r has c o m p a r e d t h e British and French
standards, a n d finds the K i l o g r a m m e des A r c h i v e s equal to
IS432-34874 g r a i n s .
F r o m t h e s e l e g a l d e f i n i t i o n s it w i l l b e s e e n t h a t w h a t is
g e n e r a l l y c a l l e d a s t a n d a r d of w e i g h t is a c e r t a i n p i e c e of

8o Elementary Dynamical Principles.
platinum—that is, a p a r t i c u l a r b o d y t h e q u a n t i t y o f m a t t e r i n
w h i c h is t a k e n a n d d e f i n e d b y t h e S t a t e t o b e a p o u n d o r a
kilogramme.
The w e i g h t s t r i c t l y s o c a l l e d — t h a t is, t h e t e n d e n c y o f t h i s
b o d y to m o v e d o w n w a r d s — i s not invariable, for it depends
on t h e p a r t o f t h e w o r l d w h e r e it is p l a c e d , its w e i g h t b e i n g
g r e a t e r at t h e p o l e s t h a n at t h e e q u a t o r , a n d g r e a t e r at the
l e v e l o f t h e s e a than at t h e t o p o f a m o u n t a i n .
W h a t is r e a l l y i n v a r i a b l e is t h e quantity o f matter in the
b o d y , o r w h a t is c a l l e d i n s c i e n t i f i c l a n g u a g e t h e m a s s o f t h e
b o d y , a n d e v e n i n c o m m e r c i a l t r a n s a c t i o n s w h a t is g e n e r a l l y
a i m e d at in w e i g h i n g g o o d s is t o estimate the quantity o f
matter, and not to determine the force with which they tend
downwards.
In fact, t h e o n l y o c c a s i o n s i n c o m m o n life i n w h i c h it is
r e q u i r e d t o e s t i m a t e w e i g h t c o n s i d e r e d as a f o r c e is w h e n w e
have to determine the strength r e q u i r e d t o lift or carry
things, o r when w e h a v e to m a k e a structure s t r o n g enough
to s u p p o r t their w e i g h t . I n all o t h e r cases the w o r d w e i g h t
must b e understood the quantity of the thing as
to mean
determined by the process of weighing against ' standard
wnghts.'
As a g r e a t d e a l o f c o n f u s i o n p r e v a i l s o n this s u b j e c t in
ordinary language, and still greater confusion has been
introduced into b o o k s o n mechanics b y the n o t i o n that a
p o u n d is a c e r t a i n f o r c e , i n s t e a d o f b e i n g , as w e h a v e s e e n , a
certain p i e c e o f platinum, or a p i e c e o f a n y other k i n d o f
matter equal in mass to the p i e c e o f platinum, I have
thought it worth while to spend some t i m e in defining
a c c u r a t e l y w h a t is m e a n t b y a p o u n d a n d a k i l o g r a m m e .
O N T H E UNIT O F TIME.
All nations derive their measures of time from the
apparent motions o f the h e a v e n l y b o d i e s . T h e motion of
rotation of the earth about its a x i s is v e r y n e a r l y i n d e e d
u n i f o r m , a n d t h e m e a s u r e o f t i m e i n w h i c h o n e d a y is e q u a l

Unit of Time. 81
t o t h e t i m e o f r e v o l u t i o n o f t h e e a r t h a b o u t its a x i s , o r m o r e
e x a c t l y t o t h e i n t e r v a l b e t w e e n s u c c e s s i v e t r a n s i t s o f t h e first
p o i n t o f A r i e s , is u s e d b y a s t r o n o m e r s under the name o f
sidereal t i m e .
S o l a r t i m e is that w h i c h is g i v e n b y a s u n - d i a l , a n d is
not uniform. A uniform measure of time, agreeing with
solar t i m e i n t h e l o n g run, is c a l l e d m e a n solar time, a n d is
that w h i c h is g i v e n b y a c o r r e c t c l o c k . A s o l a r d a y is l o n g e r
than a s i d e r e a l d a y . In all physical researches m e a n solar
t i m e is e m p l o y e d , a n d o n e s e c o n d is g e n e r a l l y t a k e n as the
unit o f t i m e .
T h e evidence- upon which w e form the conclusion that
t w o different p o r t i o n s o f t i m e a r e o r a r e n o t e q u a l c a n o n l y
be appreciated b y those w h o have mastered the principles
of dynamical reasoning. I can o n l y h e r e assert that the
c o m p a r i s o n , f o r e x a m p l e , o f t h e l e n g t h o f a d a y at present
with the l e n g t h o f a d a y 3,000 y e a r s a g o is b y n o means
an unfruitful enquiry, a n d that the r e l a t i v e length o f these
days m a y be determined to within a small fraction of a
second. This shows that time, though we c o n c e i v e it
m e r e l y as t h e s u c c e s s i o n o f o u r s t a t e s o f c o n s c i o u s n e s s , is
capable o f measurement, independently, not only of our
merjtal states, b u t o f a n y p a r t i c u l a r p h e n o m e n o n w h a t e v e r .
ON MEASUREMENTS FOUNDED ON THE THREE

FUNDAMENTAL UNITS.
I n the m e a s u r e m e n t o f quantities differing in k i n d from

the t h r e e u n i t s , w e m a y e i t h e r a d o p t a n e w u n i t i n d e p e n d e n t l y
for e a c h n e w q u a n t i t y , o r w e m a y e n d e a v o u r t o d e f i n e a u n i t
o f t h e p r o p e r k i n d f r o m t h e f u n d a m e n t a l units. I n t h e latter
c a s e w e a r e s a i d t o u s e a s y s t e m o f units. F o r instance, if
w e h a v e a d o p t e d t h e f o o t as a u n i t o f l e n g t h , t h e s y s t e m a t i c
unit o f c a p a c i t y is t h e c u b i c f o o t .
T h e g a l l o n , w h i c h is a l e g a l m e a s u r e i n t h i s c o u n t r y , is
unsystematic c o n s i d e r e d as a measure o f c a p a c i t y , as it
a
c o n t a i n s t h e a w k w a r d n u m b e r o f 277^274 c u b i c i n c h e s . The
g a l l o n , h o w e v e r , is n e v e r t e s t e d b y a d i r e c t m e a s u r e m e n t o f
its c u b i c c o n t e n t s , b u t b y t h e c o n d i t i o n t h a t i t m u s t c o n t a i n
t e n p o u n d s o f w a t e r at 62° F .
D E F I N I T I O N O F D E N S I T Y . — The density of a body is
measured by the number of units of mass in unit of volume
of the substance.
For instance, i f the foot and the p o u n d be taken as
fundamental units, then the density o f anything is the
number of pounds in a cubic foot. T h e density o f water
is a b o u t 62'5 pounds to the cubic foot. I n the metric
s y s t e m , t h e d e n s i t y o f w a t e r is o n e t o n n e t o t h e s t è r e , o n e
k i l o g r a m m e t o the litre, o n e g r a m m e t o the cubic centi-
mètre, and o n e m i l l i g r a m m e to the cubic millimètre.
We shall sometimes have to use the word rarity, to
s i g n i f y t h e i n v e r s e o f d e n s i t y , t h a t is, t h e v o l u m e o f u n i t o f
mass o f a substance.
D E F I N I T I O N O F SPECIFIC GRAVITY.—The specific gravity
of a body is the ratio of its density to that of some standard
substance, generally ivater.
Since the specific gravity o f a b o d y is t h e r a t i o o f t w o
t h i n g s o f t h e s a m e k i n d , it is a n u m e r i c a l q u a n t i t y , a n d h a s
the s a m e value, w h a t e v e r n a t i o n a l units are employed by
t h o s e w h o d e t e r m i n e it. T h u s , i f w e say that the specific
gravity o f m e r c u r y is about I 3 ' 5 , w e state t h a t m e r c u r y
is a b o u t t h i r t e e n a n d a h a l f t i m e s h e a v i e r than a n e q u a l b u l k
o f water, and this f a c t is i n d e p e n d e n t o f t h e w a y i n w h i c h
w e measure either the mass or the v o l u m e o f the liquids.
D E F I N I T I O N O F U N I F O R M VFXOCITY.-—The vehcity of a
body moving uniformly is measured by the number of units of
length travelled over in unit of time.
T h u s w e speak o f a v e l o c i t y o f so m a n y feet or mètres
per second.
D E F I N I T I O N O F M O M E N T U M . — T h e momentum of a body is
measured by the product of the velocity of the body into the
number of units of mass in the body

Measureme7tt of Force, 83
D E F I N I T I O N O F FORCE.—Farce is -whatever changes or
tends to change the motion of a body by altering either its dire
tion or its magnitude ; and a force acting on a body is measure
by the momentum it produces in its own direction in unit
of time.
T h e unit o f f o r c e is t h a t f o r c e w h i c h i f it a c t e d o n u n i t o f
mass for unit o f t i m e w o u l d p r o d u c e in it u n i t o f v e l o c i t y .
F o r t h e B r i t i s h u n i t o f f o r c e t h e n a m e o f P o u n d a l has b e e n
proposed b y Prof. James T h o m s o n . I t is t h a t f o r c e w h i c h ,
if it a c t e d f o r a s e c o n d o n a p o u n d , w o u l d p r o d u c e i n it a
velocity of one foot per second.
I n the centimetre-gramme-second system, a d o p t e d b y the
C o m m i t t e e o n U n i t s o f t h e B r i t i s h A s s o c i a t i o n , t h e unit o f
force is the Dyne. A dyne acting for one second on a
g r a m m e w o u l d g i v e it a velocity of one centimetre per
second.
T h e w e i g h t o f any b o d y at L o n d o n , acting on that b o d y
for a s e c o n d , w o u l d p r o d u c e i n it a v e l o c i t y o f 32-1889 feet
per second. H e n c e the weight o f a pound at L o n d o n is
32-1889 p o u n d a l s .
A t P a r i s t h e v e l o c i t y o f a b o d y after falling f r e e l y for- o n e
s e c o n d is 980-868 c e n t i m e s p e r s e c o n d . H e n c e the weight
o f a g r a m m e at P a r i s is 980-868 d y n e s .
I t is so c o n v e n i e n t , e s p e c i a l l y w h e n all o u r experiments
are c o n d u c t e d i n t h e s a m e p l a c e , t o e x p r e s s f o r c e s i n t e r m s
o f the w e i g h t o f a p o u n d o r a g r a m m e , that i n a l l c o u n t r i e s
the first m e a s u r e m e n t s o f f o r c e s w e r e m a d e in this w a y , a n d
a f o r c e w a s d e s c r i b e d as a f o r c e o f so m a n y p o u n d s w e i g h t
or g r a m m e s w e i g h t . I t w a s o n l y after t h e m e a s u r e m e n t s o f
forces m a d e b y p e r s o n s i n d i f f e r e n t parts o f t h e w o r l d had
to b e c o m p a r e d t h a t it w a s f o u n d that the weight of a
pound or a gramme is different in different places, and
depends o n the intensity o f gravitation, or the attraction of
the earth ; so that for purposes o f accurate c o m p a r i s o n all
forces m u s t b e r e d u c e d t o a b s o l u t e or d y n a m i c a l measure
as e x p l a i n e d a b o v e . W e shall d i s t i n g u i s h the measure b y
G 2

^4 Elementary Dynamical Principles.
c o m p a r i s o n w i t h w e i g h t as the- gravitation measure of force.

T o r e d u c e f o r c e s e x p r e s s e d in g r a v i t a t i o n m e a s u r e to abso-
lute m e a s u r e , w e must multiply the number denoting the
force in gravitation measure b y the value of the intensity o f
g r a v i t y e x p r e s s e d i n the same metrical system. T h e value
o f t h e i n t e n s i t y o f g r a v i t y is a v e r y i m p o r t a n t n u m b e r i n all
scientific calculations, a n d it is g e n e r a l l y d e n o t e d by the
letter g. The number g m a y b e defined in any of the
f o l l o w i n g ways, which are a l l equivalent :
g is a number expressing the velocity produced in a falling
body in unit of time.
g is a number expressing twice the distance through which
body falls in unit of time.
g is a number expressing the weight of unit of mass in
absolute measure.
The v a l u e o f g is g e n e r a l l y d e t e r m i n e d a t a n y p l a c e by
experiments with the pendulum. T h e s e experiments re-
quire great care, and the description of them does not
belong to our present subject. T h e value o f g may be
f o u n d w i t h sufficient a c c u r a c y for t h e p r e s e n t state o f s c i e n c e
b y means o f t h e formula,
- 1 —
g= G ( i — 0 0025&59 COS 2 X ) j ~ f ~) ~ }
I n this f o r m u l a , G is t h e i n t e n s i t y o f g r a v i t y a the m e a n
l e v e l o f the sea i n l a t i t u d e 4 5 ° :
0 = 3 2 - 1 7 5 3 p o u n d a l s t o t h e p o u n d , o r 9-80533 d y n e s t o t h e
gramme.
X is t h e l a t i t u d e o f t h e p l a c e . T h e f o r m u l a s h o w s that t h e
f o r c e o f g r a v i t y at t h e l e v e l o f t h e sea i n c r e a s e s from the
equator to the poles. T h e last f a c t o r o f t h e f o r m u l a ex-
1
presses, according to the calculations of Poisson, the
effect o f the height o f the place of observation above
the level o f t h e sea in d i m i n i s h i n g the force o f gravity.
The symbol p represents the m e a n density o f the whole
£ a r t h , w h i c h i s p r o b a b l y a b o u t $^ t i m e s t h a t o f w a t e r , p'
1
Traité de Mécanique, t. ii. p. 629.

Weight.
represents t h e m e a n d e n s i t y o f t h e g r o u n d justs b e l o w t h e
place of observation, which may be taken at a b o u t I\.
t i m e s t h e d e n s i t y o f w a t e r , s o that w e m a y w r i t e -
2 — ~2
P— = i"32 nearly.
z is the h e i g h t o f t h e p l a c e a b o v e t h e l e v e l o f t h e sea, in
feet or m e t r e s , a n d r is t h e radius o f t h e e a r t h :
r = 20,886,852 f e e t , o r 6,366,198 m e t r e s .
F o r rough purposes i t is sufficient t o r e m e m b e r t h a t in

Britain the i n t e n s i t y o f g r a v i t y is a b o u t 32-2 p o u n d a l s t o t h e
p o u n d , a n d i n F r a n c e a b o u t 980 d y n e s t o t h e g r a m m e .
T h e reason w h y , in all accurate measurements, w e h a v e
to take account o f the variation o f the intensity o f g r a v i t y in
different p l a c e s is, t h a t t h e a b s o l u t e v a l u e o f a n y f o r c e , such
as the p r e s s u r e o f air o f a given density and temperature,
depends entirely on the properties of air, and not on
the force of g r a v i t y at the place of observation. If,
therefore, this pressure has been o b s e r v e d in g r a v i t a t i o n
m e a s u r e , t h a t is, i n p o u n d s o n t h e s q u a r e i n c h , or i n i n c h e s
o f mercury, or in any w a y in w h i c h the w e i g h t o f s o m e
substance is m a d e t o furnish t h e m e a s u r e o f the p r e s s u r e ) t h e n
the results so o b t a i n e d will b e t r u e o n l y as l o n g as the
intensity o f g r a v i t y is t h e s a m e , a n d w i l l n o t b e true w i t h o u t
c o r r e c t i o n at a p l a c e i n a d i f f e r e n t l a t i t u d e f r o m t h e p l a c e o f
observation. H e n c e t h e use o f r e d u c i n g all measures o f
force t o a b s o l u t e m e a s u r e .
In a rude age, before the invention of means for
overcoming friction, the w e i g h t o f b o d i e s f o r m e d the chief
obstacle to setting them in motion. It was only after
some progress had been made in the art of throwing
missiles, and in the use o f wheel-carriages and floating
vessels, that men's minds became practically impressed
with the idea o f mass as d i s t i n g u i s h e d f r o m weight. Ac
cordingly, while almost all the metaphysicians who dis
cussed t h e q u a l i t i e s o f m a t t e r a s s i g n e d a p r o m i n e n t p l a c e tr>

weight among the primary qualities, few or none of them

perceived that tire sole unalterable property of matter is its
mass. A t the revival of science this property was expressed
by the phrase ' the inertia of matter;' but while the men o f
science understood by this term the tendency of the body
to persevere in its state o f motion (or rest), and considered
it a measurable quantity, those philosophers who were un
acquainted with science understood inertia in its literal
sense as a quality—mere want o f activity or laziness.
Even to this day those who are not practically familiar
with the free motion of large masses, though they all admit
the truth of dynamical principles, yet feel little repugnance
in accepting the theory known as Boscovich's—that sub
stances are composed of a system o f points, which are
mere centres of force, attracting or repelling each other. I t
is probable that many qualities of bodies might be explained
on this supposition, but no arrangement of centres of force,
however complicated, could account for the fact that a body
requires a certain force to produce in it a certain change
of motion, which fact we express b y saying that the body
has a certain measurable mass. N o part of this mass can
be due to the existence of the supposed centres of force.
I therefore recommend to the student that he should
impress his mind with the idea of mass by a few experiments,
such as setting in motion a grindstone or a well-balanced
wheel, and then endeavouring to stop it, twirling a long
pole, & c , till he comes to associate a set of acts and sensa
tions with the scientific doctrines o f dynamics, and he will
never afterwards be in any danger o f loose ideas on these
subjects. H e should also read Faraday's essay on Mental
1
Inertia, which will impress him with the proper meta
phorical use of the phrase to express, not laziness, but
habitude.
1
Life, by Dr. Bence Jones, voL i. p. 2 6 8 .

Work.
ON WORK A N D ENERGY.
W o r k is d o n e w h e n r e s i s t a n c e is o v e r c o m e , a n d t h e q u a n t i t y
o f w o r k d o n e is m e a s u r e d b y the product o f the resisting
force a n d the distance through w h i c h that force is over
come.
T h u s , i f o n e p o u n d is l i f t e d o n e f o o t h i g h i n o p p o s i t i o n t o
the f o r c e o f g r a v i t y , a c e r t a i n amount o f w o r k is d o n e , a n d
this q u a n t i t y is k n o w n a m o n g e n g i n e e r s as a f o o t - p o u n d .
I f a b o d y w h o s e m a s s is t w e n t y p o u n d s is l i f t e d t e n f e e t ,
this m i g h t b e d o n e b y t a k i n g o n e o f t h e p o u n d s a n d raising i t
first o n e f o o t a n d t h e n a n o t h e r t i l l it h a d risen ten feet, a n d
then d o i n g t h e s a m e w i t h e a c h o f t h e r e m a i n i n g p o u n d s , s o
that t h e quantity o f w o r k c a l l e d a f o o t - p o u n d is p e r f o r m e d
200 t i m e s i n r a i s i n g t w e n t y p o u n d s t e n f e e t . Hence the
w o r k d o n e i n l i f t i n g a b o d y is f o u n d b y m u l t i p l y i n g t h e w e i g h t
o f the b o d y i n p o u n d s b y t h e h e i g h t in feet. The result
is the w o r k i n f o o t - p o u n d s .
The foot-pound is a gravitation measure, depending on
the i n t e n s i t y o f g r a v i t y at t h e p l a c e . T o r e d u c e it t o a b s o l u t e
measure w e m u s t m u l t i p l y t h e n u m b e r o f f o o t - p o u n d s b y t h e
intensity o f g r a v i t y a t t h e p l a c e t o g e t t h e n u m b e r o f f o o t -
poundals.
The w o r k d o n e w h e n w e r a i s e a h e a v y b o d y is d o n e i n
o v e r c o m i n g the attraction o f the earth. W o r k is a l s o d o n e
when w e draw asunder t w o magnets which attract each
other, w h e n w e d r a w o u t an e l a s t i c c o r d , w h e n w e c o m p r e s s
air, a n d , i n general,- w h e n w e a p p l y f o r c e t o a n y t h i n g which
m o v e s in t h e d i r e c t i o n o f t h e f o r c e .
T h e r e is o n e c a s e o f t h e a p p l i c a t i o n o f f o r c e t o a m o v i n g
b o d y w h i c h is o f g r e a t i m p o r t a n c e , n a m e l y , w h e n t h e f o r c e
is e m p l o y e d i n c h a n g i n g t h e v e l o c i t y o f t h e b o d y .
S u p p o s e a b o d y w h o s e m a s s is M ( M p o u n d s o r M g r a m m e s )
to b e m o v i n g in a certain direction with a velocity which
we shall c a l l v, a n d l e t a f o r c e , which w e shall call F , b e

a p p l i e d t o t h e b o d y i n t h e d i r e c t i o n o f its m o t i o n . L e t us
consider the effect o f this f o r c e a c t i n g on the b o d y for a
v e r y small t i m e T , during w h i c h the b o d y m o v e s through
t h e s p a c e s, a n d at t h e e n d o f w h i c h its v e l o c i t y is v'.
T o a s c e r t a i n t h e m a g n i t u d e o f t h e f o r c e F, l e t us c o n s i d e r
the m o m e n t u m w h i c h it p r o d u c e s in the b o d y , a n d the t i m e
d u r i n g w h i c h t h e m o m e n t u m is p r o d u c e d .
T h e momentum o f t h e b e g i n n i n g o f t h e r i m e T w a s MV,
a n d at t h e e n d o f t h e t i m e T i t w a s M?/, SO t h a t t h e m o m e n t u m
p r o d u c e d b y t h e f o r c e F a c t i n g f o r t h e t i m e x is uv' — M » .
B u t since forces are measured b y the m o m e n t u m produced
in unit o f time, the m o m e n t u m produced b y F in one unit
o f t i m e is F , a n d t h e m o m e n t u m p r o d u c e d b y F i n T u n i t s o f
t i m e is F T . S i n c e the t w o values are equal,
FT — M(z/ — V).
T h i s is o n e form o f t h e f u n d a m e n t a l e q u a t i o n o f d y n a m i c s .
I f w e define the impulse o f a force as t h e a v e r a g e v a l u e o f
t h e f o r c e m u l t i p l i e d b y t h e t i m e d u r i n g w h i c h i t acts, t h e n
this e q u a t i o n may b e expressed in w o r d s b y saying that
t h e i m p u l s e o f a f o r c e is e q u a l t o t h e m o m e n t u m produced
by it
W e h a v e n e x t t o find s, t h e s p a c e d e s c r i b e d b y the b o d y
during the t i m e T. I f the velocity h a d b e e n uniform, the
space described w o u l d have b e e n the product o f the time
b y the velocity. W h e n t h e v e l o c i t y is n o t u n i f o r m t h e time
must b e multiplied b y the m e a n or average velocity to get
the space described. I n b o t h t h e s e cases i n w h i c h a v e r a g e
force or average velocity is m e n t i o n e d , the t i m e is sup
p o s e d t o b e s u b d i v i d e d i n t o a n u m b e r o f equal parts, a n d
t h e a v e r a g e is t a k e n o f t h e f o r c e o r o f t h e v e l o c i t y for a l l t h e s e
divisions o f the time. In the present case, in w h i c h the
t i m e c o n s i d e r e d is s o s m a l l t h a t t h e c h a n g e o f v e l o c i t y is a l s o
small, the a v e r a g e v e l o c i t y during the time T m a y b e taken
as t h e a r i t h m e t i c a l m e a n o f t h e v e l o c i t i e s at t h e beginning
a n d at t h e e n d o f t h e t i m e , o r ±(v + v').

Kinetic Energy. 89
H e n c e t h e s p a c e d e s c r i b e d is
s = \(v -f- v')r.
T h i s m a y b e c o n s i d e r e d as a k i n e m a t i c a l e q u a t i o n , s i n c e
it d e p e n d s o n the nature o f m o t i o n only, and n o t on that
of the m o v i n g b o d y .
I f w e multiply together these t w o equations w e g e t
2 2
ftj = 1 m ( z / — z> )t ;
and if w e d i v i d e b y T w e find
2 2
its = \yLT/ —\mv .
Now fs is t h e w o r k d o n e b y t h e f o r c e f a c t i n g o n the
b o d y w h i l e it m o v e s i n t h e d i r e c t i o n o f f t h r o u g h a s p a c e s.
2
I f w e a l s o d e n o t e £m& , t h e m a s s o f t h e b o d y m u l t i p l i e d b y
h a l f t h e s q u a r e o f its v e l o c i t y , b y t h e expression the kinetic
energy of the body, then ^mz/ 2
will b e the kinetic energy
after the a c t i o n o f t h e f o r c e f t h r o u g h a s p a c e s.
We m a y n o w express the equation in w o r d s b y saying
that t h e w o r k d o n e b y the force F in setting the b o d y in
m o t i o n is m e a s u r e d b y t h e i n c r e a s e o f k i n e t i c e n e r g y d u r i n g
t h e t i m e t h a t t h e f o r c e acts.
W e h a v e p r o v e d t h a t this is true w h e n t h e i n t e r v a l o f t i m e
d u r i n g w h i c h t h e f o r c e a c t s i s so s m a l l that w e m a y c o n s i d e r
t h e m e a n v e l o c i t y d u r i n g t h a t t i m e as e q u a l t o t h e arithme
t i c a l m e a n o f t h e v e l o c i t i e s at t h e b e g i n n i n g a n d e n d o f t h e
time. T h i s assumption, w h i c h is exactly true when the
f o r c e is u n i f o r m , is a p p r o x i m a t e l y t r u e i n e v e r y c a s e when
t h e t i m e c o n s i d e r e d is s m a l l e n o u g h .
B y d i v i d i n g the w h o l e t i m e o f a c t i o n o f the force into
s m a l l parts, a n d p r o v i n g t h a t i n e a c h o f t h e s e t h e w o r k . d o n e
b y t h e f o r c e is e q u a l t o t h e i n c r e a s e o f k i n e t i c e n e r g y o f t h e
b o d y , w e may, b y a d d i n g the different portions o f the w o r k
and the different i n c r e m e n t s o f e n e r g y , a r r i v e at t h e result
that t h e t o t a l w o r k d o n e b y t h e f o r c e is e q u a l t o t h e total
increase o f kinetic energy.
I f the force acts o n t h e b o d y i n t h e d i r e c t i o n u p p o s i t e t o
the m o t i o n , the kinetic e n e r g y o f the b o d y will b e diminished

instead o f increased, and the force, instead o f d o i n g work on
t h e b o d y , w i l l b e a r e s i s t a n c e w h i c h t h e b o d y i n its m o t i o n
overcomes. H e n c e a m o v i n g b o d y can d o w o r k in over
c o m i n g r e s i s t a n c e as l o n g as it is i n m o t i o n , a n d the work
d o n e b y t h e m o v i n g b o d y is e q u a l t o t h e diminution o f its
kinetic e n e r g y , till, w h e n t h e b o d y is b r o u g h t t o rest, t h e
w h o l e w o r k it h a s d o n e i s e q u a l t o t h e w h o l e k i n e t i c e n e r g y
w h i c h it h a d at first.
We now see the appropriateness of the name kinetic
e n e r g y , w h i c h w e h a v e h i t h e r t o u s e d m e r e l y as a n a m e f o r
2
the product -|M^ . For the energy of a body may be
d e f i n e d as t h e c a p a c i t y w h i c h i t has o f d o i n g w o r k , a n d is
measured b y the q u a n t i t y o f w o r k w h i c h it c a n do. The
kinetic energy of a body is t h e energy which it has izi
v i r t u e o f b e i n g i n motion, and w e have just shown that its
v a l u e m a y b e f o u n d b y m u l t i p l y i n g the m a s s o f t h e b o d y b y
half the square o f the v e l o c i t y .
I n our investigation w e h a v e , for the sake o f simplicity,
supposed the force to act in the same direction as the
motion. T o m a k e t h e p r o o f p e r f e c t l y g e n e r a l , as it is g i v e n
i n treatises o n d y n a m i c s , w e h a v e o n l y t o r e s o l v e t h e a c t u a l
force into t w o parts, o n e in the direction o f the m o t i o n and
the o t h e r at right a n g l e s t o it, a n d t o o b s e r v e t h a t t h e p a r t
a t right a n g l e s t o t h e m o t i o n c a n n e i t h e r d o a n y w o r k o n t h e
b o d y nor c h a n g e the v e l o c i t y or the kinetic e n e r g y , so that
t h e w h o l e effect, w h e t h e r o f w o r k o r o f a l t e r a t i o n o f k i n e t i c
energy, depends on the p a r t o f t h e f o r c e w h i c h is i n the
d i r e c t i o n o f the m o t i o n .
T h e s t u d e n t , i f n o t f a m i l i a r w i t h this s u b j e c t , s h o u l d r e f e r
to s o m e treatise o n dynamics, and c o m p a r e the investigation
there g i v e n with the outline o f the reasoning g i v e n a b o v e .
O u r o b j e c t at p r e s e n t is t o f i x i n o u r m i n d s w h a t is m e a n t
b y W o r k and Energy.
T h e great importance o f giving a name to the quantity
w h i c h w e c a l l K i n e t i c E n e r g y s e e m s t o h a v e b e e n first r e c o g
nised b y L e i b n i t z , w h o g a v e t o the p r o d u c t o f the mass b y

Kinetic and Potential Energy. 91
the s q u a r e o f t h e v e l o c i t y t h e name of Vis Viva. T h i s is
twice the kinetic e n e r g y .
N e w t o n , in a s c h o l i u m t o his T h i r d L a w o f M o t i o n , has
stated the r e l a t i o n between work and kinetic e n e r g y in a
m a n n e r so p e r f e c t that it c a n n o t be improved, but at the
s a m e t i m e w i t h s o l i t t l e a p p a r e n t effort o r d e s i r e t o a t t r a c t
a t t e n t i o n that n o o n e seems to have b e e n struck w i t h the
great importance o f the p a s s a g e till it was pointed out
recently b y T h o m s o n and T a i t .
T h e use o f t h e t e r m E n e r g y , i n a scientific s e n s e , t o e x p r e s s
the quantity o f w o r k a b o d y c a n d o , w a s i n t r o d u c e d b y D r .
Y o u n g ( ' Lectures on Natural Philosophy,' Lecture V I I I . ) .
T h e energy o f a system o f bodies acting on o n e another
w i t h forces d e p e n d i n g o n t h e i r r e l a t i v e p o s i t i o n s is d u e partly
to their m o t i o n , and partly to their relative position.
T h a t p a r t w h i c h is d u e t o t h e i r m o t i o n w a s c a l l e d A c t u a l
Energy by Rankine, and Kinetic Energy by Thomson and
Tait.
T h a t p a r t w h i c h is d u e t o t h e i r r e l a t i v e p o s i t i o n depends
u p o n the w o r k which the various forces w o u l d d o if the
bodies w e r e t o y i e l d t o the action o f these forces. This is
called the S u m o f the T e n s i o n s b y H e l m h o l t z , i n his c e l e
: 1
brated m e m o i r on the Conservation of F o r c e . ' Thomson
c a l l e d it S t a t i c a l E n e r g y , a n d R a n k i n e introduced the term
Potential E n e r g y , a v e r y felicitous name, since it not only
signifies t h e e n e r g y w h i c h t h e s y s t e m has n o t in possession,
b u t o n l y h a s t h e p o w e r t o a c q u i r e , b u t it a l s o i n d i c a t e s t h a t
it is t o b e f o u n d f r o m w h a t is c a l l e d ( o n o t h e r g r o u n d s ) t h e
Potential Function.
Thus when a h e a v y b o d y has been lifted to a certain
h e i g h t a b o v e t h e earth's surface, t h e s y s t e m o f t w o b o d i e s , i t
and the earth, h a v e potential energy equal to the work
which would be done if the h e a v y b o d y w e r e a l l o w e d to
d e s c e n d t i l l i t is s t o p p e d b y t h e surface o f t h e earth.
I f t h e b o d y w e r e a l l o w e d t o fall f r e e l y , i t w o u l d acquire
1
Berlin, 1847, Translated in Taylor's Scientific Memoirs, Feb. 1853,

9 2 Elementary Dynamical Principles.
velocity, and the kinetic energy acquired would be exactly
equal t o the potential e n e r g y lost in the same t i m e .
I t is p r o v e d i n t r e a t i s e s o n d y n a m i c s , t h a t if, in a n y s y s t e m
o f b o d i e s , t h e f o r c e w h i c h a c t s b e t w e e n a n y t w o b o d i e s is i n
the l i n e j o i n i n g them, and d e p e n d s o n l y o n their distance,
a n d n o t o n the w a y i n w h i c h t h e y are m o v i n g at the time,
then i f n o o t h e r forces act o n the system, the sum o f the
p o t e n t i a l a n d k i n e t i c e n e r g y o f all t h e b o d i e s o f t h e s y s t e m
will always remain the same.
T h i s p r i n c i p l e is c a l l e d t h e P r i n c i p l e o f t h e C o n s e r v a t i o n
o f E n e r g y ; it is o f g r e a t i m p o r t a n c e i n a l l b r a n c h e s o f s c i e n c e ,
and the recent a d v a n c e s in the science of heat have been
chiefly d u e to the a p p l i c a t i o n o f this p r i n c i p l e .
We cannot i n d e e d assume, without e v i d e n c e o f a satis
factory nature, that t h e mutual action b e t w e e n a n y t w o parts
o f a r e a l b o d y m u s t a l w a y s b e in t h e l i n e j o i n i n g t h e m , a n d
must d e p e n d o n l y on their distance. W e k n o w t h a t this is
t h e c a s e w i t h r e s p e c t t o the a t t r a c t i o n o f b o d i e s at a d i s t a n c e ,
but w e cannot make a n y such a s s u m p t i o n concerning the
internal forces o f b o d i e s o f w h o s e internal constitution we
know next to nothing.
We cannot even a s s e r t that a l l energy must be either
potential or kinetic, though w e m a y not b e a b l e t o c o n c e i v e
any other form. Nevertheless, the principle has b e e n de
m o n s t r a t e d b y d y n a m i c a l r e a s o n i n g t o b e a b s o l u t e l y true f o r
s y s t e m s fulfilling c e r t a i n c o n d i t i o n s , a n d it has b e e n p r o v e d
b y e x p e r i m e n t t o b e true within the limits o f error o f obser
vation, i n cases w h e r e the e n e r g y takes the forms o f heat,
m a g n e t i s a t i o n , e l e c t r i f i c a t i o n , & c , so t h a t t h e f o l l o w i n g state
m e n t is o n e w h i c h , i f w e c a n n o t a b s o l u t e l y affirm its n e c e s
sary truth, is w o r t h y o f b e i n g c a r e f u l l y t e s t e d , and traced
i n t o a l l t h e c o n c l u s i o n s w h i c h a r e i m p l i e d i n it.
GENERAL STATEMENT OK T H E C O N S E R V A T I O N OF ENERGY.
' The total energy of any body or system of bodies is a

quantity which can tieither be increased nor diminished by a?

Conservation of Energy. 93
mutual action of these bodies, though it may be transforme
into any of the forms of which energy is susceptible.'
I f by the application of mechanical force, heat, or any
other kind of action to a body, or system of bodies, it is
made to pass through any series of changes, and at last to
return in all respects to its original state, then the energy
communicated to the system during this cycle of operations
must be equal to the energy which the system communicates
to other bodies during the cycle.
For the system is in all respects the same at the beginning
and at the end o f the cycle, and in particular it has the same
amount of energy in i t ; and therefore, since no internal
action of the system can either produce or destroy energy,
the quantity o f energy which enters the system must be
equal to that which leaves it during the cycle.
The reason for believing heat not to be a substance
is that it can be generated, so that the quantity o f it may
be increased to any extent, and it can also b e destroyed,
though this operation requires certain conditions to be
fulfilled.
T h e reason for believing heat to be a form of energy is
that heat may be generated by the application of work, and
that for every unit of heat which is generated a certain
quantity of mechanical energy disappears. Besides, work
may be done by the action o f heat, and for every foot
pound of work so done a certain quantity of heat is put out
of existence.
N o w when the appearance of one thing is strictly con
nected with the disappearance of another, so that the
amount which exists of the one thing depends on and can
be calculated from the amount of the other which has dis
appeared, we conclude that the one has been formed at the
expense o f the other, and that they are both forms o f the
same thing.
Hence we conclude that heat is energy in a peculiar
form. T h e reasons for believing heat as it exists in a hot

94 Stresses and Strains.
b o d y to b e in the form o f kinetic energy—that is, t h a t the
particles of the hot b o d y are in actual though invisible
m o t i o n — w i l l b e discussed afterwards.
C H A P T E R V.
O N T H E M E A S U R E M E N T OF PRESSURE A N D O T H E R INTERNAL
FORCES, A N D O F T H E EFFECTS W H I C H T H E Y PRODUCE.
E V E R Y force acts b e t w e e n t w o b o d i e s or parts o f bodies,

. f w e are c o n s i d e r i n g a particular b o d y o r system o f b o d i e s ,
t h e n t h o s e f o r c e s w h i c h a c t b e t w e e n b o d i e s b e l o n g i n g t o this
system and bodies not b e l o n g i n g to the system are called
E x t e r n a l F o r c e s , a n d those w h i c h act b e t w e e n the different
parts o f the system itself are called I n t e r n a l F o r c e s .
I f w e n o w suppose the system t o b e d i v i d e d in i m a g i n a
t i o n into t w o parts, w e m a y c o n s i d e r the forces external to
o n e o f the p a r t s t o b e , first, t h o s e w h i c h act b e t w e e n that
part and bodies external to the system, and, second, those
w h i c h act b e t w e e n the t w o parts o f the system. The com
b i n e d e f f e c t o f t h e s e f o r c e s is k n o w n b y t h e a c t u a l m o t i o n
or rest o f the p a r t t o w h i c h t h e y a r e a p p l i e d , so that, i f w e
k n o w the resultant o f the external forces o n e a c h part, w e
can find that o f the internal forces acting b e t w e e n the t w o
parts.
Thus, if we consider a pillar supporting a statue, and
imagine the pillar d i v i d e d into t w o parts by a horizontal
plane at a n y distance from the ground, the internal force
b e t w e e n the t w o parts o f the pillar m a y be found b y con
sidering the w e i g h t o f the statue a n d that part o f the pillar
which is a b o v e the plane. The lower part o f the pillar
presses o n the u p p e r part w i t h a force w h i c h exactly counter
balances this weight. This force is called a Pressure.
In the same way we may find the internal force acting
through any horizontal section o f a rope which supports a

Pressures and Tensions. 95
heavy b o d y to b e a T e n s i o n equal t o the w e i g h t o f the
heavy b o d y a n d o f the part o f the r o p e b e l o w the imaginary
section.
The internal force in the p i l l a r is c a l l e d Longitudinal
Pressure, a n d t h a t i n t h e r o p e is c a l l e d L o n g i t u d i n a l T e n s i o n .
I f this p r e s s u r e o r t e n s i o n is u n i f o r m o v e r t h e w h o l e h o r i
zontal section, the amount o f it per square inch can be
found b y d i v i d i n g t h e w h o l e f o r c e b y t h e n u m b e r o f s q u a r e
inches i n t h e s e c t i o n .
T h e internal forces in a b o d y are c a l l e d Stresses, and
longitudinal pressure a n d tension are examples o f particular
k i n d s o f stress. I t is s h o w n i n treatises o n E l a s t i c i t y t h a t
the m o s t g e n e r a l k i n d o f stress at a n y p o i n t o f a b o d y m a y
be r e p r e s e n t e d b y t h r e e l o n g i t u d i n a l p r e s s u r e s o r t e n s i o n s i n
directions at right angles to each other.
For instance, a brick in a w a l l m a y s u p p o r t a v e r t i c a l
pressure d e p e n d i n g o n t h e h e i g h t o f t h e w a l l a b o v e it, a n d
also a h o r i z o n t a l p r e s s u r e i n t h e d i r e c t i o n o f t h e l e n g t h o f
the w a l l , d e p e n d i n g o n t h e thrust o f a n a r c h a b u t t i n g a g a i n s t
the w a l l , w h i l e i n t h e d i r e c t i o n p e r p e n d i c u l a r to the face o f
the w a l l t h e p r e s s u r e is t h a t o f t h e atmosphere.
I n s o l i d b o d i e s , s u c h as a b r i c k , t h e s e t h r e e p r e s s u r e s m a y
b e all i n d e p e n d e n t , t h e i r m a g n i t u d e being limited only b y
the s t r e n g t h o f t h e s o l i d , w h i c h w i l l b r e a k d o w n i f t h e f o r c e
applied to it exceeds a certain amount.
In fluids, the pressures in all directions must b e equal,
because the v e r y slightest difference b e t w e e n the pressures
in t h e t h r e e d i r e c t i o n s is sufficient t o s e t t h e fluid i n m o t i o n .
The subject of fluid p r e s s u r e is s o i m p o r t a n t to what
f o l l o w s t h a t I t h i n k it w o r t h w h i l e , at t h e r i s k o f r e p e a t i n g
w h a t t h e s t u d e n t o u g h t t o k n o w , t o state w h a t w e m e a n by
a fluid, a n d t o s h o w f r o m t h e d e f i n i t i o n that t h e p r e s s u r e s i n
all d i r e c t i o n s a r e e q u a l .
D E F I N I T I O N O F A F L U I D . — A fluid is a body the contiguous
parts of which act on one another with a pressure which is
perpendicular to the interface which separates those parts.

q6 Stresses and Strains.
S i n c e t h e p r e s s u r e is e n t i r e l y perpendicular t o t h e sur
face, there c a n b e n o friction between the parts o f a fluid
in contact.
Theorem.—The p r e s s u r e s i n a n y t w o d i r e c t i o n s at a p o i n t
o f a fluid a r e e q u a l . F o r , l e t the plane
of the p a p e r b e that o f the t w o given
directions, a n d draw an isosceles triangle
whose sides are perpendicular t o the two
directions respectively, and consider the
equilibrium of a small triangular prism
K
of which this triangle is t h e b a s e . L e t
P Q be the pressures perpendicular t o t h e sides, and R
that p e r p e n d i c u l a r to the base. Then, since these three
forces are in equilibrium, a n d since R makes equal angles
w i t h p a n d Q, p a n d Q m u s t b e e q u a l . B u t t h e forces on
which P a n d Q act are also e q u a l ; therefore t h e pressures
referred t o unit o f area o n these faces a r e equal, which was
to b e p r o v e d .
A great m a n y substances m a y b e f o u n d w h i c h perfectly

fulfil this d e f i n i t i o n o f a fluid w h e n t h e y a r e at rest, a n d t h e y
are t h e r e f o r e called fluids. B u t n o e x i s t i n g fluid fulfils the
definition w h e n it is i n m o t i o n . I n a fluid i n m o t i o n t h e
p r e s s u r e s at a p o i n t m a y b e greater in o n e direction than
in another, or, what is t h e s a m e thing, t h e force between
two parts m a y n o t b e p e r p e n d i c u l a r t o the interface which
s e p a r a t e s t h o s e parts.
If a fluid could b e found w h i c h fulfilled the definition
w h e n i n m o t i o n as w e l l as w h e n a t rest, i t w o u l d b e c a l l e d a
Perfect Fluid. A l l a c t u a l fluids u r e i m p e r f e c t , a n d e x h i b i t
the p h e n o m e n o n o f internal friction or viscosity, b y which
their m o t i o n after b e i n g s t i r r e d a b o u t i n a v e s s e l is g r a d u a l l y
stopped, a n d t h e e n e r g y o f t h e m o t i o n is c o n v e r t e d into
heat.
T h e d e g r e e o f viscosity varies from that o f tar t o that o f
w a t e r , o r e t h e r , o r h y d r o g e n g a s , b u t n o a c t u a l fluid is p e r f e c t
in t h e s e n s e o f t h e d e f i n i t i o n w h e n i n m o t i o n .

Pressure in a Fluid.
97
The pressure at any point o f a f l u i d is t h e r a t i o o f the
w h o l e p r e s s u r e o n a s m a l l surface t o t h e a r e a o f t h a t surface
w h e n t h e a r e a o f the surface is m a d e t o d i m i n i s h i n d e f i n i t e l y ,
but so that the c e n t r e o f g r a v i t y o f t h e surface a l w a y s c o i n c i d e s
w i t h the g i v e n p o i n t .
T h i s p r e s s u r e is s o m e t i m e s c a l l e d h y d r o s t a t i c p r e s s u r e , to
distinguish it from longitudinal pressure. Both kinds of
pressure are m e a s u r e d b y t h e n u m b e r o f u n i t s o f f o r c e i n t h e
pressure o n u n i t o f a r e a ; f o r i n s t a n c e , i n p o u n d s ' w e i g h t o n
the square i n c h o r s q u a r e f o o t , a n d i n k i l o g r a m m e s ' w e i g h t
o n the s q u a r e mètre. B o t h these measures are gravitation
measures, a n d m u s t b e m u l t i p l i e d b y t h e v a l u e o f t h e i n t e n -
sity o f g r a v i t y t o r e d u c e t h e m t o a b s o l u t e measures.
Pressures are also m e a s u r e d in terms o f the height o f a
c o l u m n o f w a t e r o r o f m e r c u r y , w h i c h w o u l d p r o d u c e b y its
weight an e q u a l pressure. T h u s a p r e s s u r e o f 16 f e e t o f
w a t e r is n e a r l y e q u a l t o 1,000 p o u n d s ' w e i g h t o n t h e square
foot, a n d a p r e s s u r e o f 4 i n c h e s o f w a t e r is m o r e n e a r l y e q u a l
t o 101 g r a i n s ' w e i g h t o n t h e s q u a r e i n c h .
I n the m e t r i c a l s y s t e m t h e p r e s s u r e o f w a t e r o n a surface
at any d e p t h is e x p r e s s e d b y t h e p r o d u c t o f t h e d e p t h i n t o
the area o f t h e surface. I f w e e m p l o y t h e m è t r e as the
measure o f l e n g t h , t h e pressure will b e e x p r e s s e d in t o n n e s '
weight, but if w e use t h e d e c i m e t r e , c e n t i m è t r e , or m i l l i m è t r e ,
the pressure will b e e x p r e s s e d in kilogrammes, grammes,
or m i l l i g r a m m e s r e s p e c t i v e l y , i n g r a v i t a t i o n m e a s u r e .
T h e d e n s i t y o f m e r c u r y at 0° C . is i3"5o6 t i m e s t h a t o f
0
w a t e r at 4 C. H e n c e the pressure due to a g i v e n depth o f
m e r c u r y is a b o u t i3'6 t i m e s t h a t o f a n e q u a l d e p t h o f w a t e r .
The Barometer.—The pressure o f the air is g e n e r a l l y
measured b y m e a n s o f the mercurial barometer. T h i s baro-
meter consists o f a glass tube c l o s e d at o n e e n d a n d filled
w i t h m e r c u r y , f r o m w h i c h a l l air a n d moisture are expelled
by b o i l i n g it i n t h e t u b e . T h e t u b e is t h e n p l a c e d w i t h its
o p e n e n d i n a v e s s e l o f m e r c u r y , a n d its c l o s e d e n d raised
till t h e t u b e is v e r t i c a l . T h e m e r c u r y is f o u n d t o s t a n d at
H

Stresses and Strains.
a certain level in the tube, the h e i g h t o f w h i c h a b o v e the
level o f the mercury i n t h e v e s s e l o r c i s t e r n is c a l l e d the
height o f the barometer.
T h e surface o f t h e m e r c u r y i n t h e c i s t e r n is e x p o s e d to
t h e p r e s s u r e o f t h e air, w h i l e t h e s u r f a c e o f t h e m e r c u r y in
t h e t u b e is e x p o s e d o n l y t o t h e p r e s s u r e o f w h a t e v e r is in
the t u b e a b o v e it. T h e o n l y k n o w n substance w h i c h can
b e t h e r e is t h e v a p o u r o f m e r c u r y , t h e p r e s s u r e o f w h i c h at
ordinary temperatures is so s m a l l t h a t i t m a y b e n e g l e c t e d ,
so that the pressure o f the air m a y b e m e a s u r e d b y that
due to the d i f f e r e n c e o f l e v e l o f t h e m e r c u r y in the tube
a n d in the cistern.
The pressure o f the atmosphere i s , as w e know, very
v a r i a b l e , a n d is d i f f e r e n t in d i f f e r e n t p l a c e s ; b u t f o r v a r i o u s
p u r p o s e s it is c o n v e n i e n t t o use, a s a l a r g e u n i t o f p r e s s u r e ,
a pressure n o t v e r y different from the a v e r a g e atmospheric
p r e s s u r e at t h e m e a n l e v e l o f t h e sea. T h i s unit o f pressure
is c a l l e d a n a t m o s p h e r e , a n d is u s e d i n m e a s u r i n g p r e s s u r e s
in steam-engines and boilers. Its exact v a l u e in the metrical
s y s t e m is t h e p r e s s u r e d u e t o a d e p t h o f 7 60 m i l l i m e t r e s o f
mercury at o° C. at Paris, w h e r e the force o f g r a v i t y is
9/80868 m e t r e s . T h i s is e q u a l t o i ' 0 3 3 k i l o g r a m m e s ' w e i g h t
o n the square centimetre. In absolute measure it is e q u a l
t o 1,013,237, t h e g r a m m e , t h e c e n t i m e t r e , a n d the second
b e i n g the fundamental units.
In the British system an atmosphere is d e f i n e d as the

pressure due to a depth o f 29-905 i n c h e s o f mercury at
32° F . at L o n d o n , w h e r e t h e f o r c e o f g r a v i t y is 32-1889 feet,
a n d is, r o u g h l y , 1 4 ! p o u n d s ' w e i g h t o n t h e s q u a r e i n c h . I t is
t h e r e f o r e 0-99968 o f t h e a t m o s p h e r e o f t h e m e t r i c a l s y s t e m .
ON THE ALTERATION OF T H E DIMENSIONS A N D VOLUME

OF BODIES BY MECHANICAL FORCES A N D BY HEAT.
W e h a v e seen that effects o f the s a m e k i n d in c h a n g i n g

the form or v o l u m e o f b o d i e s are p r o d u c e d by mechanical
force and b y heat. W e cannot therefore fully understand

Strains. 99
the effects o f h e a t a l o n e o n t h e s e b o d i e s w i t h o u t at t h e s a m e
time considering those o f m e c h a n i c a l force.
W e h a v e first t o e x p l a i n , f r o m a p u r e l y g e o m e t r i c a l p o i n t
of view, the various k i n d s o f c h a n g e o f form o f w h i c h a b o d y
is c a p a b l e , c o n s i d e r i n g o n l y t h o s e c a s e s in w h i c h e v e r y p a r t
o f the b o d y u n d e r g o e s a similar c h a n g e o f form. W e shall
use t h e w o r d strain t o e x p r e s s g e n e r a l l y a n y a l t e r a t i o n of
form o f a b o d y .
Longitudinal Strain.—Suppose the b o d y t o b e e l o n g a t e d
or c o m p r e s s e d in o n e d i r e c t i o n o n l y , s o that i f t w o p o i n t s
in the b o d y l i e i n a l i n e p a r a l l e l t o this direction, their
distance w i l l b e i n c r e a s e d or d i m i n i s h e d in a certain ratio,
but i f t h e l i n e j o i n i n g t h e p o i n t s b e p e r p e n d i c u l a r to this
d i r e c t i o n the l e n g t h o f t h e l i n e w i l l n o t b e a l t e r e d .
T h i s is c a l l e d l o n g i t u d i n a l e x t e n s i o n o r c o m p r e s s i o n , o r
m o r e g e n e r a l l y l o n g i t u d i n a l strain, a n d is m e a s u r e d by the
fraction o f its o r i g i n a l l e n g t h b y w h i c h a n y l o n g i t u d i n a l l i n e
in t h e b o d y is e l o n g a t e d o r c o n t r a c t e d .
General Strain.—Such an alteration o f the form o f the
body may take place simultaneously or successively in
three d i r e c t i o n s at r i g h t a n g l e s t o e a c h o t h e r . T h i s system
of three longitudinal strains is s h o w n in treatises on the
motion o f continuous b o d i e s to b e the most general kind o f
strain o f w h i c h a b o d y is c a p a b l e .
W e shall, h o w e v e r , o n l y c o n s i d e r t w o c a s e s i n p a r t i c u l a r .
ist. Isotropic Strain.—When the strains in the three
d i r e c t i o n s at r i g h t a n g l e s t o e a c h other arc all equal, the
f o r m o f t h e b o d y r e m a i n s s i m i l a r t o itself, a n d i t expands
or c o n t r a c t s e q u a l l y i n a l l d i r e c t i o n s , as m o s t s o l i d b o d i e s d o
when heated.
S i n c e e a c h o f t h e t h r e e l o n g i t u d i n a l strains o f w h i c h this
strain is c o m p o u n d e d i n c r e a s e s the volume by a fraction
of itself e q u a l to the value o f the longitudinal strain, i t
follows that w h e n each o f the strains is a v e r y s m a l l frac
tion, t h e t o t a l i n c r e m e n t o f v o l u m e is e q u a l t o t h e o r i g i n a l
v o l u m e m u l t i p l i e d b y t h e a l g e b r a i c a l s u m o f t h e t h r e e strains.
H 2

IOO Stresses and Strains.
T h e r a t i o o f t h e i n c r e m e n t o f v o l u m e t o t h e o r i g i n a l v o l u m e is
called the v o l u m i n a l expansion w h e n p o s i t i v e , or the voluminal
c o n t r a c t i o n w h e n n e g a t i v e , a n d it a p p e a r s , f r o m w h a t w e h a v e
s a i d , t h a t w h e n t h e -strains a r e s m a l l t h e v o l u m i n a l e x p a n s i o n
is e q u a l t o t h e s u m o f t h e l o n g i t u d i n a l e x t e n s i o n s , or, w h e n
these are equal, t o three t i m e s the l o n g i t u d i n a l extension.
2nd. Shearing Strain.—The o t h e r p a r t i c u l a r c a s e is w h e n
t h e d i m e n s i o n s o f t h e b o d y a r e e x t e n d e d i n o n e d i r e c t i o n in
t h e r a t i o o f a t o i , a n d c o n t r a c t e d in a p e r p e n d i c u l a r direc
t i o n i n t h e r a t i o o f i t o a. I n this c a s e t h e r e . i s n o altera
t i o n o f v o l u m e , b u t t h e b o d y is d i s t o r t e d .
WORK DONE B Y A STRESS ON A BODY WHOSE FORM IS

CHANGING O R IS U N D E R G O I N G A STRAIN.
We shall i n t h e first place suppose that the stress c o n

tinues constant during the c h a n g e of f o r m w h i c h w e consider.
I f d u r i n g a c o n s i d e r a b l e c h a n g e o f f o r m t h e stress u n d e r g o e s
considerable change, w e m a y d i v i d e the w h o l e operation into
parts, during each o f which w e m a y regard the stress as
c o n s t a n t , a n d find t h e t o t a l w o r k b y s u m m a t i o n .
The g e n e r a l r u l e is t h a t , i f t h e stress a n d t h e s t r a i n a r e o f
the same t y p e , t h e w o r k d o n e o n unit o f v o l u m e during any
strain is t h e p r o d u c t o f t h e strain i n t o t h e a v e r a g e v a l u e o f
t h e stress.
If, h o w e v e r , t h e stress b e o f a t y p e c o n j u g a t e t o t h e strain,
n o w o r k is d o n e .
T h u s , i f t h e stress b e a l o n g i t u d i n a l o n e , w e m u s t m u l t i p l y
t h e a v e r a g e v a l u e o f t h e stress b y t h e l o n g i t u d i n a l strain in
the same direction, and t h e result is n o t a f f e c t e d b y t h e
m a g n i t u d e o f t h e l o n g i t u d i n a l strains i n d i r e c t i o n s at right
a n g l e s t o t h e stress.
I f thje stress b e a h y d r o s t a t i c p r e s s u r e , w e m u s t m u l t i p l y
t h e a v e r a g e v a l u e o f this pressure b y the v o l u m i n a l com
pression t o find the work done on the b o d y per unit of
v o l u m e , a n d t h e result is n o t a f f e c t e d b y a n y strain o f d i s
tortion which d o e s not change the v o l u m e o f the b o d y .

Work done on a Fluid. IOI
H e n c e the w o r k d o n e b y external forces o n a fluid when

its volume is d i m i n i s h e d is equal t o the product o f the
average pressure into the diminution of volume, and if
the fluid e x p a n d s a n d o v e r c o m e s the resistance o f external
forces, the w o r k d o n e b y t h e f l u i d is m e a s u r e d b y the pro
duct o f the i n c r e a s e of v o l u m e , into the a v e r a g e pressure
during that i n c r e a s e .
The consideration o f t h e w o r k g a i n e d or lost during the
change o f v o l u m e o f a fluid is s o i m p o r t a n t t h a t w e shall
calculate it f r o m t h e b e g i n n i n g .
W O R K D O N E B Y A PISTON O N A FLUID.
Let us s u p p o s e t h a t t h e fluid is i n c o m m u n i c a t i o n w i t h a
c y l i n d e r i n w h i c h a p i s t o n is free F I G . 9.
to slide. J I
Let the area o f the face o f the j 1
p
piston b e d e n o t e d b y A . j I
Let the pressure o f t h e fluid j
be d e n o t e d b y p o n u n i t o f a r e a ,
T h e n the w h o l e pressure o f the fluid o n the face o f the
piston w i l l b e Ap, a n d i f P is t h e e x t e r n a l f o r c e w h i c h k e e p s
the p i s t o n i n e q u i l i b r i u m , p = Ap. N o w let the piston be
pressed inwards against the fluid through a distance .r.
The v o l u m e o f the c y l i n d e r o c c u p i e d b y t h e fluid w i l l be
diminished by a volume v = ax, because the volume of a
c y l i n d e r is e q u a l t o t h e a r e a o f its b a s e m u l t i p l i e d b y its
height.
If the force P continues u n i f o r m , o r i f P is t h e a v e r a g e
value o f the external force d u r i n g this m o t i o n , the work
d o n e b y the external force will b e w = p.*.
I f w e p u t f o r p its v a l u e i n t e r m s o f p, t h e p r e s s u r e o f t h e
fluid p e r u n i t o f area, t h i s b e c o m e s
w —- Apx ;
a n d i f w e r e m e m b e r t h a t ax is e q u a l t o v , this b e c o m e s
w = yp,

or the work done b y the piston against the fluid is equal to

the diminution of the volume o f the fluid multiplied by the
average value of the hydrostatic pressure.
It will be observed that this result is independent of the
area of the piston, and of the form and capacity of the
vessel with which the cylinder communicates.
If, for convenience, we suppose that the area of the piston
is unity, then putting A = i we shall have p — p and V = x,
so that the linear distance travelled b y the piston is nu
merically equal to the volume displaced.
ON INDICATOR DIAGRAMS.
I shall now describe a

method o f studying the action
of a fluid o f variable volume,
which was invented b y James
Watt, as a practical method of
determining the work done by
the steam-engine, and of which
the construction has been
gradually perfected, till it is
„ now capable o f tracing every
part of the action of the steam
in the most rapidly working engines.
A t present, however, I shall use this method as a means
of explaining and representing to the e y e the working o f a
fluid. This use o f the indicator diagram, which was intro
duced b y Clapeyron, has been greatly developed by Rankine
in his work on the steam-engine.
Let O v be a horizontal straight line, and op a vertical
line. On o v (which we shall call the line o f volumes) take
distances o a, o l>, o c to represent the volume occupied by
the fluid at different times, and at: a b c erect perpendiculars
a A, b B, c c, representing, on a convenient scale, the pressure
of the fluid at these different times.

Indicator Diagram.
( F o r i n s t a n c e , w e m a y s u p p o s e that, in t h e s c a l e o f v o l u m e s ,
one inch, m e a s u r e d h o r i z o n t a l l y , represents a v o l u m e equal
t o a c u b i c f o o t ; a n d that i n t h e s c a l e o f p r e s s u r e s , o n e i n c h ,
measured vertically, represents a pressure o f 1,000 pounds'
weight on the square foot.)
L e t us n o w s u p p o s e t h a t t h e v o l u m e i n c r e a s e s f r o m o a
t o o b, w h i l e t h e p r e s s u r e r e m a i n s c o n s t a n t , s o that a A = b B.
T h e n the i n c r e a s e o f v o l u m e is m e a s u r e d b y a b, a n d t h e
pressure w h i c h is o v e r c o m e b y t h e e x p a n s i o n o f t h e fluid b y
a A or b B , s o t h a t t h e w o r k d o n e b y t h e f l u i d is r e p r e s e n t e d
by the product o f t h e s e q u a n t i t i e s , o r a b, a A , that is, t h e
area o f t h e r e c t a n g l e a a b b.
O n the scale w h i c h w e h a v e assumed, e v e r y square inch
o f the a r e a o f t h e f i g u r e A B b a r e p r e s e n t s 1,000 f o o t - p o u n d s
of w o r k .
W e h a v e s u p p o s e d the pressure t o r e m a i n constant during
the c h a n g e o f v o l u m e . I f this is n o t t h e c a s e , b u t if the
pressure c h a n g e s f r o m b B t o c c, w h i l e t h e v o l u m e c h a n g e s
from o b t o O f , t h e n i f w e take b c small enough, w e m a y
suppose the pressure to change uniformly from the one
value to the other, so that w e m a y take the m e a n v a l u e o f
the pressure t o b e -|-(B b + c c). M u l t i p l y i n g this b y b c,
w e g e t -J(B b + - c c) b c, w h i c h is t h e w e l l - k n o w n expression
for th*e a r e a o f the strip E C f J , supposing B c a straight
line.
T h e w o r k d o n e b y t h e f l u i d is t h e r e f o r e still e q u a l t o t h e
area e n c l o s e d b y B C , t h e t w o v e r t i c a l l i n e s f r o m its e x t r e
mities, a n d t h e h o r i z o n t a l l i n e o v.
I n g e n e r a l , i f t h e v o l u m e a n d p r e s s u r e o f t h e fluid are m a d e
t o v a r y i n a n y m a n n e r w h a t e v e r , a n d i f a p o i n t p b e m a d e at
the s a m e t i m e t o m o v e s o t h a t its h o r i z o n t a l d i s t a n c e f r o m the
line o / represents t h e v o l u m e w h i c h t h e fluid o c c u p i e s at
that i n s t a n t , w h i l e its v e r t i c a l d i s t a n c e f r o m o v represents
t h e h y d r o s t a t i c p r e s s u r e o f t h e fluid at t h e s a m e i n s t a n t , a n d
if, at the b e g i n n i n g a n d e n d o f t h e p a t h t r a c e d b y P , v e r t i c a l
l i n e s b e d r a w n t o m e e t o v, t h e n , i f t h e p a t h of P does not

i n t e r s e c t itself, t h e a r e a b e t w e e n t h e s e b o u n d a r i e s represents
the w o r k d o n e b y the fluid against external f o r c e s , if it
lies on the right-hand side of the path o f the tracing
point. I f t h e a r e a l i e s o n t h e l e f t - h a n d s i d e o f t h e p a t h , it
represents the work d o n e b y the external forces on the
fluid.
I f t h e p a t h o f P r e t u r n s i n t o i t s e l f s o as t o f o r m a l o o p or
Fig. n.
Richards's Indicator.
closed figure, t h e n t h e v e r t i c a l l i n e s at t h e b e g i n n i n g a n d e n d
o f t h e p a t h w i l l c o i n c i d e , so t h a t it is u n n e c e s s a r y t o d r a w
them, and the w o r k will b e represented b y the area o f the
l o o p itself. I f P i n its c i r c u i t g o e s r o u n d t h e l o o p in the
direction o f the hands o f a watch, then the area represents
the w o r k d o n e b y the fluid against external forces ; but if P
g o e s r o u n d t h e l o o p in t h e o p p o s i t e d i r e c t i o n , t h e area o f

Action of the Indicator.
the l o o p r e p r e s e n t s t h e w o r k d o n e b y t h e e x t e r n a l f o r c e s o n
the fluid.
I n the i n d i c a t o r as c o n s t r u c t e d b y W a t t a n d i m p r o v e d b y
M c N a u g h t and R i c h a r d s , the steam or other fluid is p u t i n
connection w i t h a small cylinder containing a piston. When
the fluid p r e s s e s this p i s t o n a n d r a i s e s it, t h e p i s t o n presses
against a spiral spring, so. constructed that the distance
through which the spring is c o m p r e s s e d is proportional
to the pressure o n the piston. I n this w a y t h e h e i g h t o f t h e
p i s t o n o f t h e i n d i c a t o r is at all t i m e s a m e a s u r e o f t h e p r e s s u r e
o f the fluid.
T h e piston also carries a pencil, the p o i n t o f which presses
l i g h t l y a g a i n s t a s h e e t o f p a p e r w h i c h is w r a p p e d r o u n d a
v e r t i c a l c y l i n d e r c a p a b l e o f t u r n i n g r o u n d its a x i s .
T h i s c y l i n d e r is c o n n e c t e d w i t h t h e w o r k i n g p i s t o n o f t h e
engine, o r with s o m e part o f the e n g i n e which m o v e s a l o n g
with t h e p i s t o n , i n s u c h a w a y t h a t t h e a n g l e t h r o u g h w h i c h
the c y l i n d e r t u r n s is always proportional to the distance
t h r o u g h w h i c h t h e w o r k i n g p i s t o n has m o v e d .
I f the i n d i c a t o r is n o t c o n n e c t e d w i t h the steam pipe,
the c y l i n d e r w i l l t u r n b e n e a t h the p o i n t o f the pencil, a n d
a horizontal l i n e w i l l b e d r a w n o n the paper. T h i s line
c o r r e s p o n d s t o o v, a n d is c a l l e d t h e l i n e o f n o p r e s s u r e .
But if the steam b e a d m i t t e d b e l o w the i n d i c a t o r piston,
the p e n c i l w i l l m o v e up and down, while the paper m o v e s
h o r i z o n t a l l y b e n e a t h it, a n d t h e c o m b i n e d m o t i o n w i l l trace
o u t a l i n e o n t h e p a p e r , w h i c h is c a l l e d a n i n d i c a t o r d i a g r a m .
W h e n t h e e n g i n e w o r k s r e g u l a r l y , so that e a c h s t r o k e is
s i m i l a r t o t h e last, t h e p e n c i l w i l l t r a c e o u t t h e s a m e curve
at e v e r y s t r o k e , a n d b y e x a m i n i n g this c u r v e w e m a y learn
much about the action o f the engine. I n particular, the area
of the curve represents the amount o f work done b y the
s t e a m at e a c h s t r o k e o f t h e e n g i n e .
If the indicator had been connected with a p u m p , in
w h i c h t h e e x t e r n a l f o r c e s d o w o r k o n t h e fluid, t h e t r a c i n g
point would move in the opposite direction round the

io6 Stresses and Strains.
diagram, and its area would indicate the amount of work

done on the fluid during the stroke.
Hitherto we have confined our attention to the work done
by the pressure on the piston, and have not been concerned
with the cause of the alteration of volume of the fluid. T h e
increase o f volume may, for anything w e know, arise from
an additional supply being introduced into the cylinder, as
when steam is introduced from the boiler, and the dimi
nution of volume may arise from the escape of the fluid
from the cylinder.
A s we are now going to use the diagram for the purpose
of explaining the properties of bodies when acted on by heat
and b y mechanical force, w e shall suppose that the body,
whether fluid or partly solid, is placed in a cylinder with
one end closed, and that its volume is measured by the
distance o f the piston from the closed end o f the cylinder.
Tf at any instant the volume
of the body is v and its pres
sure p, w e represent this fact
by means o f the point P in the
diagram, drawing o L along
the line o f volumes to repre
sent v, and L p vertical to re
present p.
I n this way the position of
a point in the diagram may be
made to indicate the volume
and the pressure of a body at
any instant.
N o w let the pressure be increased, the temperature re
maining the same, then the volume o f the fluid will be
diminished. ( I t is manifest that an increase o f pressure can
never produce an increase of volume, for in that case the
force would produce a motion in the contrary direction to
that in which it acts, and w e should have a source of inex
haustible energy.)

Elasticity. 107
L e t t h e pressure, t h e r e f o r e , i n c r e a s e f r o m o F t o o G , a n d
let the consequent diminution o f v o l u m e b e from O L to
O M , and c o m p l e t e the rectangle o G Q M .
Then the p o i n t p indicates the original a n d Q the final
c o n d i t i o n o f t h e fluid w i t h r e s p e c t t o p r e s s u r e a n d volume,
a n d a l l t h e i n t e r m e d i a t e states o f t h e fluid will be repre
s e n t e d b y p o i n t s in a l i n e , s t r a i g h t o r c u r v e d , w h i c h j o i n s P
a n d Q.
T h e w o r k d o n e b y t h e p r e s s u r e o n t h e fluid is r e p r e s e n t e d
b y t h e a r e a o f t h e figure p Q M L , w h i c h is o n t h e left hand
o f the t r a c i n g p o i n t as i t m o v e s a l o n g p Q.
I f P F and Q M intersect in R , then p R represents the
actual d i m i n u t i o n o f v o l u m e , a n d R q t h e a c t u a l i n c r e a s e o f
pressure. T h e a c t u a l v o l u m e i s r e p r e s e n t e d b y F P , so t h a t
t h e v o l u m i n a l c o m p r e s s i o n is r e p r e s e n t e d b y t h e r a t i o o f P R
to F p .
DEFINITION O F T H E ELASTICITY OF A FLUID. — The
elasticity of a fluid under any given conditions is the ratio
of any small increase of pressure to the voluminal compression
hereby produced.
S i n c e t h e v o l u m i n a l c o m p r e s s i o n is a n u m e r i c a l quantity,
the e l a s t i c i t y is a q u a n t i t y o f t h e s a m e k i n d as a pressure.
To express the elasticity o f the fluid by means of the
diagram, join p Q b y a s t r a i g h t l i n e , a n d p r o d u c e i t till i t
m e e t s t h e v e r t i c a l l i n e op in E ; t h e n F K is a p r e s s u r e e q u a l
to t h e e l a s t i c i t y o f t h e fluid i n t h e s t a t e r e p r e s e n t e d b y p,
and under c o n d i t i o n s w h i c h cause its s t a t e t o v a r y i n a
m a n n e r r e p r e s e n t e d b y t h e l i n e P Q.
F o r it is p l a i n t h a t F E is t o R Q i n t h e r a t i o o f p F t o P R ,
„. „ R Q i n c r e m e n t o f pressure , .- -.
or F E = — - = .— c . — = elasticity.
p R voluminal compression
p F
H e n c e if the relation b e t w e e n the v o l u m e and the pres
sure o f a fluid u n d e r c e r t a i n c o n d i t i o n s , as f o r i n s t a n c e a t a
g i v e n t e m p e r a t u r e , is r e p r e s e n t e d b y a c u r v e t r a c e d out b y P,
t h e e l a s t i c i t y o f t h e fluid w h e n i n t h e state r e p r e s e n t e d b y p
io8 Isothermal Curves,
may b e found b y drawing p E a tangent t o the c u r v e at P,

and P F a horizontal line. T h e p o r t i o n F E o f t h e vertical
l i n e o p c u t o f f b e t w e e n t h e s e l i n e s r e p r e s e n t s , o n t h e scale
o f p r e s s u r e s , t h e e l a s t i c i t y o f t h e fluid.
We h a v e hitherto supposed t h a t t h e t e m p e r a t u r e o f the
body remains the same during its c o m p r e s s i o n f r o m the
v o l u m e P F to the v o l u m e Q G. T h i s is t h e m o s t common
s u p p o s i t i o n w h e n t h e e l a s t i c i t y o f a fluid is t o b e measured,
B u t i n m o s t b o d i e s a c o m p r e s s i o n p r o d u c e s a rise o f t e m p e
r a t u r e , a n d i f t h e h e a t is n o t a l l o w e d t o e s c a p e , t h e effect o f
this w i l l b e t o m a k e t h e i n c r e m e n t o f p r e s s u r e g r e a t e r than
in t h e c a s e o f c o n s t a n t t e m p e r a t u r e . H e n c e e v e r y substance
has t w o elasticities, o n e c o r r e s p o n d i n g t o constant tempera
ture, a n d t h e o t h e r c o r r e s p o n d i n g t o t h e c a s e w h e r e n o h e a t
is a l l o w e d t o e s c a p e . T h e first v a l u e is a p p l i c a b l e t o stresses
a n d strains w h i c h a r e l o n g c o n t i n u e d , s o that t h e substance
acquires the temperature of surrounding bodies. The
s e c o n d v a l u e is a p p l i c a b l e t o t h e c a s e o f r a p i d l y c h a n g i n g
f o r c e s , as in the case o f the vibrations o f bodies which
p r o d u c e s o u n d s , i n w h i c h t h e r e is n o t t i m e f o r t h e tempe
rature t o b e equalised b y conduction. The elasticity in
t h e s e c a s e s is a l w a y s g r e a t e r t h a n i n t h e case o f uniform
temperature.
CHAPTER V I .
O N LINES O F E Q U A L T E M P E R A T U R E , O R I S O T H E R M A L LINES
O N T H E INDICATOR DIAGRAM.
IF t h e p r e s s u r e is m a d e t o v a r y w h i l e the temperature re

mains constant, the v o l u m e will diminish as the pressure
increases, a n d the point p will trace out a line i n the diagram
w h i c h is c a l l e d a l i n e o f e q u a l t e m p e r a t u r e , o r a n i s o t h e r m a l
line. B y m e a n s o f this l i n e w e c a n s h o w t h e w h o l e b e h a v i o u r

Tlieir Construction. 109
o f the substance u n d e r various pressures at that particular

temperature.
By making experiments on the substance at o t h e r t e m
peratures, and drawing the isothermal lines belonging to
these temperatures, w e c a n express all the relations b e t w e e n
the pressure, v o l u m e , a n d t e m p e r a t u r e o f t h e s u b s t a n c e .
I n the d i a g r a m , e a c h i s o t h e r m a l l i n e s h o u l d b e marked
with the temperature t o w h i c h it corresponds in degrees,
and the lines should b e d r a w n for e v e r y d e g r e e , o r for e v e r y
ten or every hundred d e g r e e s , a c c o r d i n g t o the p u r p o s e for
w h i c h the d i a g r a m is i n t e n d e d .
When the volume and the pressure are known, the
temperature is a d e t e r m i n a t e q u a n t i t y , a n d i t is e a s y t o s e e
how from any t w o o f these three quantities w e can deter
m i n e t h e third. T h u s i f the c u r v e d lines in the diagram
are the lines o f e q u a l temperature, the temperature cor
responding to each b e i n g i n d i c a t e d b y the numeral at the
e n d o f the line, w e can solve three p r o b l e m s b y means of
this d i a g r a m .
r. G i v e n t h e p r e s s u r e a n d t h e v o l u m e , t o find t h e t e m p e
rature.
L a y off o L o n the line o f v o l u m e s to represent the g i v e n
volume, and o F o n t h e l i n e o f pressures t o represent the
g i v e n pressure, t h e n d r a w F P h o r i z o n t a l a n d L P v e r t i c a l , t o
d e t e r m i n e t h e p o i n t p. I f the p o i n t P falls o n o n e o f t h e
fines o f e q u a l t e m p e r a t u r e , t h e n u m e r a l a t t a c h e d t o t h a t l i n e
indicates the temperature. I f t h e p o i n t P falls b e t w e e n t w o
o f the lines, w e must estimate its distance from the two
nearest l i n e s , a n d t h e n as t h e s u m o f t h e s e d i s t a n c e s is t o t h e
distance from the l o w e r l i n e o f t e m p e r a t u r e , so is t h e dif
ference o f t e m p e r a t u r e o f the t w o lines to the excess o f the
true t e m p e r a t u r e a b o v e t h a t o f t h e l o w e r l i n e .
2. G i v e n t h e v o l u m e and temperature to find the pres
sure.
L a y off o L to represent the v o l u m e and draw L P vertical,
and let p b e the p o i n t w h e r e this l i n e cuts t h e l i n e o f t h e

HO Isothermal Curves.
given temperature. Then L P represents the required
pressure.
3. Given the pressure and temperature, to find the
volume.
Fig. 33.
0 L «
Lay o f f o F t o r e p r e s e n t t h e p r e s s u r e and d r a w F P hori
zontal t i l l i t m e e t s t h e l i n e o f t h e g i v e n t e m p e r a t u r e i n P,
then F p represents the r e q u i r e d v o l u m e .
O N T H E F O R M O F T H E ISOTHERMAL CURVES IN DIFFERENT

CASES.
The Gaseous State.
I f t h e s u b s t a n c e is i n t h e g a s e o u s state, as c o m m o n air is
at e v e r y p r e s s u r e and temperature to which w e have been
able to subject it, t h e n i t is e a s y t o d r a w t h e isothermal
curves b y taking a c c o u n t o f the laws o f B o y l e a n d Charles.
By B o y l e ' s l a w t h e p r o d u c t o f t h e v o l u m e a n d t h e p r e s -

Their Characteristics.
sure is a l w a y s the s a m e f o r t h e s a m e t e m p e r a t u r e . Hence,

in t h e c u r v e , t h e a r e a o f t h e r e c t a n g l e o L P F w i l l b e the
same p r o v i d e d p b e a p o i n t i n t h e s a m e i s o t h e r m a l c u r v e .
T h e c u r v e w h i c h has this p r o p e r t y is k n o w n i n g e o m e t r y
b y the n a m e o f t h e r e c t a n g u l a r h y p e r b o l a , t h e l i n e s o v a n d
o / b e i n g t h e a s y m p t o t e s o f t h e h y p e r b o l a s i n fig. 13. The
asymptotes are lines such that a p o i n t t r a v e l l i n g a l o n g the
curve in either direction continually approaches one or
o t h e r o f t h e a s y m p t o t e s , b u t n e v e r r e a c h e s it. T h e physical
i n t e r p r e t a t i o n o f this is t h a t i f a g a s fulfils Boyle's law, a n d
if t h e t e m p e r a t u r e r e m a i n t h e s a m e —
1. S u p p o s e w e travel along the curve in the direction
l e a d i n g t o w a r d o p, that is t o s a y , s u p p o s e the pressure
is g r a d u a l l y increased, then the volume will continually
diminish, b u t a l w a y s s l o w e r a n d s l o w e r ; for, h o w e v e r much
we increase the pressure, w e c a n n e v e r r e d u c e t h e v o l u m e t o
nothing, so that t h e i s o t h e r m a l l i n e w i l l n e v e r r e a c h t h e l i n e
o t h o u g h it c o n t i n u a l l y a p p r o a c h e s i t A t the same time,
if B o y l e ' s l a w is f u l f i l l e d w e c a n always, b y doubling the
pressure, r e d u c e t h e v o l u m e t o o n e half, s o t h a t b y a suffi
cient i n c r e a s e o f p r e s s u r e t h e v o l u m e m a y b e r e d u c e d till i t
is s m a l l e r t h a n a n y p r e s c r i b e d quantity.
2. S u p p o s e we travel in the other direction along the
c u r v e , that is t o s a y , s u p p o s e w e i n c r e a s e t h e v o l u m e o f t h e
vessel w h i c h c o n t a i n s t h e g a s , t h e n t h e point p approaches
nearer a n d n e a r e r t o t h e l i n e o v, b u t n e v e r a c t u a l l y r e a c h e s
it. T h i s s h o w s that the gas will a l w a y s e x p a n d so as t o fill
the v e s s e l , a n d p r e s s u p o n it w i t h a f o r c e r e p r e s e n t e d b y the
distance f r o m o v, a n d t h i s p r e s s u r e , t h o u g h it d i m i n i s h e s as
the v e s s e l is enlarged, will never b e reduced to nothing,
however large the vessel m a y b e c o m e .
Elasticity of a Perfect Gas.—Another property of the
h y p e r b o l a is t h a t i f p E b e d r a w n a t a n g e n t to the curve
at p till i t m e e t s the asymptote, F E = o F. NOW F E
represents the elasticity o f the substance, a n d o F the pres
sure. H e n c e the e l a s t i c i t y o f a p e r f e c t g a s is n u m e r i c a l l y

112 Isothermal Curves.
e q u a l t o t h e p r e s s u r e , w h e n t h e t e m p e r a t u r e is s u p p o s e d to
remain constant during the compression.
The Liquid State.

I n most liquids, the compression p r o d u c e d b y the pres
sures w h i c h w e are a b l e t o a p p l y is e x c e e d i n g l y s m a l l . In
the c a s e o f w a t e r , f o r e x a m p l e , u n d e r o r d i n a r y circumstances
as t o t e m p e r a t u r e , the a p p l i c a t i o n o f a p r e s s u r e e q u a l t o o n e
atmosphere produces a c o m p r e s s i o n o f a b o u t 46 millionth
parts o f the v o l u m e , or o'oooo46. H e n c e i n d r a w i n g an
i n d i c a t o r d i a g r a m for a l i q u i d w e m u s t r e p r e s e n t c h a n g e s o f
v o l u m e on a m u c h larger scale than in the case o f gases, i f
the diagram is to h a v e any v i s i b l e features at all. The
m o s t c o n v e n i e n t w a y is to suppose the line o L to represent,
n o t t h e w h o l e v o l u m e , but t h e e x c e s s o f t h e v o l u m e a b o v e a
t h o u s a n d o r a m i l l i o n o f the units w e e m p l o y .
I t is m a n i f e s t that t h e r e l a t i o n b e t w e e n t h e p r e s s u r e a n d
the v o l u m e o f a n y substance must b e such that n o pressure,
h o w e v e r great, can r e d u c e the v o l u m e t o n o t h i n g . Hence
the isothermal lines cannot b e straight lines, for a straight
l i n e , h o w e v e r s l i g h t l y i n c l i n e d t o t h e l i n e o f n o v o l u m e s o F,
and h o w e v e r distant from it, m u s t c u t t h a t l i n e s o m e w h e r e .
T h e l i m i t e d r a n g e o f pressures w h i c h w e are a b l e t o p r o d u c e
d o e s n o t in s o m e c a s e s c a u s e sufficient c h a n g e o f v o l u m e t o
indicate the curvature of the isothermal lines. We may
s u p p o s e that f o r t h e small p o r t i o n w e are a b l e t o o b s e r v e
t h e y a r e n e a r l y s t r a i g h t lines.
T h e expansion due t o an i n c r e a s e o f t e m p e r a t u r e is a l s o
much smaller in the case o f l i q u i d s than in the case of
gases.
If, therefore, w e w e r e to d r a w the indicator diagram o f a
liquid o n the same scale as t h a t o f a g a s , t h e isothermal
lines w o u l d consist o f a number o f lines v e r y close together,
n e a r l y v e r t i c a l , b u t v e r y s l i g h t l y i n c l i n e d t o w a r d s t h e l i n e o F.
If, h o w e v e r , w e r e t a i n t h e s c a l e o f p r e s s u r e s a n d g r e a t l y
m a g n i f y the scale o f v o l u m e s , the i s o t h e r m a l lines will be

Saturated Vapour. 113
more inclined t o the vertical a n d w i d e r apart, but still v e r y
nearly straight l i n e s . L i q u i d s , h o w e v e r , which are near the
critical p o i n t d e s c r i b e d a t t h e e n d o f this c h a p t e r are m o r e
compressible than e v e n a gas.
The Solid State.

I n solid b o d i e s t h e c o m p r e s s i b i l i t y a n d t h e e x p a n s i o n by
heat are in g e n e r a l s m a l l e r t h a n i n l i q u i d s . T h e i r indicator
diagrams w i l l t h e r e f o r e h a v e t h e s a m e g e n e r a l characteristics
as those o f l i q u i d s .
1
INDICATOR DIAGRAM OF A S U B S T A N C E PART OF WHICH
IS LIQUID A N D PART VAPOUR.
L e t us s u p p o s e t h a t a p o u n d o f w a t e r is p l a c e d i n a v e s s e l
0
and brought t o a g i v e n t e m p e r a t u r e , say 2 1 2 F., and that
by means o f a piston the capacity o f the v e s s e l is made
larger or s m a l l e r , t h e t e m p e r a t u r e r e m a i n i n g the same. If
we suppose t h e v e s s e l t o b e o r i g i n a l l y v e r y l a r g e , say 100 c u b i c
feet, a n d t o b e m a i n t a i n e d at 212° F . , then the w h o l e o f the
water w i l l b e c o n v e r t e d i n t o s t e a m , w h i c h w i l l fill t h e v e s s e l
a n d w i l l e x e r t o n it a p r e s s u r e o f a b o u t 575 pounds' weight
o n the s q u a r e f o o t . I f w e n o w press d o w n the piston, and
so cause t h e c a p a c i t y o f t h e v e s s e l t o d i m i n i s h , t h e pressure
will i n c r e a s e n e a r l y i n t h e s a m e p r o p o r t i o n as t h e volume
diminishes, s o that t h e p r o d u c t o f t h e n u m b e r s representing
the pressure a n d v o l u m e w i l l b e nearly constant. When,
h o w e v e r , t h e v o l u m e is c o n s i d e r a b l y d i m i n i s h e d , this p r o d u c t
b e g i n s t o d i m i n i s h , t h a t is t o s a y , t h e p r e s s u r e d o e s n o t in
crease so fast as i t o u g h t t o d o b y B o y l e ' s l a w i f t h e s t e a m
were a perfect gas. In the d i a g r a m , fig. 14, p . 114, the
0
relations b e t w e e n t h e p r e s s u r e a n d v o l u m e o f s t e a m at 212
are i n d i c a t e d b y the c u r v e a b. T h e pressure in atmo
spheres is m a r k e d o n t h e r i g h t h a n d o f t h e d i a g r a m , a n d t h e
v o l u m e o f o n e p o u n d , in c u b i c feet, at t h e b o t t o m .
W h e n t h e v o l u m e is d i m i n i s h e d t o 26^6 cubic feet the

1
aa 30 40
C U B I C FEET
Isothermals for Steam and Water.

Water and Steam.
pressure is 2,116 lb., so that t h e product o f the volume

and pressure, i n s t e a d o f 57,500, is n o w r e d u c e d to 55,770.
This departure from the l a w o f B o y l e , though n o t v e r y large,
is quite d e c i d e d . T h e pressure and v o l u m e o f the steam in
this state are i n d i c a t e d b y t h e p o i n t b i n t h e d i a g r a m .
I f we now diminish the v o l u m e and still m a i n t a i n the
same t e m p e r a t u r e , t h e p r e s s u r e w i l l n o l o n g e r i n c r e a s e , but
part o f the s t e a m w i l l b e c o n v e r t e d i n t o w a t e r ; a n d as the
volume continues to d i m m i s h , m o r e a n d m o r e o f the steam
will h e c o n d e n s e d into the liquid form, while the pressure
remains e x a c t l y t h e s a m e , n a m e l y , 2,116 pounds' weight on
the square f o o t , o r o n e a t m o s p h e r e . T h i s is i n d i c a t e d b y
the h o r i z o n t a l l i n e b c i n t h e d i a g r a m .
This pressure will c o n t i n u e the same till a l l t h e s t e a m is
0
c o n d e n s e d i n t o w a t e r at 2 1 2 , t h e v o l u m e o f w h i c h w i l l be
0-016 o f a c u b i c f o o t , a q u a n t i t y t o o s m a l l t o b e r e p r e s e n t e d
clearly in t h e d i a g r a m .
A s s o o n as the v o l u m e , t h e r e f o r e , is r e d u c e d t o t h i s v a l u e
there w i l l b e n o m o r e s t e a m t o c o n d e n s e , a n d any further
r e d u c t i o n o f v o l u m e is r e s i s t e d b y t h e e l a s t i c i t y o f w a t e r ,
which, as w e h a v e s e e n , is v e r y l a r g e c o m p a r e d w i t h t h a t o f
a gas.
W e are n o w able to trace the isothermal line for w a t e r
corresponding to the temperature 212°. W h e n v is very
great t h e c u r v e is n e a r l y o f t h e form o f an hyperbola for
which v p = 57,5°°- A s v d i m i n i s h e s , t h e c u r v e falls s l i g h t l y
b e l o w t h e h y p e r b o l a , s o t h a t w h e n v = 26-36, v p = 55,77°·
H e r e , h o w e v e r , the l i n e s u d d e n l y and c o m p l e t e l y alters its
character, a n d b e c o m e s the h o r i z o n t a l straight l i n e b c, f o r
which p = 2,116, and this straight line extends from
v = 26-36 to v = 0-016, when another equally sudden
change takes p l a c e , a n d the line, from b e i n g exactly h o r i z o n
tal, b e c o m e s nearly but not quite vertical, nearly in the
d i r e c t i o n c p, for the pressure must b e increased beyond
the limits o f our experimental methods long before any
very c o n s i d e r a b l e c h a n g e is m a d e i n t h e v o l u m e o f t h e w a t e r .
11
n6 Isothermal Curves.
T h e i s o t h e r m a l l i n e i n a c a s e o f this k i n d c o n s i s t s o f three
parts. I n t h e first part, a b, it r e s e m b l e s t h e i s o t h e r m a l l i n e s o f a
p e r f e c t g a s , b u t as t h e v o l u m e d i m i n i s h e s t h e p r e s s u r e b e g i n s
t o b e s o m e w h a t less t h a n it s h o u l d b e b y B o y l e ' s l a w . This
h o w e v e r , is o n l y w h e n t h e l i n e a p p r o a c h e s t h e s e c o n d part
o f its c o u r s e , be, in w h i c h it is a c c u r a t e l y h o r i z o n t a l . T h i s part
c o r r e s p o n d s t o a s t a t e in w h i c h t h e s u b s t a n c e e x i s t s partly
i n t h e l i q u i d a n d p a r t l y in t h e g a s e o u s s t a t e , a n d it extends
f r o m t h e v o l u m e o f t h e g a s t o t h e v o l u m e o f t h e l i q u i d at
the same temperature and pressure. T h e t h i r d p a r t o f the
i s o t h e r m a l l i n e is t h a t c o r r e s p o n d i n g t o t h e l i q u i d state o f
t h e s u b s t a n c e , a n d it m a y b e c o n s i d e r e d as a l i n e w h i c h o n
the scale o f our diagrams w o u l d be very nearly vertical,
a n d so n e a r t o t h e l i n e c p t h a t i t c a n n o t be distinguished
f r o m it.
In t h e d i a g r a m , fig. 14, t h e i s o t h e r m a l l i n e o f w a t e r for

the t e m p e r a t u r e 2 1 2 ° F . , t h e o r d i n a r y b o i l i n g p o i n t , is r e
p r e s e n t e d b y a b cp, a n d t h a t f o r 30 2° F . b y d ef p.
A t t h e t e m p e r a t u r e o f 3 0 2 ° F . t h e p r e s s u r e at w h i c h c o n
densation t a k e s p l a c e is m u c h g r e a t e r , b e i n g 9,966 p o u n d s '
w e i g h t o n the square foot; and t h e v o l u m e t o w h i c h the
steam is reduced before condensation begins is much
smaller, b e i n g 6 T 5 3 c u b i c feet. T h i s is i n d i c a t e d b y the
point £ A t this p o i n t t h e p r o d u c t v p is 6 r , 3 2 t , w h i c h is
c o n s i d e r a b l y less t h a n 65,209, its v a l u e w h e n t h e v o l u m e is
very great
At this p o i n t c o n d e n s a t i o n b e g i n s a n d g o e s o n till the
w h o l e s t e a m is c o n d e n s e d i n t o w a t e r at 3 0 2 ° F . , t h e v o l u m e
o f w h i c h is o ' o i 6 6 c u b i c feet. T h i s v o l u m e is s o m e w h a t
g r e a t e r t h a n the v o l u m e o f t h e s a m e w a t e r at 212° F .
It appears, therefore, that as t h e temperature rises the
p r e s s u r e at w h i c h c o n d e n s a t i o n o c c u r s is g r e a t e r . It also
a p p e a r s that t h e d i m i n u t i o n o f v o l u m e w h e n condensation
takes place is less t h a n at l o w t e m p e r a t u r e s , a n d this for
t w o reasons. The first is, that t h e steam must be reduced
to a smaller v o l u m e before condensation begins; and the

Steam L ine and Water L ine. 117
s e c o n d is, that the v o l u m e o f t h e l i q u i d w h e n c o n d e n s e d is
greater.
The d o t t e d line in the d i a g r a m indicates the pressures
and the volumes at which condensation b e g i n s at the
various t e m p e r a t u r e s m a r k e d o n the h o r i z o n t a l parts o f the
isothermal l i n e s .
W h e n the pressure and v o l u m e are those indicated by
points a b o v e o r o n t h e r i g h t h a n d o f this c u r v e t h e w h o l e
substance is in t h e g a s e o u s state. W e m a y c a l l this l i n e t h e
steam line. I t is n o t an i s o t h e r m a l l i n e .
I f the s c a l e c f t h e d i a g r a m h a d b e e n l a r g e e n o u g h t o h a v e
represented the v o l u m e o f the c o n d e n s e d water, w e should
have had another d o t t e d l i n e near the line o s u c h that for
points o n t h e left h a n d o f t h i s l i n e t h e w h o l e s u b s t a n c e is in
the l i q u i d state. We may call t h i s t h e water line. For
conditions o f pressure a n d volume indicated by points
between the t w o d o t t e d lines, the s u b s t a n c e is p a r t l y i n t h e
l i q u i d a n d p a r t l y in the g a s e o u s state. I f w e draw a hori
zontal l i n e t h r o u g h the g i v e n p o i n t till it m e e t s the two
dotted lines, then t h e w e i g h t o f steam is t o t h e w e i g h t o f
w a t e r as t h e segment b e t w e e n the point and the water line
is to the s e g m e n t b e t w e e n t h e p o i n t a n d t h e s t e a m l i n e . In
the lower part o f the d i a g r a m f o r c a r b o n i c a c i d , fig. 1 5 ,
p . 120, t h e i s o t h e r m a l l i n e s are s e e n t o c o n s i s t o f a c u r v e d
portion on the right hand representing the gaseous
state, a h o r i z o n t a l p o r t i o n r e p r e s e n t i n g t h e p r o c e s s o f c o n
densation, and a nearly vertical portion representing
the l i q u i d state. The right-hand branch o f the dotted
line, w h i c h w e must here call t h e gas line, corresponds
t o the s t e a m l i n e ; a n d t h e left-hand b r a n c h , o r l i q u i d l i n e ,
corresponds to the water line, which was not distinguish
a b l e in fig. 14.
. Since these t w o lines, w h i c h w e h a v e called the steam line

a n d the w a t e r l i n e , c o n t i n u a l l y a p p r o a c h each o t h e r as the
t e m p e r a t u r e is r a i s e d , t h e q u e s t i o n n a t u r a l l y arises, D o t h e y
ever meet ? T h e peculiarity o f the c o n d i t i o n s indicated by

ri8 IsotJiermal Curves.
p o i n t s b e t w e e n t h e s e l i n e s is t h a t t h e l i q u i d a n d its vapour
c a n e x i s t t o g e t h e r u n d e r t h e s a m e c o n d i t i o n s as t o t e m p e r a -
l u r e a n d p r e s s u r e w i t h o u t t h e v a p o u r b e i n g l i q u e f i e d o r the
liquid evaporated. Outside o f this region the substance
must b e either all v a p o u r o r all liquid.
I f t h e t w o l i n e s m e e t , t h e n at the pressure indicated b y
the point o f meeting there is n o t e m p e r a t u r e at w h i c h the
s u b s t a n c e c a n e x i s t p a r t l y as a l i q u i d a n d p a r t l y as a v a p o u r ,
but the substance must either be entirely c o n v e r t e d from
the state o f v a p o u r i n t o the state o f liquid at o n c e a n d with
out condensation, o r , s i n c e in t h i s c a s e t h e liquid and the
v a p o u r h a v e t h e s a m e d e n s i t y , it m a y b e s u s p e c t e d t h a t the
distinctions we have been accustomed to draw between
liquids and vapours h a v e lost their m e a n i n g .
The a n s w e r t o this q u e s t i o n has b e e n to a great extent
s u p p l i e d b y a series o f v e r y interesting researches.
1
In 1822 M . C a g n i a r d d e l a T o u r o b s e r v e d t h e effect o f
a h i g h t e m p e r a t u r e u p o n l i q u i d s e n c l o s e d in glass tubes o f a
c a p a c i t y n o t m u c h g r e a t e r t h a n t h a t o f t h e l i q u i d itself. He
found that w h e n the t e m p e r a t u r e was raised to a certain
point, the s u b s t a n c e , w h i c h till t h e n w a s p a r t l y l i q u i d and
partly gaseous, suddenly became uniform in appearance
t h r o u g h o u t , w i t h o u t a n y v i s i b l e surface o f s e p a r a t i o n , o r a n y
e v i d e n c e that the s u b s t a n c e i n t h e t u b e w a s p a r t l y in one
state and partly in another.
H e c o n c l u d e d t h a t at this t e m p e r a t u r e the w h o l e b e c a m e
gaseous. T h e t r u e c o n c l u s i o n , as D r . A n d r e w s has s h o w n , is
that the properties o f the liquid and those o f the vapour
c o n t i n u a l l y a p p r o a c h t o s i m i l a r i t y , a n d that, a b o v e a c e r t a i n
temperature, the properties o f the l i q u i d are n o t separated
from those o f the vapour b y any apparent distinction be
tween them.
In 1823, t h e y e a r following the researches of Cagniard
d e la T o u r , F a r a d a y s u c c e e d e d in liquefying s e v e r a l b o d i e s
h i t h e r t o k n o w n o n l y in t h e g a s e o u s f o r m , b y p r e s s u r e a l o n e ,
1 ratf
Annales de Chimie, z série, xxi. et xxii.

Carbonic Acid. 119
and in 1 8 2 6 ' h e g r e a t l y e x t e n d e d our k n o w l e d g e o f the
effects o f t e m p e r a t u r e a n d p r e s s u r e o n g a s e s . H e considers
that a b o v e a c e r t a i n t e m p e r a t u r e , w h i c h , i n t h e l a n g u a g e o f
Dr. A n d r e w s , w e m a y call the critical temperature for the
substance, n o a m o u n t o f pressure will p r o d u c e the pheno
m e n o n w h i c h w e call c o n d e n s a t i o n , a n d he supposes that the
temperature o f 166° F . b e l o w z e r o is p r o b a b l y a b o v e the
critical t e m p e r a t u r e f o r o x y g e n , h y d r o g e n , a n d n i t r o g e n .
D r . A n d r e w s has examined carbonic acid under varied
c o n d i t i o n s o f t e m p e r a t u r e a n d pressure, i n o r d e r t o a s c e r t a i n
the relations of the liquid and gaseous states, a n d has
arrived at t h e c o n c l u s i o n t h a t t h e g a s e o u s a n d l i q u i d states
are o n l y w i d e l y s e p a r a t e d forms o f the same condition o f
matter, a n d m a y b e m a d e t o pass o n e i n t o t h e o t h e r w i t h
1
out a n y i n t e r r u p t i o n o r b r e a c h o f c o n t i n u i t y .
C a r b o n i c a c i d is a s u b s t a n c e w h i c h at ordinary tempera
tures a n d p r e s s u r e s is k n o w n as a g a s . The measurements
o f R e g n a u l t a n d o t h e r s s h o w t h a t as t h e p r e s s u r e increases
the v o l u m e d i m i n i s h e s faster t h a n t h a t o f a g a s w h i c h o b e y s
the l a w o f B o y l e , a n d t h a t as t h e t e m p e r a t u r e rises the ex
p a n s i o n is g r e a t e r t h a n t h a t a s s i g n e d b y t h e l a w o f C h a r l e s .
T h e i s o t h e r m a l l i n e s o f t h e d i a g r a m o f c a r b o n i c a c i d at
ordinary temperatures a n d pressures are therefore s o m e w h a t
flatter and also somewhat w i d e r apart than those o f the
more perfect gases.
T h e d i a g r a m ( p . 120) f o r c a r b o n i c a c i d is t a k e n f r o m D r .
Andrews's paper, with the exception o f the dotted line
showing the r e g i o n within which the substance can exist
as a l i q u i d in p r e s e n c e o f its v a p o u r . T h e base line o f the
d i a g r a m c o r r e s p o n d s , n o t t o z e r o pressure, b u t t o a p r e s s u r e
o f 47 atmospheres.
T h e l o w e s t o f t h e i s o t h e r m a l l i n e s is t h a t o f i 3 ° " i C . o r
SS°-6F._
T h i s l i n e s h o w s t h a t a t a p r e s s u r e o f a b o u t 47 atmospheres
condensation occurs. The s u b s t a n c e is s e e n to become
1
Phil. Trans. 1869, p. 575-

I20 Isothermal Curves.
F I G . 15.
Isothermal? of Carbonio Acid.

Experiments of A ndrews. 121
separated into two distinct portions, the upper portion being

in the state of vapour or gas, and the lower in the state of
liquid. T h e upper surface of the liquid can be distinctly
seen, and where this surface is close to the sides o f the glass
containing the substance it is seen to be curved, as the
surface of water is in small tubes.
As the volume is diminished, more of the substance is
liquefied, till at last the whole is compressed into the liquid
form.
I have described this isothermal line at greater length,
that the student may compare the properties of carbonic acid
at 55°'6 F. with those o f water at 212" F.
1. T h e steam before condensation begins has properties
agreeing nearly, though not quite, with those of a perfect gas.
In carbonic acid the volume just before liquefaction com
mences is little more than three-fifths of that o f a perfect
gas at the same temperature and pressure. T h e corresponding
isothermal lines for air are given in the diagram, and it
will be seen how much the carbonic acid isothermal has
fallen below that of air before liquefaction begins.
2. T h e steam when condensed into water occupies less
than the sixteen-hundredth part o f the volume o f the steam.
The liquid carbonic acid, on the other hand, occupies nearly
a fifth part o f its volume just before condensation. W e are
therefore able to draw the dotted line of complete conden
sation in this diagram, though in the case o f water it would
have required a microscope to distinguish it from the line of
no volume.
3. T h e steam when condensed into water at 2 i 2 ° h a s
properties not differing greatly from those of cold water.
Its dilatability by heat and its compressibility by pressure
are probably somewhat greater than when cold, but not
enough to be noticed when the measurements are not very
precise.
Liquid carbonic acid, as was first observed b y Thilorier,
dilates as the temperature rises to a greater degree than even

a g a s , a n d , as D r . A n d r e w s h a s s h o w n , it y i e l d s t o pressure
m u c h m o r e than a n y ordinary liquid. F r o m Dr. Andrews's
experiments it a l s o a p p e a r s t h a t its compressibility dimi
n i s h e s as t h e p r e s s u r e i n c r e a s e s . T h e s e results are apparent
e v e n in the diagram. I t is, t h e r e f o r e , f a r m o r e c o m p r e s s i b l e
than a n y o r d i n a r y l i q u i d , a n d it a p p e a r s from the experi
m e n t s o f A n d r e w s t h a t its c o m p r e s s i b i l i t y d i m i n i s h e s as the
v o l u m e is r e d u c e d .
I t appears, therefore, that the b e h a v i o u r o f liquid carbonic
a c i d u n d e r t h e a c t i o n o f h e a t a n d p r e s s u r e is v e r y different
from that o f ordinary liquids, and in s o m e respects approaches
to that o f a gas.
I f w e e x a m i n e the n e x t o f the isothermals o f the diagram,
-
that for 2 i ° 5 C . o r 7 o ° 7 F . , the a p p r o x i m a t i o n b e t w e e n the
l i q u i d a n d t h e g a s e o u s s t a t e s is still m o r e a p p a r e n t . Here
condensation takes place at about 6 0 a t m o s p h e r e s o f pres
sure, a n d the l i q u i d o c c u p i e s n e a r l y a t h i r d o f t h e v o l u m e o f
the gas. T h e e x c e e d i n g l y d e n s e g a s is a p p r o a c h i n g i n its
properties to the e x c e e d i n g l y light liquid. S t i l l t h e r e is a
distinct separation b e t w e e n the gaseous and liquid states,
though w e are approaching the critical temperature. This
c r i t i c a l t e m p e r a t u r e has b e e n d e t e r m i n e d b y D r . A n d r e w s t o
-
be 3o Q ,
g2 C . o r 87° 7 F . A t this t e m p e r a t u r e , a n d at a
p r e s s u r e o f f r o m 73 t o 75 a t m o s p h e r e s , c a r b o n i c a c i d a p p e a r s
t o b e in t h e c r i t i c a l c o n d i t i o n . N o separation into liquid and
vapour can b e d e t e c t e d , but at the same t i m e v e r y small
v a r i a t i o n s o f p r e s s u r e o r o f t e m p e r a t u r e p r o d u c e such g r e a t
variations o f density that nickering m o v e m e n t s are o b s e r v e d
in t h e t u b e ' r e s e m b l i n g in an e x a g g e r a t e d f o r m t h e a p p e a r
ances e x h i b i t e d during the mixture o f liquids o f different
densities, or w h e n columns o f heated air ascend through
c o l d e r strata.'
T h e isothermal line for 3 i ° ' i C . o r 88° F . p a s s e s a b o v e

this c r i t i c a l p o i n t . D u r i n g the w h o l e compression the sub
s t a n c e is n e v e r i n t w o d i s t i n c t c o n d i t i o n s i n d i f f e r e n t p a r t s o f
the tube. W h e n t h e p r e s s u r e is less t h a n 73 atmospheres

Continuity of tlte Liquid and Gaseous States. 123
the i s o t h e r m a l l i n e , t h o u g h g r e a t l y flatter t h a n t h a t o f a p e r f e c t
gas, r e s e m b l e s it i n g e n e r a l features. F r o m 73 t o 75 a t m o
spheres t h e v o l u m e d i m i n i s h e s v e r y r a p i d l y , b u t b y n o m e a n s
suddenly, a n d a b o v e this p r e s s u r e t h e v o l u m e diminishes
m o r e g r a d u a l l y t h a n i n t h e c a s e o f a p e r f e c t g a s , b u t still
m o r e r a p i d l y t h a n in m o s t l i q u i d s .
I n the isothermals for 3 2 5 0 ,
C. o r go D ,
5
-
F . a n d for 35° 5 C.
or 95°'9 F . w e c a n still o b s e r v e a s l i g h t i n c r e a s e o f c o m p r e s
sibility near the same part o f the diagram, but in the
isothermal l i n e f o r 48° 1 C. o r ir8°-6 F . t h e c u r v e is c o n
c a v e u p w a r d s t h r o u g h o u t its w h o l e c o u r s e , a n d differs from
the c o r r e s p o n d i n g i s o t h e r m a l l i n e f o r a p e r f e c t g a s o n l y b y
being s o m e w h a t flatter, s h o w i n g that f o r all o r d i n a r y pres
sures t h e v o l u m e is s o m e w h a t less t h a n t h a t a s s i g n e d b y
Boyle's law.
Still at t h e t e m p e r a t u r e o f 118°-6 F . c a r b o n i c a c i d has a l l
the p r o p e r t i e s o f a g a s , a n d t h e effects o f h e a t a n d p r e s s u r e o n
it differ f r o m t h e i r effects o n a p e r f e c t g a s o n l y b y q u a n t i t i e s
r e q u i r i n g careful e x p e r i m e n t s t o d e t e c t t h e m .
We have n o reason t o b e l i e v e that any phenomenon
similar t o condensation would occur, however great a
pressure w e r e a p p l i e d t o c a r b o n i c a c i d at this t e m p e r a t u r e .
I n fact, by a proper management w e can convert car
bonic acid gas into a liquid without any sudden change
o f state.
I f w e b e g i n w i t h c a r b o n i c a c i d g a s a t 5 0 ° F . w e m a y first
heat it till its t e m p e r a t u r e is a b o v e 88° F . , t h e c r i t i c a l p o i n t .
W e then g r a d u a l l y increase t h e pressure to, say, 1 0 0 a t m o
spheres. D u r i n g this p r o c e s s n o s i g n o f l i q u e f a c t i o n o c c u r s .
Finally w e c o o l t h e substance, still u n d e r t h e p r e s s u r e o f
1 0 0 atmospheres, to 5 0 ° F. D u r i n g this p r o c e s s n o s u d d e n
c h a n g e o f state c a n b e o b s e r v e d , b u t c a r b o n i c a c i d at 5 0 ° F .
and u n d e r a p r e s s u r e o f 1 0 0 a t m o s p h e r e s has all t h e p r o
perties o f a liquid. A t the temperature o f 5 0 ° F. w e cannot
convert carbonic acid gas into a liquid without a sudden
c o n d e n s a t i o n , b u t b y this p r o c e s s , in w h i c h t h e p r e s s u r e is

a p p l i e d a t a h i g h t e m p e r a t u r e , w e h a v e c a u s e d t h e substance
to pass from an undoubtedly gaseous to an undoubtedly
l i q u i d state w i t h o u t a t a n y t i m e u n d e r g o i n g a n a b r u p t change
similar t o ordinary liquefaction.
I h a v e d e s c r i b e d t h e e x p e r i m e n t s o f D r . A n d r e w s o n car
b o n i c a c i d at greater length because t h e y furnish the most'
complete v i e w hitherto given o f t h e r e l a t i o n b e t w e e n the
l i q u i d a n d t h e g a s e o u s state, a n d o f t h e m o d e i n w h i c h the
properties o f a gas m a y b e continuously a n d imperceptibly
c h a n g e d into those o f a liquid.
The critical temperatures o f most ordinary liquids are
m u c h h i g h e r t h a n t h a t o f c a r b o n i c a c i d , a n d t h e i r pressure
i n t h e c r i t i c a l state is v e r y g r e a t , s o t h a t e x p e r i m e n t s o n the
c r i t i c a l state o f o r d i n a r y l i q u i d s a r e difficult a n d d a n g e r o u s .
M . C a g n i a r d d e l a T o u r e s t i m a t e d t h e t e m p e r a t u r e a n d pres
sure o f t h e c r i t i c a l state t o b e :
Tenirjerature Pressure
h ahr. (Atmospheres)
Ether 369° 5 37-5
Alcohol 497°'5 H9'0
0
Bisulphide of Carbon . . . 5O4 '5 66-5
Water . . . . . . 773°'o —
In the case o f water the critical temperature w a s so

high that the water b e g a n t o dissolve t h e glass tube which
c o n t a i n e d it.
T h e critical temperature o f w h a t are called the permanent
g a s e s is p r o b a b l y e x c e e d i n g l y l o w , s o t h a t w e c a n n o t b y a n y
known method produce a degree o f cold sufficient, even
when applied along with enormous pressure, to condense
t h e m i n t o t h e l i q u i d state.
1
I t has b e e n suggested b y Professor J a m e s T h o m s o n that
the isothermal curves for temperatures below t h e critical
temperature are o n l y apparently, a n d n o t really, discon
t i n u o u s , a n d that t h e i r t r a e f o r m is s o m e w h a t s i m i l a r i n its
g e n e r a l features t o t h e c u r v e A B C D E F G H K .
T h e p e c u l i a r i t y o f this c u r v e is, that b e t w e e n t h e p r e s s u r e s
1
Proceedings of the Royal Society, 1871, No. 130.

Retardation of boiling and of Condensation. 125
indicated b y the horizontal lines B F and D H , a n y horizon
tal l i n e such as C E G cuts the curve in three different
points. The literal interpretation o f t h i s g e o m e t r i c a l cir
c u m s t a n c e w o u l d b e t h a t t h e fluid at this p r e s s u r e , a n d at
the t e m p e r a t u r e o f t h e i s o t h e r m a l l i n e , is c a p a b l e o f e x i s t i n g
in t h r e e different states. One o f these, indicated by c,
evidently corresponds to the l i q u i d state. A n o t h e r , indi
c a t e d b y G , c o r r e s p o n d s t o t h e g a s e o u s state. A t t h e inter
mediate point E the s l o p e o f the curve indicates that the
volume and the pressure increase and diminish together.
F L G . 16.
N o s u b s t a n c e h a v i n g this p r o p e r t y c a n e x i s t i n s t a b l e e q u i l i
b r i u m , f o r t h e v e r y s l i g h t e s t d i s t u r b a n c e w o u l d m a k e i t rush
into the liquid or the gaseous state. W e may therefore
confine o u r a t t e n t i o n t o t h e p o i n t s c a n d G,
A c c o r d i n g t o t h e t h e o r y o f e x c h a n g e s , as e x p l a i n e d at p . 3 0 3 ,
w h e n t h e l i q u i d is i n c o n t a c t w i t h its v a p o u r t h e r a t e o f e v a p o
ration d e p e n d s o n t h e t e m p e r a t u r e o f the liquid, a n d the rate
of condensation o n the density o f the vapour. H e n c e for
e v e r y t e m p e r a t u r e t h e r e is a d e t e r m i n a t e v a p o u r - d e n s i t y , and
therefore a d e t e r m i n a t e pressure, r e p r e s e n t e d b y the h o r i z o n
tal l i n e c G, at w h i c h t h e e v a p o r a t i o n e x a c t l y b a l a n c e s t h e c o n -
densation. A t t h e p r e s s u r e i n d i c a t e d b y this h o r i z o n t a l line

t h e l i q u i d w i l l b e i n e q u i l i b r i u m w i t h its v a p o u r . A t all greater
p r e s s u r e s t h e v a p o u r , i f i n c o n t a c t w i t h the l i q u i d , w i l l b e c o n
d e n s e d ; a n d at a l l s m a l l e r p r e s s u r e s t h e l i q u i d , i f i n c o n t a c t
w i t h its v a p o u r , w i l l e v a p o r a t e . H e n c e t h e i s o t h e r m a l l i n e , as
d e d u c e d f r o m e x p e r i m e n t s o f t h e o r d i n a r y k i n d , w i l l consist o f
t h e c u r v e A B C, t h e s t r a i g h t l i n e c G, a n d t h e c u r v e a k.
But it has been pointed o u t b y P r o f . J. T h o m s o n that
by suitable contrivances we may detect the existence of
other parts o f the isothermal curve. We k n o w that the
portion of the curve corresponding t o t h e l i q u i d state e x
t e n d s b e y o n d t h e p o i n t C; f o r i f t h e l i q u i d is c a r e f u l l y freed
from air and other impurities, and is n o t in contact with
anything but the sides of a v e s s e l t o w h i c h i t c l o s e l y ad
h e r e s , t h e p r e s s u r e m a y b e r e d u c e d c o n s i d e r a b l y b e l o w that
indicated b y t h e p o i n t c , t i l l at last, at s o m e p o i n t b e t w e e n
c and D , the phenomenon of boiling with bumping com
m e n c e s , as d e s c r i b e d at p . 2 5 .
L e t us n e x t c o n s i d e r t h e s u b s t a n c e w h o l l y i n t h e s t a t e o f
v a p o u r , as i n d i c a t e d b y t h e p o i n t K , a n d l e t i t b e k e p t at the
s a m e t e m p e r a t u r e a n d g r a d u a l l y c o m p r e s s e d t i l l it is in the
s t a t e i n d i c a t e d b y t h e p o i n t G. I f there are any drops of
t h e l i q u i d i n t h e v e s s e l , o r i f t h e v e s s e l is c a p a b l e o f b e i n g
wetted b y the liquid, condensation will n o w begin. But if
there are n o facilities for condensation, the pressure m a y be
increased and the v o l u m e d i m i n i s h e d till the state o f the
v a p o u r is t h a t w h i c h is r e p r e s e n t e d b y t h e p o i n t F . A t this
point condensation must take place i f i t has not begun
1
before.
The e x i s t e n c e o f this variability in the c i r c u m s t a n c e ; of
condensation, though seemingly probable, is not as yet
established b y e x p e r i m e n t , l i k e that o f the variability in the
circumstances o f evaporation. P r o f . J. Thomson suggests
that by investigating the condensation produced by the
rapid expansion of vapour in a vessel p r o v i d e d with a
1
See the chapter on Capillarity.

Adiabatic Curves. 137
steam-jacket, the e x i s t e n c e o f this part o f the isothermal

curve might b e established.
T h e state o f t h i n g s , h o w e v e r , r e p r e s e n t e d b y the p o r t i o n
o f the i s o t h e r m a l curve D E F , can never b e realised in a
h o m o g e n e o u s m a s s , f o r t h e s u b s t a n c e is t h e n i n a n e s s e n t i a l l y
unstable condition, since the pressure increases with the
volume. W e cannot, therefore, expect any experimental
e v i d e n c e o f t h e e x i s t e n c e o f t h i s p a r t o f t h e c u r v e , u n l e s s , as
Prof. J . T h o m s o n suggests, t h i s state o f t h i n g s m a y exist
in some part o f the thin superficial stratum o f transition
from a l i q u i d t o its o w n g a s , i n w h i c h t h e p h e n o m e n a of
capillarity take p l a c e .
CHAPTER VII.
O N T H E P R O P E R T I E S O F A S U B S T A N C E W H E N H E A T
IS P R E V E N T E D F R O M E N T E R I N G O R L E A V I N G I T .
H I T H E R T O w e h a v e considered the properties o f substance

only with respect to the v o l u m e o c c u p i e d b y a p o u n d o f the
s u b s t a n c e , the p r e s s u r e a c t i n g o n e v e r y s q u a r e foot or inch,
and the temperature o f the substance, w h i c h w e h a v e assumed
to b e uniform. W e suppose the temperature measured by a
thermometer, and when, in o r d e r t o c h a n g e t h e s t a t e o f t h e
b o d y , heat m u s t b e s u p p l i e d t o it o r t a k e n f r o m it, w e h a v e
supposed this t o b e d o n e w i t h o u t p a y i n g a n y attention to
the q u a n t i t y o f h e a t required in each case. F o r the actual
measurements o f such quantities o f heat w e must e m p l o y the
processes d e s c r i b e d in our c h a p t e r o n C a l o r i m e t r y , o r others
equivalent to them. Before entering on these considerations,
h o w e v e r , w e s h a l l e x a m i n e t h e v e r y i m p o r t a n t c a s e in w h i c h
the changes which take place are effected without any
passage o f h e a t e i t h e r i n t o t h e s u b s t a n c e f r o m w i t h o u t o r o u t
o f the s u b s t a n c e i n t o o t h e r b o d i e s .
F o r t h e s a k e o f a s s o c i a t i n g t h e s t a t e m e n t b f s c i e n t i f i c facts

128 Adiabalic Curves.
with m e n t a l i m a g e s w h i c h are easily f o r m e d , a n d w h i c h pre-

s e r v e t h e s t a t e m e n t s in a f o r m a l w a y s r e a d y f o r use, w e shall
s u p p o s e t h a t t h e s u b s t a n c e is c o n t a i n e d i n a c y l i n d e r fitted
with a piston, and that b o t h the c y l i n d e r a n d the piston are
absolutely impermeable t o heat, so that n o t o n l y is heat
prevented from getting out or in b y passing completely
through the c y l i n d e r or piston, but n o heat can pass b e t w e e n
the e n c l o s e d substance and the matter o f the c y l i n d e r or
p i s t o n itself.
N o s u b s t a n c e i n n a t u r e is a b s o l u t e l y i r n p e r m e a b l e t o heat,
s o t h a t t h e i m a g e w e h a v e f o r m e d c a n n e v e r b e fully r e a l i s e d ;
b u t it is a l w a y s p o s s i b l e t o a s c e r t a i n , in e a c h p a r t i c u l a r case,
t h a t h e a t has n o t e n t e r e d or left the substance, though the
methods b y w h i c h this is d o n e and the arrangements by
which the c o n d i t i o n is fulfilled are complicated. In the
present discussion it w o u l d o n l y distract our attention from
the most important facts t o d e s c r i b e t h e details o f physical
experiments. W e t h e r e f o r e r e s e r v e a n y d e s c r i p t i o n o f actual
e x p e r i m e n t a l m e t h o d s till w e c a n e x p l a i n t h e m i n c o n n e x i o n
with the principles o n w h i c h they are f o u n d e d . I n explain
i n g t h e s e p r i n c i p l e s w e m a k e u s e o f t h e m o s t s u i t a b l e illus
t r a t i o n s , w i t h o u t a s s u m i n g that t h e y a r e p h y s i c a l l y p o s s i b l e .
W e therefore suppose the substance p l a c e d in a cylinder,

a n d its v o l u m e a n d pressure regulated and measured by a
piston, and w e suppose that during the changes o f v o l u m e
and pressure o f the substance n o heat either enters i t or
l e a v e s it.
I n order to represent the relation b e t w e e n the v o l u m e and
the pressure, w e suppose a curve traced on the indicator
d i a g r a m d u r i n g t h e m o t i o n o f t h e p i s t o n , e x a c t l y as i n the
case o f the isothermal lines formerly described. T h e only
difference is t h a t w h e r e a s in the case o f the isothermal
lines the s u b s t a n c e w a s m a i n t a i n e d a l w a y s at o n e a n d the
sume temperature, in the present case n o heat is allowed
to enter o r l e a v e t h e s u b s t a n c e , w h i c h , as w e shall s e e , is
a c o n d i t i o n o f quite a different kind.

Their Definition.
T h e line d r a w n o n the i n d i c a t o r d i a g r a m in the latter case

has b e e n n a m e d b y Professor R a n k i n e an A d i a b a t i c line,
because it is d e f i n e d b y t h e c o n d i t i o n t h a t h e a t is n o t a l l o w e d
to pass through (StafiaiveLi') t h e v e s s e l w h i c h c o n f i n e s the
substance.
Since the properties o f the substance u n d e r this c o n d i t i o n
are c o m p l e t e l y d e f i n e d b y its a d i a b a t i c l i n e s , it w i l l assist us
in understanding these properties i f w e associate t h e m w i t h
the c o r r e s p o n d i n g features o f t h e a d i a b a t i c l i n e s .
T h e first t h i n g t o b e o b s e r v e d is t h a t as t h e v o l u m e d i m i
nishes the pressure i n v a r i a b l y i n c r e a s e s . I n fact, i f u n d e r a n y
circumstances t h e p r e s s u r e w e r e t o d i m i n i s h as t h e v o l u m e
diminishes, t h e s u b s t a n c e w o u l d b e i n a n u n s t a b l e state, a n d
would either c o l l a p s e o r e x p l o d e till i t a t t a i n e d a c o n d i t i o n
in w h i c h t h e p r e s s u r e i n c r e a s e d as t h e v o l u m e d i m i n i s h e d .
H e n c e the a d i a b a t i c l i n e s s l o p e d o w n w a r d s f r o m left to
right in the i n d i c a t o r d i a g r a m as w e h a v e d r a w n it.
I f the p r e s s u r e b e c o n t i n u a l l y i n c r e a s e d , u p t o t h e g r e a t e s t
pressure w h i c h w e can produce, the volume continually
diminishes, b u t a l w a y s s l o w e r a n d s l o w e r , so t h a t w e c a n n o t
tell w h e t h e r t h e r e is o r is n o t a l i m i t i n g v o l u m e such t h a t n o
pressure, h o w e v e r g r e a t , c a n c o m p r e s s t h e s u b s t a n c e t o a
smaller v o l u m e .
W e cannot, in fact, trace the lines upward beyond a
certain d i s t a n c e , a n d t h e r e f o r e w e c a n n o t a s s e r t a n y t h i n g o f
the upper p a r t o f t h e i r c o u r s e , e x c e p t t h a t t h e y c a n n o t r e c e d e
from the l i n e o f p r e s s u r e s , b e c a u s e i n t h a t c a s e t h e v o l u m e
would increase o n a c c o u n t o f an increase o f pressure.
If, on t h e o t h e r h a n d , w e s u p p o s e t h e p i s t o n t o b e d r a w n
out so as t o a l l o w t h e v o l u m e t o i n c r e a s e , t h e p r e s s u r e will
diminish.
I f the s u b s t a n c e is i n t h e g a s e o u s f o r m , o r a s s u m e s t h a t
form d u r i n g t h e p r o c e s s , t h e s u b s t a n c e w i l l c o n t i n u e t o e x e r t
pressure o n t h e p i s t o n e v e n t h o u g h t h e v o l u m e is e n o r m o u s l y
increased, a n d w e h a v e n o experimental reason to believe
that the p r e s s u r e w o u l d b e r e d u c e d t o n o t h i n g , h o w e v e r m u c h
K

Adiabatic Curves.
the v o l u m e w e r e increased. F o r gaseous bodies, therefoie,

the lines' e x t e n d i n d e f i n i t e l y in the direction of the l i n e of
v o l u m e s , c o n t i n u a l l y a p p r o a c h i n g b u t n e v e r r e a c h i n g it.
W i t h r e s p e c t t o s u b s t a n c e s w h i c h a r e n o t o r i g i n a l l y in the
g a s e o u s f o r m , s o m e o f t h e m , w h e n t h e p r e s s u r e is sufficiently
d i m i n i s h e d , are k n o w n t o a s s u m e t h a t f o r m , a n d it is plausibly
a r g u e d that w e h a v e n o e v i d e n c e that any substance, h o w e v e r
solid and h o w e v e r c o l d , if entirely free from e x t e r n a l pres
sure, w o u l d n o t sooner o r later b e c o m e dissipated through
space b y a k i n d o f evaporation.
The s m e l l b y w h i c h s u c h m e t a l s as i r o n a n d c o p p e r m a y
be recognised is adduced as an indication that bodies,
apparently very fixed, are continually throwing off portions
o f t h e m s e l v e s i n s o m e v e r y a t t e n u a t e d f o r m , a n d i f in these
cases w e h a v e n o m e a n s o f detecting the effluvium except by
the smell, i n o t h e r cases w e m a y b e d e p r i v e d o f this e v i d e n c e
by the circumstance that the e f f l u v i u m d o e s n o t affect our
sense o f s m e l l at all.
B e this a s i t m a y , t h e r e a r e m a n y s u b s t a n c e s t h e pressure
of which seems to cease entirely when the volume has
F I G . «T- reached a certain value. Be-
( yond this the pressure, i f it
\ e x i s t s , is far t o o small to b e
\\ measured. T h e l i n e s o f such
\ ^ substances may without sen
's "--isothermal sible error be considered as
S
"V^__Adkbati6 meeting the line of volumes
« w i t h i n the limits o f the diagram.
The n e x t t h i n g t o b e o b s e r v e d a b o u t t h e a d i a b a t i c l i n e s is
that w h e r e they cross the isothermal lines t h e y are always
i n c l i n e d at a g r e a t e r a n g l e t o the horizontal line than the
isothermal lines.
In other w o r d s , to diminish the v o l u m e o f a substance b y
a g i v e n a m o u n t requires a greater increase o f pressure w h e n
t h e s u b s t a n c e is p r e v e n t e d f r o m g a i n i n g o r l o s i n g h e a t t h a n
w h e n it is k e p t at a c o n s t a n t temperature.

Their Relation to the Isothermals. 131
T h i s is an i l l u s t r a t i o n o f t h e g e n e r a l p r i n c i p l e t h a t w h e n
the state o f a b o d y is c h a n g e d i n a n y w a y b y t h e a p p l i c a t i o n
o f force i n a n y f o r m , a n d i f i n o n e c a s e t h e b o d y is s u b j e c t e d
t o s o m e c o n s t r a i n t , w h i l e i n a n o t h e r c a s e it is f r e e f r o m this
constraint b u t similarly c i r c u m s t a n c e d in all other respects,
then i f d u r i n g t h e c h a n g e t h e b o d y t a k e s a d v a n t a g e o f this
f r e e d o m , less f o r c e w i l l b e r e q u i r e d t o p r o d u c e t h e c h a n g e
than w h e n t h e b o d y is s u b j e c t e d t o c o n s t r a i n t .
I n the c a s e b e f o r e us w e m a y s u p p o s e the condition of
constant t e m p e r a t u r e t o b e o b t a i n e d b y m a k i n g t h e c y l i n d e r
of a substance w h i c h is a p e r f e c t c o n d u c t o r o f heat, and
surrounding it w i t h a v e r y l a r g e b a t h o f a fluid w h i c h is a l s o a
perfect c o n d u c t o r o f h e a t , a n d w h i c h has so g r e a t a c a p a c i t y
for heat that a l l t h e h e a t it r e c e i v e s f r o m or g i v e s o f f t o t h e sub
stance in the c y l i n d e r d o e s n o t s e n s i b l y a l t e r its t e m p e r a t u r e .
T h e c y l i n d e r i n this c a s e is c a p a b l e o f c o n s t r a i n i n g the
substance itself, b e c a u s e i t c a n n o t g e t t h r o u g h t h e sides o f
the c y l i n d e r ; b u t it is n o t c a p a b l e o f c o n s t r a i n i n g t h e h e a t o f
the substance, w h i c h c a n p a s s f r e e l y o u t o r i n t h r o u g h the
walls o f the c y l i n d e r .
I f w e n o w suppose the walls o f the cylinder t o b e c o m e
perfect n o n - c o n d u c t o r s o f h e a t , e v e r y t h i n g r e m a i n s t h e s a m e ,
e x c e p t that the h e a t is n o l o n g e r f r e e t o p a s s i n t o o r o u t o f
the c y l i n d e r .
I f in the first c a s e t h e m o t i o n o f t h e p i s t o n g i v e s rise to
any m o t i o n o f t h e heat through the walls, then in the
s e c o n d c a s e , w h e n this m o t i o n is p r e v e n t e d , m o r e f o r c e w i l l
be r e q u i r e d t o p r o d u c e a g i v e n m o t i o n o f t h e c y l i n d e r on
a c c o u n t o f t h e g r e a t e r c o n s t r a i n t o f t h e s y s t e m o n w h i c h the
force acts.
F r o m this w e m a y d e d u c e t h e effect w h i c h t h e c o m p r e s s i o n
o f a s u b s t a n c e has o n its t e m p e r a t u r e w h e n h e a t is p r e v e n t e d
from e n t e r i n g o r l e a v i n g t h e substance.
• W e h a v e seen that in e v e r y case the pressure increases
m o r e t h a n it d o e s w h e n t h e t e m p e r a t u r e r e m a i n s c o n s t a n t , o r
if the i n c r e a s e o f p r e s s u r e b e s u p p o s e d g i v e n , t h e d i m i n u t i o n
k"2

Adiabatic Curved
F I G . I8.
Thermal Lines for A i r .

IsotlLtu m a i s
Adiaba t i c s - - -

Effect of Pressure on Temperature. 133
of v o l u m e is l e s s w h e n the heat is c o n f i n e d . Hence the

v o l u m e after t h e p r e s s u r e is a p p l i e d is g r e a t e r w h e n t h e h e a t
is c o n f i n e d t h a n w h e n t h e t e m p e r a t u r e is c o n s t a n t .
F a r the g r e a t e r n u m b e r o f s u b s t a n c e s e x p a n d w h e n t h e i r
t e m p e r a t u r e is r a i s e d , s o t h a t for t h e s a m e p r e s s u r e a g r e a t e r
volume corresponds to a higher temperature. I n t h e s e sub
stances, t h e r e f o r e , c o m p r e s s i o n p r o d u c e s a rise o f t e m p e r a t u r e
if heat is n o t allowed to e s c a p e ,· b u t i f the walls o f the
cylinder p e r m i t t h e p a s s a g e o f h e a t , as s o o n as t h e tempe
rature has b e g u n t o rise h e a t w i l l b e g i n to. f l o w o u t , so t h a t
if the c o m p r e s s i o n is e f f e c t e d s l o w l y t h e p r i n c i p a l thermal
effect o f the c o m p r e s s i o n w i l l b e t o m a k e the s u b s t a n c e p a r t
with s o m e o f its h e a t . T h e isothermal and adiabatic lines
of air are g i v e n i n fig. 18, p . 132. T h e adiabatic lines are
more inclined to the horizontal than t h e isothermal lines.
T h e r e are, h o w e v e r , certain substances w h i c h contract

instead of expanding when their temperature is raised.
W h e n pressure is a p p l i e d t o t h e s e s u b s t a n c e s t h e c o m p r e s s i o n
p r o d u c e d is, as i n t h e f o r m e r c a s e , l e s s w h e n h e a t is p r e
v e n t e d from p a s s i n g t h a n w h e n t h e t e m p e r a t u r e is m a i n t a i n e d
constant. T h e v o l u m e after t h e a p p l i c a t i o n o f p r e s s u r e is
therefore, as b e f o r e , g r e a t e r t h a n w h e n t h e t e m p e r a t u r e is c o n
stant ; b u t s i n c e i n t h e s e s u b s t a n c e s a n i n c r e a s e o f v o l u m e
indicates a fall o f t e m p e r a t u r e , it f o l l o w s that, i n s t e a d o f b e i n g
heated, t h e y are c o o l e d b y c o m p r e s s i o n , a n d that, i f t h e w a l l s
of the c y l i n d e r p e r m i t t h e p a s s a g e o f h e a t , h e a t w i l l flow i n
from w i t h o u t t o r e s t o r e t h e e q u i l i b r i u m o f t e m p e r a t u r e .
D u r i n g a* c h a n g e o f s t a t e , w h e n , at a g i v e n p r e s s u r e , the
v o l u m e alters c o n s i d e r a b l y w i t h o u t c h a n g e o f t e m p e r a t u r e , as
successive p o r t i o n s o f t h e s u b s t a n c e p a s s f r o m t h e o n e state
t o the o t h e r , t h e i s o t h e r m a l l i n e s a r e , as w e h a v e already
remarked, horizontal. The adiabatic lines, h o w e v e r , are
inclined downwards from left to right. A n y increase of
pressure w i l l c a u s e a p o r t i o n o f t h e substance t o pass into
that o n e o f t h e t w o states i n w h i c h its v o l u m e is least. In
so d o i n g it w i l l g i v e o u t h e a t if, as in t h e case o f a l i q u i d a n d
its v a p o u r , t h e s u b s t a n c e g i v e s o u t h e a t i n p a s s i n g i n t o t h e

134 Adiabatic Curves.
d e n s e r s t a t e ; b u t if, as i n t h e c a s e o f i c e a n d w a t e r , the ice

r e q u i r e s h e a t t o m e l t it i n t o t h e d e n s e r f o r m o f w a t e r , then
an increase o f pressure will cause s o m e o f t h e i c e t o melt,
and the mixture will b e c o m e colder.
T h e isothermal and adiabatic lines for steam in presence
o f w a t e r a r e g i v e n i n fig. 19, p . 135. T h e i s o t h e r m a l lines
are here horizontal.
The steam l i n e v v, w h i c h i n d i c a t e s t h e v o l u m e o f o n e
p o u n d o f s a t u r a t e d s t e a m , is a l s o d r a w n o n t h e d i a g r a m . Its
inclination to t h e h o r i z o n t a l l i n e is less t h a n t h a t o f the
adiabatic lines. H e n c e when n o heat is a l l o w e d t o escape,
an increase o f pressure causes s o m e o f the w a t e r to b e c o m e
steam, and a diminution o f pressure causes s o m e o f the
steam to b e c o n d e n s e d into water. T h i s w a s first s h o w n b y
Clausius a n d R a n k i n e .
By means of diagrams of the isothermal and adiabatic
lines the thermal properties of a substance can be com
p l e t e l y d e f i n e d , as w e shall s h o w i n t h e s u b s e q u e n t chapters
A s a s c i e n t i f i c m e t h o d , this m o d e o f r e p r e s e n t i n g t h e p r o
p e r t i e s o f t h e s u b s t a n c e is b y far t h e b e s t , b u t i n o r d e r to
interpret the diagrams, s o m e k n o w l e d g e o f thermodynamics
is r e q u i r e d . A s a m e r e a i d t o the student in remembering
the p r o p e r t i e s o f a s u b s t a n c e , t h e f o l l o w i n g m o d e o f t r a c i n g
t h e c h a n g e s o f v o l u m e a n d t e m p e r a t u r e at a c o n s t a n t pres
sure may be found useful, though it is q u i t e destitute of
those scientific merits w h i c h r e n d e r the indicator diagrams
so v a l u a b l e i n t h e i n v e s t i g a t i o n o f p h y s i c a l p h e n o m e n a .
T h e d i a g r a m o n p . 137 r e p r e s e n t s the effect o f the appli

cation o f heat to a p o u n d o f i c e at 0 ° F . T h e quantity o f
h e a t a p p l i e d t o t h e i c e is i n d i c a t e d b y t h e d i s t a n c e measured
J
a l o n g the base line m a r k e d ' units o f heat. The volume
of the substance is i n d i c a t e d by the length of the per
pendicular from the base line cut off by the 'line of
volume,' and the temperature .is indicated b y the length
cut o f f b y the d o t t e d ' l i n e o f temperature.'
The specific heat o f i c e is a b o u t o'5, so t h a t i t requires
16 units o f h e a t t o r a i s e its t e m p e r a t u r e f r o m 0 ° F . t o 32° F .
0
T h e s p e c i f i c g r a v i t y o f i c e at 3 2 F . is, a c c o r d i n g t o B u n s e n ,
Adiabatic Curves. 13 S
Thermal Lines of Steam and Water.

Tsothcrmals • •
Adiabaties - - —.
Steam L i n e v v

3°" Diagram of Effects of Heat.
0-91674, so t h a t its v o l u m e , as c o m p a r e d w i t h w a t e r at 39°-i,
is 1 '0908.
The ice n o w begins to melt, the temperature remains
constant at 32° F . , but the v o l u m e o f ice diminishes and
the volume of water increases, as is r e p r e s e n t e d by the
line marked 'volume o f ice.' The latent h e a t o f i c e is
0
144 F . , s o t h a t t h e p r o c e s s o f m e l t i n g g o e s o n t i l l 1 4 4 units
of heat have b e e n applied to the substance, a n d the w h o l e
is c o n v e r t e d i n t o w a t e r at 3 2 ° F .
The volume of the water at 32° F. is, a c c o r d i n g to
M\ Despretz, i'oooi27. I t s s p e c i f i c h e a t is a t this tem
perature a v e r y little greater t h a n u n i t y ; i t is e x a c t l y unity
at 39°'i F., and as t h e t e m p e r a t u r e rises t h e s p e c i f i c h e a t
i n c r e a s e s , s o t h a t t o h e a t t h e w a t e r f r o m 3 2 ° F . t o 212° F .
requires 182 units instead of 180. T h e volume of the
water diminishes as t h e temperature rises from 32° F . to
3 9 ° ' i F . , w h e r e i t is e x a c t l y 1. I t t h e n e x p a n d s , s l o w l y at
0
first, b u t m o r e r a p i d l y as t h e t e m p e r a t u r e rises, till at 2 1 2 F
' h e v o l u m e o f t h e w a t e r is 1'04315.
I f w e continue to apply heat to the water, the pressure

b e i n g still t h a t o f t h e a t m o s p h e r e , t h e w a t e r b e g i n s t o boil.
For e v e r y unit o f heat, o n e nine hundred and sixty-fifth
part o f the p o u n d o f w a t e r is b o i l e d a w a y a n d is c o n v e r t e d
i n t o s t e a m , t h e v o l u m e o f w h i c h is a b o u t 1,700 t i m e s that o f
t h e w a t e r f r o m w h i c h it w a s f o r m e d . T h e diagram might be
e x t e n d e d on a larger sheet o f p a p e r t o represent the w h o l e
process o f b o i l i n g the water away. T h i s process w o u l d re
q u i r e 965 u n i t s o f h e a t , so t h a t t h e w h o l e l e n g t h o f t h e b a s e
l i n e f r o m o w o u l d b e 11-07 i n c h e s . A t this p o i n t t h e w a t e r
would be all b o i l e d away, a n d the steam w o u l d occupy a
v o l u m e o f 1,700 t i m e s t h a t o f t h e w a t e r , T h e vertical line
on the diagram which w o u l d represent t h e v o l u m e o f the
steam w o u l d b e 3,400 i n c h e s , o r m o r e t h a n 286 feet long.
T h e t e m p e r a t u r e w o u l d b e still 212° F . I f w e continue to
apply heat t o the s t e a m , still at t h e atmospheric pressure,
its t e m p e r a t u r e w i l l rise i n a perfectly uniform manner at

138 Heat Engines.
-
the rate o f 2° o8 degrees for every unit of heat, the specific
heat of steam being o'4.8c>5.
T h e volume of the superheated steam also increases in a
regular manner, being proportional to its absolute tempe
rature reckoned from — 4 6 0 ° F .
CHAPTER VIII.
ON HEAT ENGINES.
H I T H E R T O the only use we have made o f the indicator

diagram is to explain the relation between the volume and the
pressure of a substance placed in certain thermal conditions.
The condition that the temperature is constant gave us the
isothermal lines, and the condition that no communication
of heat takes place gave us the adiabatic lines. W e have
now to consider the application of the same method to the
measurements of quantities of heat and quantities of me
chanical work.
A t p. 1 0 2 it was shown that if the pencil of the indicator
moves from B to c, this shows that the volume o f the sub
stance has increased from o b to 0 c, under a pressure which
was originally B b and finally c c.
T h e work done by the pressure o f the substance against
the piston during this motion is represented by the area
B c c b, and since the volume increases during the process,
it is the substance which does the work on the piston,
and not the piston which does the work on the substance.
In heat engines of ordinary construction, such as steam
engines and air engines, the form of the path described by
the pencil depends on the mechanical arrangements o f the
engine, such as the opening and shutting of the valves which
admit or carry off the steam.
For the purposes of scientific illustration, and for obtaining
clear views of the dynamical theory of heat, w e shall describe

Carnot's Engine. 139
the working of an engine of a species entirely imaginary—
one which it is impossible to construct, but very easy to
understand.
This engine was invented and described by Sadi Camot,
in his ' Reflexions sur la Puissance motrice du Peu,' pub
lished in 1824. I t is called Carnot's Reversible Engine for
reasons which we shall explain.
All the arrangements connected with this engine are con
trived for the sake of being explained, and are not intended
to represent anything in thé working of real engines.
Camot himself was a believer in the material nature of
heat, and was in consequence led to an erroneous statement
of the quantities of heat which must enter and leave the
engine. As our object is to understand the theory o f heat,
and not to give an historical account of the theory, we shall
avail ourselves of the important step which C a m o t made,
while we avoid the error into which he fell.
T
B
COLD
Let D be the working substance, which may be any sub

stance whatever which is in any way affected by heat, but,
for the sake of precision, we shall suppose it to be either air
or steam, or partly steam and partly condensed water at the
same temperature.
The working substance is contained in a cylinder fitted
with a piston. T h e walls of the cylinder and the pistou are

140 Heat Engines.
supposed to be perfect non-conductors o f heat, but the
b o t t o m o f t h e c y l i n d e r is a p e r f e c t c o n d u c t o r o f heat, a n d has
s o s m a l l a c a p a c i t y for h e a t that t h e a m o u n t o f h e a t r e q u i r e d
t o r a i s e its t e m p e r a t u r e m a y b e left o u t o f a c c o u n t . A l l the
c o m m u n i c a t i o n o f heat b e t w e e n the w o r k i n g substance and
things outside the c y l i n d e r is supposed to take place
t h r o u g h this c o n d u c t i n g b o t t o m , a n d t h e q u a n t i t i e s o f heat
a r e s u p p o s e d t o b e m e a s u r e d as t h e y p a s s t h r o u g h .
A and n are two b o d i e s the temperatures o f w h i c h are
maintained uniform. A is k e p t a l w a y s h o t , at a t e m p e r a t u r e
s, a n d B is k e p t a l w a y s c o l d , at a t e m p e r a t u r e T . c is a
s t a n d t o set t h e c y l i n d e r o n , t h e u p p e r s u r f a c e o f w h i c h is a
perfect non-conductor o f heat.
L e t us s u p p o s e t h a t t h e w o r k i n g s u b s t a n c e is at the t e m
perature T o f the cold body E, a n d t h a t its v o l u m e and
F l G 2 a p r e s s u r e a r e r e p r e s e n t e d i n the in
d i c a t o r d i a g r a m b y o a a n d a A , the
p o i n t A b e i n g o n the isothermal line
A D corresponding to the lower tem
p e r a t u r e T.
First Operation.—We now place
the cylinder o n the non-conducting
s t a n d c, s o t h a t n o h e a t c a n e s c a p e ,
and w e then force the piston d o w n ,
so as t o d i m i n i s h t h e v o l u m e o f the
substance. A s n o heat can escape,
t h e t e m p e r a t u r e rises, a n d t h e rela
tion b e t w e e n v o l u m e and pressure
at a n y i n s t a n t w i l l b e e x p r e s s e d b y
t h e p e n c i l t r a c i n g t h e a d i a b a t i c l i n e A B.
W e c o n t i n u e this p r o c e s s till t h e t e m p e r a t u r e has r i s e n t o
s, t h a t o f t h e h o t b o d y A . D u r i n g this p r o c e s s w e h a v e e x
p e n d e d an a m o u n t of w o r k o n the substance w h i c h is r e
p r e s e n t e d b y t h e a r e a A B b a. I f w o r k is r e c k o n e d n e g a t i v e
w h e n i t is s p e n t on the substance, w e must regard that
e m p l o y e d i n this first o p e r a t i o n as n e g a t i v e .

Carito?s Four Operations. 141
Second Operation.—We n o w transfer t h e c y l i n d e r t o the
h o t b o d y A, a n d a l l o w t h e p i s t o n g r a d u a l l y t o rise. The
i m m e d i a t e effect o f the expansion o f the substance is t o
m a k e its t e m p e r a t u r e fall, b u t as s o o n as the temperature
b e g i n s t o fall, h e a t flows i n f r o m t h e h o t b o d y A t h r o u g h t h e
perfectly c o n d u c t i n g b o t t o m , a n d k e e p s the t e m p e r a t u r e from
falling b e l o w t h e t e m p e r a t u r e s.
T h e s u b s t a n c e w i l l t h e r e f o r e e x p a n d at t h e t e m p e r a t u r e s,
a n d the p e n c i l w i l l t r a c e o u t t h e l i n e B C, w h i c h is p a r t o f the
i s o t h e r m a l l i n e c o r r e s p o n d i n g t o t h e u p p e r t e m p e r a t u r e s.
During this p r o c e s s t h e s u b s t a n c e is d o i n g w o r k b y its
pressure o n the p i s t o n . T h e amount o f this w o r k is r e
presented b y the area B C c 6, a n d it is t o b e r e c k o n e d
positive.
A t the s a m e t i m e a certain a m o u n t o f heat, w h i c h w e shall
call 11, has p a s s e d from the hot b o d y A i n t o the working
substance.
Third Operation.—The c y l i n d e r is n o w t r a n s f e r r e d f r o m t h e
h o t b o d y A t o t h e n o n - c o n d u c t i n g b o d y c, a n d t h e p i s t o n is
allowed t o rise. T h e indicating pencil will trace out the
a d i a b a t i c l i n e c D , s i n c e t h e r e is n o c o m m u n i c a t i o n o f heat,
a n d t h e t e m p e r a t u r e w i l l fall during the process. When
the t e m p e r a t u r e has fallen to T , that of the cold body,
let the o p e r a t i o n b e s t o p p e d . T h e pencil will then have
a r r i v e d at D , a p o i n t o n t h e i s o t h e r m a l l i n e f o r t h e lower
t e m p e r a t u r e T.
T h e w o r k d o n e b y the substance d u r i n g this p r o c e s s is
r e p r e s e n t e d b y t h e a r e a c D d c, a n d is p o s i t i v e .
Fourth Operation.—The c y l i n d e r is p l a c e d o n t h e cold
b o d y B. I t has t h e s a m e t e m p e r a t u r e as B , s o t h a t t h e r e is n o
transfer o f h e a t . B u t as s o o n a s w e b e g i n t o p r e s s d o w n t h e
p i s t o n h e a t f l o w s f r o m t h e w o r k i n g s u b s t a n c e i n t o B , s o that
the temperature remains sensibly equal to x during the
operation. T h e piston must be forced down till i t has
r e a c h e d t h e p o i n t at w h i c h it w a s at t h e b e g i n n i n g o f t h e
first o p e r a t i o n , a n d , s i n c e t h e t e m p e r a t u r e is a l s o t h e s a m e ,

142 Heat Engines.
the pressure will be the same as a t first. The working
s u b s t a n c e , t h e r e f o r e , after t h e s e f o u r o p e r a t i o n s , h a s returned
e x a c t l y t o its o r i g i n a l s t a t e as r e g a r d s v o l u m e , p r e s s u r e , and
temperature.
D u r i n g t h e f o u r t h o p e r a t i o n , i n w h i c h t h e p e n c i l t r a c e s the
portion D A o f the isothermal line for the l o w e r temperature,
the piston d o e s w o r k o n the substance, the a m o u n t o f which
is t o b e r e c k o n e d n e g a t i v e , a n d w h i c h is r e p r e s e n t e d b y the
a r e a D A a d.
A t t h e s a m e t i m e a c e r t a i n a m o u n t o f h e a t , w h i c h w e shall
d e n o t e b y h, has f l o w e d f r o m t h e w o r k i n g s u b s t a n c e i n t o the
cold b o d y B.
D E F I N I T I O N O F A CYCXF..—A series of operations by ivhich
the substance isfinallybrought to the same state in all respec
as atfirstis called a Cycle of operations.
Total Work done during the Cycle.—When t h e p i s t o n is
r i s i n g t h e s u b s t a n c e is g i v i n g o u t w o r k · this is t h e c a s e i n
the s e c o n d and third operations. W h e n t h e p i s t o n is s i n k i n g it
is p e r f o r m i n g w o r k o n t h e s u b s t a n c e w h i c h is t o b e r e c k o n e d
negative. H e n c e , t o find t h e w o r k p e r f o r m e d b y t h e s u b s t a n c e
w e m u s t s u b t r a c t t h e a r e a D A B b d, r e p r e s e n t i n g t h e n e g a t i v e
work, from t h e p o s i t i v e w o r k , B C D d b. T h e remainder,
A B c D, r e p r e s e n t s t h e useful w o r k p e r f o r m e d by- t h e sub
s t a n c e d u r i n g the c y c l e o f o p e r a t i o n s . I f w e h a v e a n y diffi
c u l t y in u n d e r s t a n d i n g h o w this amount o f w o r k can be
o b t a i n e d i n a useful f o r m d u r i n g t h e w o r k i n g o f t h e e n g i n e ,
w e h a v e o n l y to suppose that the piston w h e n it rises is
e m p l o y e d in lifting weights, a n d that a p o r t i o n o f the weight
lifted is e m p l o y e d t o f o r c e t h e p i s t o n d o w n a g a i n . A s the
p r e s s u r e o f t h e s u b s t a n c e is less w h e n t h e p i s t o n is s i n k i n g
t h a n w h e n it is r i s i n g , it is p l a i n t h a t t h e e n g i n e c a n r a i s e a
g r e a t e r w e i g h t t h a n t h a t w h i c h is r e q u i r e d t o c o m p l e t e t h e
c y c l e o f o p e r a t i o n s , so t h a t o n t h e w h o l e t h e r e is a b a l a n c e
o f useful w o r k .
Transference of Heat during the Cycle.—It is o n l y i n t h e

second and fourth o p e r a t i o n s that t h e r e is a n y transfer o f

Comparison of Thermal and Mechanical Effects. 143
heat, -for i n t h e first a n d t h i r d t h e h e a t is c o n f i n e d b y t h e

n o n - c o n d u c t i n g stand.
In the s e c o n d o p e r a t i o n a q u a n t i t y o f h e a t r e p r e s e n t e d b y
H passes f r o m t h e h o t b o d y A i n t o t h e w o r k i n g s u b s t a n c e at
the upper temperature s, and in the fourth operation a
quantity o f heat r e p r e s e n t e d b y h passes f r o m the working
substance i n t o t h e c o l d b o d y B at t h e l o w e r t e m p e r a t u r e T.
The w o r k i n g s u b s t a n c e is left after t h e c y c l e o f o p e r a t i o n s
in p r e c i s e l y the s a m e s t a t e as it w a s a t first, s o t h a t t h e w h o l e
p h y s i c a l r e s u l t o f t h e c y c l e is—•
1. A q u a n t i t y , H , o f h e a t t a k e n f r o m A at t h e t e m p e r a t u r e s.
2. T h e p e r f o r m a n c e b y t h e substance o f a quantity o f
w o r k r e p r e s e n t e d b y A B C D.
3. A q u a n t i t y , h, o f h e a t c o m m u n i c a t e d t o B at t h e t e m
perature T.
APPLICATION O F T H E PRINCIPLE O F T H E CONSERVATION

OF ENERGY.
It has l o n g b e e n t h o u g h t b y t h o s e w h o study natural

forces that i n a l l o b s e r v e d a c t i o n s a m o n g b o d i e s t h e work
w h i c h is d o n e is m e r e l y t r a n s f e r r e d f r o m o n e b o d y i n w h i c h
there is a s t o r e o f e n e r g y i n t o a n o t h e r , s o as t o i n c r e a s e t h e
store o f e n e r g y i n t h e l a t t e r b o d y .
The word e n e r g y is e m p l o y e d to denote the capacity
which a b o d y has o f p e r f o r m i n g w o r k , w h e t h e r t h i s c a p a c i t y
arises f r o m t h e m o t i o n o f t h e b o d y , as i n t h e c a s e o f a c a n n o n -
ball, w h i c h i s . a b l e t o b a t t e r d o w n a w a l l b e f o r e i t c a n b e
s t o p p e d ; o r f r o m its p o s i t i o n , as i n t h e c a s e o f t h e w e i g h t o f a
c l o c k w h e n w o u n d u p , w h i c h is a b l e t o k e e p t h e c l o c k g o i n g
for a w e e k ; o r f r o m a n y o t h e r c a u s e , such as t h e e l a s t i c i t y o f
a watch-spring, the magnetisation o f a c o m p a s s needle, the
c h e m i c a l p r o p e r t i e s o f a n a c i d , o r the h e a t o f a h o t b o d y .
The d o c t r i n e o f t h e c o n s e r v a t i o n o f e n e r g y asserts t h a t a l l
these d i f f e r e n t f o r m s o f e n e r g y c a n b e m e a s u r e d i n t h e s a m e
way that m e c h a n i c a l w o r k is m e a s u r e d , a n d t h a t i f t h e w h o l e
e n e r g y o f a n y s y s t e m w e r e m e a s u r e d i n this w a y t h e mutual

144 Heat Engines.
a c t i o n o f the parts o f the s y s t e m c a n neither increase nor

d i m i n i s h its t o t a l s t o c k o f e n e r g y .
H e n c e a n y i n c r e a s e o r d i m i n u t i o n o f e n e r g y i n a system
must be traced to the action o f bodies external to the
system.
T h e b e l i e f in the d o c t r i n e o f t h e c o n s e r v a t i o n o f energy
has greatly assisted the progress o f physical science, especially
s i n c e 1840. T h e numerous investigations which have been
m a d e into the m e c h a n i c a l value o f various forms o f energy
w e r e a l l u n d e r t a k e n b y m e n w h o b e l i e v e d t h a t in so d o i n g
they w e r e l a y i n g a foundation for a m o r e accurate k n o w l e d g e
o f p h y s i c a l a c t i o n s c o n s i d e r e d as f o r m s o f e n e r g y . T h e fact
that so many forms o f energy can be measured on the
hypothesis that t h e y are a l l e q u i v a l e n t t o m e c h a n i c a l energy,
and that m e a s u r e m e n t s c o n d u c t e d b y d i f f e r e n t m e t h o d s are
consistent with each other, shows that the doctrine con
tains scientific truth.
T o e s t i m a t e its truth f r o m a d e m o n s t r a t i v e p o i n t o f v i e w
w e m u s t c o n s i d e r , as w e h a v e a l w a y s t o d o i n m a k i n g such
e s t i m a t e s , w h a t is i n v o l v e d i n a d i r e c t c o n t r a d i c t i o n o f the
doctrine. I f t h e d o c t r i n e is n o t true, t h e n it is p o s s i b l e for
the parts o f a m a t e r i a l system, b y t h e i r mutual action alone,
and without b e i n g themselves altered in a n y permanent way,
either to d o w o r k o n external b o d i e s or to h a v e w o r k done
o n them b y external bodies. S i n c e w e h a v e s u p p o s e d the
s y s t e m after a c y c l e o f o p e r a t i o n s t o b e i n e x a c t l y t h e s a m e
s t a t e as at first, w e m a y s u p p o s e t h e c y c l e o f o p e r a t i o n s t o
b e r e p e a t e d a n i n d e f i n i t e n u m b e r o f times, a n d t h e r e f o r e the
s y s t e m is c a p a b l e i n t h e first case of doing an indefinite
q u a n t i t y o f w o r k w i t h o u t a n y t h i n g b e i n g s u p p l i e d t o it, a n d
in the second o f absorbing an indefinite quantity o f work
w i t h o u t s h o w i n g a n y result.
T h a t the doctrine o f the c o n s e r v a t i o n o f e n e r g y is not

s e l f - e v i d e n t is s h o w n b y t h e r e p e a t e d a t t e m p t s to discover
a perpetual m o t i v e p o w e r , and though such attempts have
b e e n l o n g c o n s i d e r e d h o p e l e s s b y scientific m e n , these men

Conservation of Energy. 145
themselves had repeatedly observed the apparent loss o f

e n e r g y i n friction a n d o t h e r n a t u r a l a c t i o n s , w i t h o u t m a k i n g
any attempt or e v e n s h o w i n g any desire t o ascertain what
b e c o m e s o f this e n e r g y .
T h e e v i d e n c e , h o w e v e r , w h i c h w e h a v e o f t h e d o c t r i n e is
nearly i f n o t q u i t e as c o m p l e t e as t h a t o f t h e c o n s e r v a t i o n of
m a t t e r — t h e d o c t r i n e t h a t i n n a t u r a l o p e r a t i o n s the quantity
o f m a t t e r i n a s y s t e m a l w a y s r e m a i n s t h e s a m e t h o u g h it m a y
change its f o r m .
N o g o o d e v i d e n c e has b e e n b r o u g h t against either o f these
doctrines, arid t h e y a r e as c e r t a i n as a n y o t h e r p a r t o f our
knowledge o f natural things.
T h e g r e a t m e r i t o f C a m o t ' s m e t h o d is that h e a r r a n g e s his
operations i n a c y c l e , s o as t o l e a v e t h e w o r k i n g s u b s t a n c e
in p r e c i s e l y t h e s a m e condition as he found it. We are
therefore sure that the energy r e m a i n i n g in the working
substance i s t h e s a m e i n a m o u n t as at t h e b e g i n n i n g o f t h e
cycle. I f this c o n d i t i o n is n o t fulfilled, w e s h o u l d h a v e to
discover the e n e r g y r e q u i r e d t o c h a n g e the substance from
its o r i g i n a l t o its final state before we could make any
assertion b a s e d u p o n t h e c o n s e r v a t i o n o f e n e r g y .
We have therefore g o t rid o f the consideration of the
e n e r g y r e s i d i n g i n t h e w o r k i n g s u b s t a n c e , w h i c h is c a l l e d its
intrinsic energy, a n d w e h a v e o n l y t o c o m p a r e —
1. T h e o r i g i n a l e n e r g y , w h i c h is a q u a n t i t y H o f h e a t at t h e
temperature s o f the h o t b o d y . This being communicated to
the w o r k i n g s u b s t a n c e , w e g e t for t h e r e s u l t i n g e n e r g y —
2. A q u a n t i t y o f w o r k d o n e , r e p r e s e n t e d b y A B C D J and
3. A q u a n t i t y h o f h e a t at t h e t e m p e r a t u r e T o f t h e cold
body.
T h e p r i n c i p l e o f t h e c o n s e r v a t i o n o f e n e r g y tells us that
the e n e r g y o f t h e h e a t H a t t h e t e m p e r a t u r e s e x c e e d s that
o f the h e a t h at t h e t e m p e r a t u r e T b y a quantity of me
chanical e n e r g y r e p r e s e n t e d b y A B C D , w h i c h c a n b e e a s i l y
expressed in foot-pounds. T h i s is a d m i t t e d b y all.
Now Carnot b e l i e v e d heat to b e a material substance,
L
146 Heat Engines.
c a l l e d caloric, w h i c h o f course c a n n o t b e created or destroyed.

H e t h e r e f o r e c o n c l u d e d that, s i n c e t h e q u a n t i t y o f h e a t re
m a i n i n g in t h e s u b s t a n c e is t h e s a m e as at first, H , the quantity
of heat communicated to it, a n d h, the q u a n t i t y o f heat
abstracted f r o m it, m u s t b e t h e s a m e .
These two portions of h e a t , h o w e v e r , are, as Carnot
o b s e r v e d , i n d i f f e r e n t c o n d i t i o n s , f o r H is a t t h e temperature
o f t h e h o t b o d y , a n d h at that o f t h e c o l d b o d y , a n d Carnot
concluded that the w o r k o f the engine was done at the
expense of the fall o f temperature, the energy of any
d i s t r i b u t i o n o f h e a t b e i n g g r e a t e r t h e h o t t e r t h e b o d y which
c o n t a i n s it.
H e illustrated this t h e o r y v e r y c l e a r l y b y the a n a l o g y of a
water-mill. W h e n w a t e r d r i v e s a m i l l t h e w a t e r w h i c h enter?
t h e m i l l l e a v e s i t a g a i n u n c h a n g e d i n q u a n t i t y , b u t at a lower
level. C o m p a r i n g h e a t w i t h w a t e r , w e m u s t c o m p a r e heat
a t h i g h t e m p e r a t u r e w i t h w a t e r at a h i g h l e v e l . W a t e r tends
t o flow f r o m h i g h g r o u n d t o l o w g r o u n d , just as h e a t tends to
flow from hot bodies t o cold ones. A w a t e r - m i l l m a k e s use
o f t h i s t e n d e n c y o f w a t e r , a n d a h e a t e n g i n e m a k e s use o f the
corresponding property o f heat.
T h e m e a s u r e m e n t o f q u a n t i t i e s o f h e a t , e s p e c i a l l y w h e n it
has t o b e d o n e i n a n e n g i n e at w o r k , is an o p e r a t i o n o f great
d i f f i c u l t y , a n d it w a s n o t till 1862 t h a t i t w a s s h o w n experi
m e n t a l l y b y H i r n that h, t h e h e a t e m i t t e d , is r e a l l y less than
H , the heat r e c e i v e d b y the e n g i n e . But it is e a s y t o see
t h a t t h e a s s u m p t i o n t h a t H is e q u a l t o h m u s t b e w r o n g .
F o r i f w e were to e m p l o y the e n g i n e in stirring a l i q u i d ,
t h e n t h e w o r k A B C D s p e n t i n this w a y w o u l d g e n e r a t e an
a m o u n t o f h e a t w h i c h w e m a y d e n o t e b y •§ in t h e l i q u i d .
T h e h e a t H at t h e h i g h t e m p e r a t u r e has therefore been
used, and we find instead o f it a quantity h at t h e l o w
temperature, a n d a l s o >§ at t h e t e m p e r a t u r e o f the liquid,
w h a t e v e r it is.
B u t i f h e a t is m a t e r i a l , a n d t h e r e f o r e H = k, t h e n h + >§
is g r e a t e r t h a n t h e o r i g i n a l q u a n t i t y H , a n d h e a t has been

Heat is not a Substance. H7
created, which is contrary to the hypothesis that it is
material.
B e s i d e s this, w e m i g h t h a v e a l l o w e d t h e heat H to pass
from the h o t b o d y t o t h e c o l d b o d y b y c o n d u c t i o n , either
directly or t h r o u g h one or m o r e conducting bodies, and in
this case w e k n o w that t h e h e a t r e c e i v e d b y t h e c o l d body
would b e e q u a l t o t h e h e a t t a k e n from the h o t body, since
conduction does not alter the quantity o f heat. Hence in
this case H = h, b u t n o w o r k is d o n e d u r i n g t h e transfer of
heat. W h e n , i n a d d i t i o n t o t h e transfer o f heat, w o r k is d o n e
by the e n g i n e , t h e r e o u g h t t o b e s o m e d i f f e r e n c e i n t h e final
result, b u t t h e r e w i l l b e n o d i f f e r e n c e i f h is still e q u a l t o H .
T h e h y p o t h e s i s o f c a l o r i c , o r t h e t h e o r y t h a t h e a t is a k i n d
o f matter, is r e n d e r e d u n t e n a b l e , first b y t h e p r o o f g i v e n by
Rumford, and m o r e c o m p l e t e l y b y D a v y , that heat can be
generated at the e x p e n s e o f m e c h a n i c a l w o r k ; a n d , s e c o n d ,
b y the m e a s u r e m e n t s o f I l i r n , w h i c h s h o w that w h e n heat
does w o r k i n a n e n g i n e , a p o r t i o n o f t h e h e a t disappears.
T h e determination o f the m e c h a n i c a l equivalent o f heat b y
Joule e n a b l e s us t o assert t h a t t h e h e a t w h i c h is r e q u i r e d t o
raise a p o u n d o f w a t e r f r o m 3 9 ° F . t o 4 0 ° F . is m e c h a n i c a l l y
equivalent to 7 7 2 f o o t - p o u n d s o f w o r k .
I t is t o b e o b s e r v e d t h a t i n this s t a t e m e n t n o t h i n g is s a i d
about the t e m p e r a t u r e o f t h e b o d y in w h i c h t h e h e a t exists.
T h e heat w h i c h raises the pound o f water from 3 9 ° F . to
0 0
40 F. m a y b e taken from a vessel o f c o l d water at 5 0 F . ,
from a r e d - h o t i r o n h e a t e r at 7 0 0 0
F . , or f r o m t h e sun at a
t e m p e r a t u r e far a b o v e a n y e x p e r i m e n t a l d e t e r m i n a t i o n , and
y e t the h e a t i n g e f f e c t o f t h e h e a t is the s a m e w h a t e v e r b e t h e
source f r o m w h i c h i t flows. W h e n h e a t is m e a s u r e d as a
quantity, n o r e g a r d w h a t e v e r is p a i d t o t h e t e m p e r a t u r e of
the b o d y i n w h i c h t h e h e a t exists, a n y m o r e t h a n t o t h e size,
weight, o r p r e s s u r e o f that b o d y , j u s t a s when we deter
m i n e the w e i g h t o f a b o d y w e p a y n o a t t e n t i o n t o its other
properties.
H e n c e i f a b o d y in a c e r t a i n state, as to t e m p e r a t u r e , &c,

L 2
148 Heat Engines.
is c a p a b l e o f h e a t i n g so m a n y p o u n d s o f w a t e r f r o m 39° F . to
4 0 ° F . b e f o r e i t is i t s e l f c o o l e d to a g i v e n temperature, say
4 0 ° F . , t h e n i f t h a t b o d y , i n its o r i g i n a l s t a t e , is stirred a b o u t
a n d its p a r t s r u b b e d t o g e t h e r so as t o e x p e n d 772 f o o t - p o u n d s
o f w o r k in the process, it will b e a b l e to heat one pound
m o r e o f w a t e r f r o m 3 9 ° F . t o 4 0 ° F . b e f o r e it is c o o l e d t o the
given temperature.
Carnot, therefore, was wrong in supposing that the
mechanical energy o f a given quantity of heat is greater
w h e n it exists i n a h o t b o d y t h a n w h e n it exists i n a cold
body. W e n o w k n o w t h a t its m e c h a n i c a l e n e r g y is e x a c t l y
t h e s a m e i n b o t h c a s e s , a l t h o u g h w h e n in t h e h o t b o d y it is
m o r e a v a i l a b l e for the p u r p o s e o f d r i v i n g an e n g i n e .
T n o u r s t a t e m e n t o f t h e four o p e r a t i o n s o f C a r n o t ' s e n g i n e
w e arranged them s o as t o l e a v e t h e r e s u l t in a state in
w h i c h w e c a n i n t e r p r e t it e i t h e r as C a r n o t d i d , o r a c c o r d i n g
to the d y n a m i c a l t h e o r y o f heat. C a r n o t h i m s e l f b e g a n with
the o p e r a t i o n w h i c h w e h a v e p l a c e d second, the expansion
at t h e u p p e r t e m p e r a t u r e , a n d h e d i r e c t s u s t o c o n t i n u e the
f o u r t h o p e r a t i o n , c o m p r e s s i o n at t h e l o w e r t e m p e r a t u r e , till
e x a c t l y as m u c h h e a t h a s left t h e s u b s t a n c e as e n t e r e d during
t h e e x p a n s i o n at t h e u p p e r t e m p e r a t u r e . T h e result o f this
o p e r a t i o n w o u l d b e , as w e n o w k n o w , t o expel too much
heat, so that after t h e substance h a d been compressed on
t h e n o n - c o n d u c t i n g s t a n d t o its o r i g i n a l v o l u m e , its t e m p e r a
ture a n d p r e s s u r e w o u l d b e t o o l o w . I t is e a s y t o a m e n d the
d i r e c t i o n s f o r t h e e x t e n t t o w h i c h t h e o u t f l o w o f h e a t is t o b e
permitted, but it is still e a s i e r t o avoid the difficulty by
p l a c i n g this o p e r a t i o n last, as w e h a v e d o n e .
W e a r e n o w a b l e t o s t a t e p r e c i s e l y t h e r e l a t i o n b e t w e e n h,
the quantity o f heat which leaves the engine, and H , the
q u a n t i t y r e c e i v e d b y it. H is e x a c t l y e q u a l t o t h e s u m o f h,
and the heat t o w h i c h the m e c h a n i c a l w o r k represented b y
A B c D is e q u i v a l e n t .
I n all s t a t e m e n t s c o n n e c t e d w i t h t h e d y n a m i c a l t h e o r y o f
heat it is e x c e e d i n g l y c o n v e n i e n t t o s t a t e q u a n t i t i e s o f heat

Heat expressed in Foot-pounds. 149
in f o o t - p o u n d s at o n c e , i n s t e a d o f first e x p r e s s i n g t h e m in
thermal units a n d t h e n r e d u c i n g t h e r e s u l t t o f o o t - p o u n d s b y
means o f J o u l e ' s e q u i v a l e n t o f h e a t . I n fact, t h e thermal
unit d e p e n d s for its d e f i n i t i o n o n t h e choice o f a standard
substance to which heat is to be applied, on the
choice of a standard quantity o f that substance, and
on the c h o i c e o f the effect to b e produced b y the heat.
According as w e choose water or ice, the grain or the
g r a m m e , the F a h r e n h e i t o r t h e C e n t i g r a d e s c a l e o f t e m p e r a
tures, w e o b t a i n different thermal u n i t s , all of which have
b e e n used i n d i f f e r e n t i m p o r t a n t r e s e a r c h e s . B y expressing
quantities o f h e a t i n f o o t - p o u n d s w e avoid ambiguity, and,
especially i n theoretical reasonings about the working of
engines, w e s a v e a g r e a t d e a l o f u s e l e s s p h r a s e o l o g y .
As w e have already shown h o w an area on the indicator

diagram represents a quantity o f w o r k , w e shall have no
difficulty i n u n d e r s t a n d i n g t h a t i t m a y a l s o b e t a k e n t o r e
present a q u a n t i t y o f h e a t e q u i v a l e n t t o t h e s a m e q u a n t i t y o f
work, that is t h e s a m e n u m b e r o f f o o t - p o u n d s o f h e a t . ,
We may therefore express the relation between H and h
still m o r e c o n c i s e l y thus :
The quantity, H, o f heat taken into the engine at the
upper t e m p e r a t u r e s e x c e e d s t h e q u a n t i t y , k, o f h e a t given
out b y t h e e n g i n e at t h e l o w e r t e m p e r a t u r e T b y a quantity
of heat r e p r e s e n t e d by t h e a r e a AB CD on the indicator
diagram.
T h i s q u a n t i t y o f h e a t is, as w e h a v e a l r e a d y s h o w n , c o n
verted into m e c h a n i c a l w o r k b y the e n g i n e .
O N T H E R E V E R S E D ACTION O F CARNOT'S ENGINE.
The peculiarity o f Carnot's e n g i n e is, t h a t w h e t h e r i t is

receiving heat from the h o t b o d y , o r g i v i n g it out to the
cold b o d y , the temperature o f the substance in the engine
differs e x t r e m e l y l i t t l e f r o m that o f t h e b o d y in thermal
communication w i t h it. B y supposing the conductivity o f

Heat Engines.
the bottom o f the cylinder to be sufficiently g r e a t , o r by

supposing the motions of the piston to be sufficiently
slow, w e m a y make the actual difference of temperature
w h i c h causes the flow o f h e a t to take p l a c e as s m a l l as w e
please.
I f w e r e v e r s e t h e m o t i o n o f t h e p i s t o n w h e n t h e substance
is i n t h e r m a l c o m m u n i c a t i o n w i t h A o r B , t h e first effect w i l l
b e t o alter the temperature o f the w o r k i n g s u b s t a n c e , but
an e x c e e d i n g l y small alteration o f t e m p e r a t u r e w i l l b e suf
ficient to reverse the flow o f h e a t , i f t h e m o t i o n is slow
enough.
N o w l e t us s u p p o s e the engine to b e w o r k e d backwards
by e x a c t l y reversing all the operations already described.
B e g i n n i n g at t h e l o w e r t e m p e r a t u r e a n d v o l u m e o a, l e t it
b e p l a c e d o n the c o l d b o d y a n d expand f r o m v o l u m e o a to
o d. I t w i l l r e c e i v e f r o m t h e c o l d b o d y a q u a n t i t y o f heat
h. Then l e t it b e c o m p r e s s e d w i t h o u t l o s i n g h e a t t o o c.
I t will then have the upper temperature s. L e t it t h e n b e
placed, o n the h o t b o d y a n d compressed t o v o l u m e o b. It
will g i v e out a quantity o f heat H t o the h o t b o d y . Finally,
l e t it b e a l l o w e d t o e x p a n d w i t h o u t r e c e i v i n g h e a t t o v o l u m e
o a, a n d i t w i l l r e t u r n t o its o r i g i n a l state. T h e o n l y d i f f e r e n c e
between the direct and the r e v e r s e a c t i o n o f t h e e n g i n e is,
that in the direct action the w o r k i n g substance must b e a
l i t t l e c o o l e r t h a n A w h e n i t r e c e i v e s its heat, a n d a little
w a r m e r than B w h e n it g i v e s it o u t ; whereas in the reverse
a c t i o n i t m u s t b e w a r m e r t h a n A w h e n i t g i v e s o u t heat, a n d
c o o l e r than B w h e n it t a k e s h e a t in. But b y w o r k i n g the
e n g i n e sufficiently s l o w l y t h e s e d i f f e r e n c e s m a y b e reduced
within a n y limits we please to assign, so that for theo
retical purposes w e m a y regard Carnot's e n g i n e as strictly
reversible.
I n the reverse action a q u a n t i t y h o f h e a t is t a k e n f r o m

the cold b o d y B, and a greater quantity H is g i v e n t o t h e
h o t b o d y A , this b e i n g d o n e at t h e e x p e n s e o f a q u a n t i t y o f
w o r k measured b y the area A D C B , w h i c h also measures

Carnofs Engine Reversed.
the quantity o f heat into w h i c h this w o r k is transformed

during the p r o c e s s .
T h e reverse action o f Carnot's e n g i n e s h o w s us t h a t it i s
possible t o transfer heat from a c o l d b o d y to a hot one,
but that this o p e r a t i o n c a n o n l y b e d o n e a t t h e e x p e n s e o f
a certain q u a n t i t y o f m e c h a n i c a l w o r k .
The transference o f heat from a hot body to a cold one
may b e effected by means o f a heat engine, in which case
part o f it is c o n v e r t e d i n t o mechanical work, or it m a y
take place by conduction, which goes on o f itself, but
without any conversion o f heat into work. It appears,
therefore, that h e a t m a y pass f r o m h o t b o d i e s t o c o l d ones
in t w o different w a y s . One o f these, in w h i c h a h i g h l y
artificial e n g i n e is m a d e u s e of, is nearly, but not quite
c o m p l e t e l y , r e v e r s i b l e , so that b y spending the work we
have gained, w e c a n r e s t o r e a l m o s t t h e w h o l e o f the heat
from the c o l d b o d y t o t h e h o t . T h e other m o d e o f trans
fer, w h i c h t a k e s p l a c e o f i t s e l f w h e n e v e r a h o t a n d a c o l d
body are b r o u g h t near each other, appears to b e irreversible,
for heat n e v e r p a s s e s f r o m a cold b o d y to a hot one of
itself, but o n l y w h e n t h e o p e r a t i o n is e f f e c t e d b y t h e artificial
engine at the e x p e n s e o f m e c h a n i c a l w o r k .
We n o w c o m e to an important p r i n c i p l e , w h i c h is en
tirely d u e t o C a r n o t . I f a g i v e n reversible engine, working
between the upper temperature s and the l o w e r tempera
ture T , a n d receiving a quantity H o f h e a t at the upper
temperature, produces a quantity w of mechanical work,
then n o other engine, whatever be its c o n s t r u c t i o n , can
produce a greater quantity o f w o r k , w h e n supplied with
the s a m e a m o u n t o f heat, and w o r k i n g b e t w e e n the same
temperatures.
is the supply of heat,

DEFINITION' O F E F F I C I E N C Y . — I f H
and w the work done by an engine, both measured in foot
pounds, then the fraction — is called the Efficiency of the
engine.
Heat Engines.
C a r n o t ' s p r i n c i p l e , t h e n , is t h a t t h e e f f i c i e n c y o f a rever
s i b l e e n g i n e is t h e g r e a t e s t t h a t c a n b e o b t a i n e d w i t h a g i v e n
range o f temperature.
F o r suppose a certain e n g i n e , M , has a g r e a t e r efficiency
b e t w e e n the temperatures s a n d T than a r e v e r s i b l e engine
N, then if w e connect the t w o engines, so that M by its
d i r e c t a c t i o n d r i v e s N i n t h e r e v e r s e d i r e c t i o n , at e a c h stroke
o f the compound engine N will take from the cold body
B t h e h e a t A, a n d b y t h e e x p e n d i t u r e o f w o r k "w g i v e t o the
hot b o d y A the h e a t H. The engine M w i l l r e c e i v e this
heat H , and b y hypothesis will d o m o r e w o r k w h i l e trans
ferring it to B than is r e q u i r e d to drive the engine N.
Hence at e v e r y stroke there will b e an excess of useful
w o r k d o n e b y the c o m b i n e d engine.
W e m u s t n o t s u p p o s e , h o w e v e r , t h a t this is a v i o l a t i o n o f
the principle o f conservation o f energy, for if M does more
w o r k t h a n N w o u l d d o , it c o n v e r t s m o r e h e a t i n t o w o r k in
e v e r y stroke, and therefore M restores to the c o l d b o d y a
s m a l l e r q u a n t i t y o f h e a t t h a n N t a k e s f r o m it. H e n c e , the
l e g i t i m a t e conclusion from the hypothesis is, t h a t the c o m
bined e n g i n e w i l l , b y its u n a i d e d action, c o n v e r t the heat
o f the cold b o d y B into mechanical work, and t h a t this
p r o c e s s m a y g o o n t i l l all t h e h e a t i n t h e s y s t e m is c o n v e r t e d
into work.
T h i s is m a n i f e s t l y c o n t r a r y t o e x p e r i e n c e , a n d therefore
w e m u s t a d m i t t h a t n o e n g i n e c a n h a v e an e f f i c i e n c y g r e a t e r
than that o f a reversible e n g i n e w o r k i n g b e t w e e n the same
temperatures. But before w e consider t h e results o f Car
not's principle w e must endeavour to express clearly the
l a w w h i c h lies a t t h e b o t t o m o f t h e reasoning.
T h e principle o f the c o n s e r v a t i o n o f e n e r g y , w h e n a p p l i e d
to heat, is c o m m o n l y called the First L a w of Thermo
d y n a m i c s . I t m a y b e s t a t e d thus : W h e n w o r k is t r a n s f o r m e d
into heat, or heat into work, the quantity of work is
m e c h a n i c a l l y e q u i v a l e n t to the quantity o f heat.
T h e application o f the law i n v o l v e s the existence o f the
mechanical equivalent o f heat.

First and Second Laws of Thermodynamics. 153
Carnot's principle is not deduced from this law, and

indeed Carnot's own statement involved a violation of it.
The law from which Carnot's principle is deduced has been
called the Second L a w of Thermodynamics.
Admitting heat to be a form o f energy, the second law
asserts that it is impossible, by the unaided action of natural
processes, to transform any part of the heat of a body into
mechanical work, except b y allowing heat to pass from that
body into another at a lower temperature. Clausius, who
first stated the principle of Carnot in a manner consistent
with the true theory of heat, expresses this law as follows : —
I t is impossible for a self-acting machine, unaided by any
external agency, to convey heat from one body to another
at a higher temperature.
Thomson gives it a slightly different f o r m : —
I t is impossible, by means o f inanimate material agency,
to derive mechanical effect from any portion o f matter b y
cooling it below the temperature o f the coldest of the sur
rounding objects.
By comparing together these statements, the student will
be able to make himself master of the fact which they em
body, an acquisition which will be o f much greater import
ance to him than any form o f words on which a demon
stration may b e more or less compactly constructed.
Suppose that a body contains energy in the form of heat,
what are the conditions under which this energy or any
part of it may be removed from the b o d y ? I f heat in a
body consists in a motion of its parts, and i f we were able
to distinguish these parts, and to guide and control their
motions by any kind of mechanism, then b y arranging our
apparatus so as to lay hold of every moving part o f the
body, we could, b y a suitable train of mechanism, transfer
the energy of the moving parts o f the heated body to any
other body in the form o f ordinary motion. T h e heated
body would thus be rendered perfectly cold, and all its
thermal energy would be converted into the visible motion
of some other body.

154 Heat Engines.
N o w this supposition involves a direct contradiction to
the second law o f thermodynamics, but is c o n s i s t e n t w i t h
t h e first l a w . T h e s e c o n d l a w is t h e r e f o r e equivalent to a
d e n i a l o f our p o w e r to p e r f o r m the o p e r a t i o n just described,
either b y a train o f m e c h a n i s m , or b y any other m e t h o d yet
discovered. H e n c e , i f the heat o f a b o d y consists in the
motion o f its p a r t s , t h e separate parts w h i c h m o v e must
b e s o s m a l l o r so i m p a l p a b l e t h a t w e c a n n o t in a n y w a y l a y
h o l d o f them t o stop them.
I n fact, h e a t , i n t h e f o r m o f h e a t , n e v e r p a s s e s o u t o f a
b o d y e x c e p t w h e n i t flows b y c o n d u c t i o n o r r a d i a t i o n i n t o a
colder body.
T h e r e are several processes b y which the temperature of
a b o d y m a y b e l o w e r e d w i t h o u t r e m o v i n g h e a t f r o m it, such
as expansion, evaporation, and liquefaction, and certain
chemical and electrical processes. Every one of these,
h o w e v e r , is a r e v e r s i b l e p r o c e s s , s o t h a t w h e n the b o d y is
b r o u g h t b a c k b y a n y s e r i e s o f o p e r a t i o n s t o its o r i g i n a l state,
without any heat b e i n g a l l o w e d to enter or escape during
t h e p r o c e s s , t h e t e m p e r a t u r e w i l l b e t h e s a m e as b e f o r e , in
virtue o f the reversal of the processes b y which the tempera
ture was lowered. But if, during the operations, heat
has passed from hot parts o f the system t o cold b y con
duction, or if anything of the n a t u r e o f f r i c t i o n has t a k e n
place, then to bring the system t o its o r i g i n a l s t a t e will
require the expenditure o f w o r k , and t h e r e m o v a l o f heat.
W e m u s t n o w return t o the i m p o r t a n t result demonstrated
b y Carnot, that a reversible engine, working between two
g i v e n t e m p e r a t u r e s , a n d r e c e i v i n g at t h e h i g h e r temperature
a given q u a n t i t y o f h e a t , p e r f o r m s at l e a s t as m u c h work
as any other engine whatever w o r k i n g under the same
conditions. It f o l l o w s f r o m this t h a t a l l r e v e r s i b l e e n g i n e s ,
whatever b e the working substance employed, have the
same efficiency, provided they work between the same
temperature o f the source o f heat A and the same tempera
ture o f t h e r e f r i g e r a t o r R.
Hence Carnot s h o w e d t h a t if w e c h o o s e t w o tempera-

Carnot's Function.
a
tures differing v e r y slightly, s a y b y -nnj-ff °f degree, the
efficiency o f a n e n g i n e w o r k i n g b e t w e e n t h e s e temperatures
will d e p e n d o n the t e m p e r a t u r e o n l y , a n d n o t o n t h e sub
stance e m p l o y e d , a n d this e f f i c i e n c y divided b y the differ
ence o f t e m p e r a t u r e s is t h e q u a n t i t y c a l l e d Carnot's function,
a quantity d e p e n d i n g o n t h e t e m p e r a t u r e o n l y .
Carnot, o f course, understood the temperature to be
estimated i n the ordinary way by means o f a thermometer
of a s e l e c t e d s u b s t a n c e graduated according to one o f the
established scales, a n d h i s f u n c t i o n is e x p r e s s e d i n t e r m s o f
the t e m p e r a t u r e s o d e t e r m i n e d . B u t W . T h o m s o n , i n 1848,
was the first t o p o i n t o u t t h a t C a r n o t ' s result leads to a
method of defining temperature which is much more
scientific t h a n a n y o f t h o s e derived from the behaviour of
one selected substance o r class o f substances, and which
is perfectly i n d e p e n d e n t o f the nature of the substance
e m p l o y e d i n d e f i n i n g it.
T H O M S O N ' S A B S O L U T E S C A L E OF TEMPERATURE.
Let T A B c represent the isothermal line corresponding

to temperature r for a certain substance. F o r the sake o f
distinctness i n t h e figure, I h a v e supposed the substance t o
be partly in the liquid a n d p a r t l y i n t h e g a s e o u s state, s o
that t h e isothermal lines are horizontal, and easily dis
tinguished f r o m t h e a d i a b a t i c l i n e s , w h i c h s l o p e d o w n w a r d s
to the right. T h e i n v e s t i g a t i o n , h o w e v e r , is q u i t e i n d e p e n
d e n t o f a n y such r e s t r i c t i o n as t o t h e n a t u r e o f t h e w o r k i n g
substance. W h e n the v o l u m e and pressure o f the substance
are t h o s e indicated b y the point A , let heat b e a p p l i e d
a n d let the s u b s t a n c e e x p a n d , a l w a y s a t t h e t e m p e r a t u r e T,
till a q u a n t i t y o f h e a t H has e n t e r e d , a n d l e t the state of
the substance be then indicated b y the p o i n t u. Let
t h e p r o c e s s g o o n till a n o t h e r e q u a l q u a n t i t y , H , o f h e a t has
e n t e r e d , a n d l e t c i n d i c a t e t h e r e s u l t i n g state. T h e process
may b e c a r r i e d o n s o as to find any number of points on

i 6
5
Heat Engines.
the isothermal line, such that for each p o i n t passed daring

t h e e x p a n s i o n o f t h e s u b s t a n c e a q u a n t i t y H o f h e a t has b e e n
c o m m u n i c a t e d t o it.
N o w l e t A A' A", B B' B", C C' C " b e a d i a b a t i c l i n e s d r a w n
through A B C , t h a t is, lines
F I G . 23.
representing the relation be
tween volume and pressure
w h e n t h e s u b s t a n c e is a l l o w e d
to expand without receiving
heat from without.
L e t T' A' B' C ' a n d T " A" B " C"
be isothermal lines corre
sponding to the temperatures
T ' a n d T".
We have already followed
Carnot's p r o o f that in a re
versible e n g i n e , w o r k i n g from
t h e t e m p e r a t u r e T o f t h e s o u r c e o f h e a t t o t h e t e m p e r a t u r e T'
o f the refrigerator, the w o r k w p r o d u c e d b y the quantity o f
h e a t H d r a w n f r o m t h e s o u r c e d e p e n d s o n l y o n T a n d T'.
H e n c e , since A B a n d B C c o r r e s p o n d to equal quantities
o f heat H r e c e i v e d from the s o u r c e , t h e a r e a s A B B' A ' a n d
B c c' B', which represent the corresponding w o r k performed,
must b e equal.
T h e s a m e is true o f t h e a r e a s c u t o f f b y t h e a d i a b a t i c l i n e s
from the space b e t w e e n any other pair o f isothermal lines.
H e n c e i f a series o f a d i a b a t i c l i n e s b e d r a w n s o t h a t the
p o i n t s a t w h i c h t h e y cut o n e o f the isothermal lines corre
spond to successive equal additions o f heat to the substance
at t h a t t e m p e r a t u r e , t h e n t h i s s e r i e s o f a d i a b a t i c l i n e s w i l l cut
o f f a series o f e q u a l a r e a s f r o m t h e strip b o u n d e d b y a n y t w o
isothermal lines.
N o w T h o m s o n ' s m e t h o d o f graduating a scale o f tempera
t u r e is e q u i v a l e n t t o c h o o s i n g t h e p o i n t s A A' A " , f r o m w h i c h
t o d r a w a series o f i s o t h e r m a l l i n e s , so t h a t t h e a r e a A B B' A'
c o n t a i n e d b e t w e e n t w o c o n s e c u t i v e i s o t h e r m a l s T a n d T ' shall

A bsohite Scale of Temperature. 15 7
be equal to the area A' B' B " A " contained between any other
pair of consecutive isothennals x'T".
It is the same as saying that the number of degrees between
the temperature T and the temperature T " is to b e reckoned
proportional to the area A B B " A".
Of course two things remain arbitrary, the standard tem
perature which is to be reckoned zero, and the size of the
degrees, and these may be chosen so that the absolute scale
corresponds with one of the ordinary scales at the two
standard temperatures, but as soon as these are determined
the numerical measure of every other temperature is settled,
in a manner independent of the laws of expansion of any
one substance—by a method, in fact, which leads to the same
result whatever be the substance employed.
It is true that the experiments and measurements required
to graduate a thermometer on the principle here pointed out
would be far more difficult than those required b y the
ordinary method described in the chapter on Thermometry.
But we are not, in this chapter, describing convenient methods
or good working engines. Our objects are intellectual,
not practical, and when we have established theoretically
the scientific advantages of this method of graduation, w e
shall be better able to understand the practical methods by
which it can be realised.
W e now draw the series o f isothermal and adiabatic lines
in the following way :
A particular isothermal line, that o f temperature T , is cut
by the adiabatic lines, so that the expansion of the substance
between consecutive adiabatic lines corresponds to successive
quantities of heat, each equal to H , applied to the substance.
This determines the series of adiabatic lines.
T h e isothermal lines are drawn so that the successive
isothermals cut off from the space between the pair of
adiabatic lines A A' A " and B B' B " equal areas A B B ' A',
A' B' B " A " , & c .
T h e isothermal lines so determined cut off equal areas

Heat Engines.
from e v e r y o t h e r p a i r o f a d i a b a t i c lines, so that the two

systems o f lines are such that all the quadrilaterals formed
by t w o pairs o f c o n s e c u t i v e lines are equal in area.
We have n o w graduated the isothermals on the diagram
by a m e t h o d f o u n d e d o n C a m o t ' s p r i n c i p l e a l o n e , a n d in
d e p e n d e n t o f t h e n a t u r e o f t h e w o r k i n g s u b s t a n c e , a n d it is
easy t o see h o w b y altering, i f necessary, the interval b e t w e e n
the lines a n d the line c h o s e n for zero, w e can m a k e the
graduation agree, at t h e two standard temperatures, with
the o r d i n a r y scale.
EFFICIENCY O F A H E A T E N G I N E .
Let us n o w c o n s i d e r t h e r e l a t i o n b e t w e e n t h e h e a t s u p p l i e d
to an e n g i n e a n d the w o r k d o n e b y it as e x p r e s s e d in terms
o f the n e w s c a l e o f t e m p e r a t u r e .
I f t h e t e m p e r a t u r e o f the s o u r c e o f h e a t is T, a n d i f H is
t h e q u a n t i t y o f h e a t s u p p l i e d t o t h e e n g i n e at t h a t t e m p e r a
ture, t h e n t h e w o r k d o n e b y this h e a t d e p e n d s e n t i r e l y o n
the temperature o f the refrigerator. L e t T " b e the tempera
ture o f t h e r e f r i g e r a t o r , t h e n t h e w o r k d o n e b y n is r e p r e s e n t e d
{
by the a r e a A B B' A " , o r , s i n c e a l l t h e areas b e t w e e n the
isothermals a n d the adiabatics are equal, let H c b e the area
of o n e o f the quadrilaterals, then the w o r k d o n e b y H will b e
H c (T — T"). T h e quantity c depends o n l y on the tem
perature T . I t is c a l l e d C a m o t ' s F u n c t i o n o f the tempera
ture. W e shall f i n d a s i m p l e e x p r e s s i o n f o r i t a t p a g e 160.
T h i s , t h e r e f o r e , is a c o m p l e t e d e t e r m i n a t i o n o f t h e w o r k
d o n e w h e n the temperature o f the source o f heat is T. It
d e p e n d s o n l y o n C a m o t ' s p r i n c i p l e , and is true w h e t h e r w e
a d m i t t h e first l a w o f t h e r m o d y n a m i c s o r n o t .
I f t h e t e m p e r a t u r e o f t h e s o u r c e is n o t T , b u t T ' , w e must
c o n s i d e r w h a t q u a n t i t y o f h e a t is r e p r e s e n t e d b y the expan
s i o n A' B ' a l o n g t h e isothermal T'. C a l l i n g this q u a n t i t y o f
heat H ' , the w o r k d o n e b y an e n g i n e w o r k i n g b e t w e e n the
t e m p e r a t u r e s T' a n d T" is
w - H / C (T' — T").

Their Efficiency. 159
Now Camot supposed that H ' = H , which would make
the efficiency o f the engine simply ^ = c (T/ — T " ) , where c

u
is Carnot's function, a constant quantity on this supposition.
But according to the dynamical theory of heat, we get b y the
first law of thermodynamics
H ' = H — A B B' A',
the heat being measured as mechanical work, or
H ' = H — H c ( T — T ). /
On this theory, therefore, the efficiency of the engine

working between T ' and T " is
w _ H c ( T — T") 7
H' H — H C (T —
ryl r^lt
7
~ — + T — T.
c
ON A B S O L U T E TEMPERATURE.
We have now obtained a method o f expressing differences

of temperature in such a way that the difference o f two
temperatures may be compared with the difference of two
other temperatures. But w e are able to go a step farther
than this, and to reckon temperature from a zero point
defined on thermodynamic principles independently of the
properties of a selected substance. W e must carefully
distinguish between what we are doing now on really scientific
principles from what we did for the sake o f convenience in
describing the air thermometer. Absolute temperature on
the air thermometer is merely a convenient expression of the
laws of gases. T h e absolute temperature as now defined
is independent of the nature of the thermometric substance.
It so happens, however, that the difference between these
two scales of temperature is very small. T h e reason of this
will be explained afterwards.

i6o Heat Engines.
I t is p l a i n t h a t t h e work which a given q u a n t i t y o f heat

H can perform in an engine can n e v e r b e greater t h a n the
mechanical e q u i v a l e n t o f that heat, t h o u g h t h e c o l d e r the
r e f r i g e r a t o r t h e g r e a t e r p r o p o r t i o n o f h e a t is c o n v e r t e d into
work. I t is p l a i n , t h e r e f o r e , t h a t i f w e d e t e r m i n e T " the
temperature o f the refrigerator, s o as t o m a k e w the w o r k
mechanically equivalent to H , the heat received by the
e n g i n e , w e shall o b t a i n a n e x p r e s s i o n f o r a s t a t e o f t h i n g s in
w h i c h the e n g i n e w o u l d c o n v e r t the w h o l e heat into work,
and n o b o d y c a n p o s s i b l y b e at a l o w e r t e m p e r a t u r e than
t h e v a l u e thus a s s i g n e d t o T".
Putting w = H ' , w e find T " = T — -.
T h i s is t h e l o w e s t t e m p e r a t u r e any b o d y can have. Call

i n g this t e m p e r a t u r e z e r o , w c find
or the temperature reckoned from absolute zero is the

r e c i p r o c a l o f C a r n o t ' s f u n c t i o n c.
W e h a v e t h e r e f o r e a r r i v e d a t a c o m p l e t e d e f i n i t i o n o f the
measure o f temperature, in which nothing remains to be
determined except the size o f the degrees. Hitherto the
s i z e o f t h e d e g r e e s h a s b e e n c h o s e n so as t o b e e q u a l t o tire
m e a n value o f those o f the ordinary scales. T o c o n v e r t the
o r d i n a r y expressions into absolute temperatures w e must add
to the ordinary expression a constant number o f degrees,
w h i c h m a y b e c a l l e d the absolute t e m p e r a t u r e o f the zero of
the scale. T h e r e is a l s o a c o r r e c t i o n v a r y i n g at different
parts o f the s c a l e , w h i c h is n e v e r v e r y g r e a t w h e n t h e t e m
p e r a t u r e is m e a s u r e d b y t h e air t h e r m o m e t e r . W e may now
express the efficiency o f a r e v e r s i b l e heat e n g i n e in terms o f
the absolute temperature s o f the source o f heat, and the
absolute temperature T o f the refrigerator. I f 11 is the
q u a n t i t y o f h e a t s u p p l i e d t o t h e e n g i n e , a n d w is t h e quantity
o f w o r k p e r f o r m e d , b o t h e s t i m a t e d in d y n a m i c a l m e a s u r e ,
w s — T
H S

Absolute Temperature.
T h e quantity o f h e a t w h i c h is g i v e n o u t t o t h e refrigerator
T
at temperature T is A = H — w = H — whence
s
H _ hQ R H _ S
s T h T
that is, i n a r e v e r s i b l e e n g i n e t h e r a t i o o f t h e h e a t r e c e i v e d t o
the heat r e j e c t e d is that o f t h e n u m b e r s e x p r e s s i n g o n an a b s o
lute scale t h e t e m p e r a t u r e s o f t h e s o u r c e a n d t h e r e f r i g e r a t o r .
T h i s r e l a t i o n furnishes us w i t h a m e t h o d o f determining
the ratio o f t w o t e m p e r a t u r e s o n t h e a b s o l u t e scale. I t is
independent o f the nature o f the substance e m p l o y e d in the
reversible e n g i n e , a n d is t h e r e f o r e a perfect method con
sidered from a theoretical point of view. The practical
difficulties o f fulfilling the required conditions and making
the n e c e s s a r y measurements have not hitherto been over
c o m e , s o that t h e c o m p a r i s o n o f t h e a b s o l u t e scale o f t e m
perature w i t h t h e o r d i n a r y s c a l e m u s t b e m a d e i n a d i f f e r e n t
way. (See p. 213.)
L e t us n o w return t o t h e d i a g r a m fig. 23 ( p . 156), o n w h i c h
we have traced t w o systems o f lines, the isothermals and
the adiabatics. T o draw an isothermal line through a g i v e n
point r e q u i r e s o n l y a series o f e x p e r i m e n t s o n t h e s u b s t a n c e
at a g i v e n t e m p e r a t u r e , as s h o w n b y a t h e r m o m e t e r o f a n y
kind. T o d r a w a series o f t h e s e l i n e s t o r e p r e s e n t succes
sive d e g r e e s o f t e m p e r a t u r e is e q u i v a l e n t t o fixing a s c a l e o f
temperature.
Such a s c a l e m i g h t b e d e f i n e d i n m a n y d i f f e r e n t ways,
each o f w h i c h d e p e n d s o n t h e p r o p e r t i e s o f s o m e selected
substance. F o r instance, the scale m i g h t b e f o u n d e d on the
e x p a n s i o n o f a p a r t i c u l a r s u b s t a n c e at s o m e s t a n d a r d p r e s s u r e .
I n this c a s e , if a h o r i z o n t a l l i n e is d r a w n t o r e p r e s e n t the
standard pressure, t h e n t h e i s o t h e r m a l l i n e s o f t h e selected
substance w i l l cut t h i s l i n e at e q u a l i n t e r v a l s . If, however,
the nature o f t h e substance or the s t a n d a r d pressure be
different, t h e t h e r m o m e t r i c scale w i l l b e i n g e n e r a l different.
T h e scale m i g h t a l s o b e f o u n d e d o n t h e v a r i a t i o n o f p r e s s u r e
M

Thermodynamics.
of a substance confined in a given space, as in the case of

certain applications of the air thermometer.
It has also been proposed to define temperature so that
equal increments of heat applied to a standard substance
will produce equal increments of temperature. This method
also fails to give results consistent for all substances, because
the specific heats of different substances are not in the same
ratio at different temperatures.
T h e only method which is certain to give consistent re
sults, whatever be the substance employed, is that which is
founded on Carnot's Function, and the most convenient
form in which this method can be applied is that which de
fines the absolute temperature as the reciprocal of Carnot's
Function. W e shall see afterwards how a comparison can
be made between the absolute temperature on the thermo
dynamic scale and the temperature as indicated by a
thermometer of a particular kind o f gas. (See p. 2 1 3 . )
ON ENTROPY.
W e have next to consider the series of adiabatic lines as

indicating a series of degrees of another property of the
body, expressed as a measurable quantity, such that when
there is no communication o f heat this quantity remains
constant, but when heat enters or leaves the body the quan
tity increases or diminishes.
W e shall adopt the name given b y Clausius to this quan
tity, and call it the entropy o f the body. Rankine, in whose
investigations this quantity also plays an important part, calls
it the thermodynamic function. This term, however, is not
so appropriate, as the name might have been assigned to any
one of several important quantities in thermodynamics.
W e must regard the entropy o f a body, like its volume,
pressure, and temperature, as a distinct physical property of
the body depending on its actual state.
T h e proper zero of entropy is that of the body when entirely
deprived of heat, but as we cannot bring the body into this
condition it is more convenient to reckon entropy from a
standard state defined by a standard temperature and pressure.
Entropy. 163
The entropy o f the b o d y in a n y other c o n d i t i o n is then
m e a s u r e d thus. L e t the b o d y e x p a n d ( o r c o n t r a c t ) w i t h o u t
c o m m u n i c a t i o n o f h e a t till it r e a c h e s t h e standard tempera
ture, the v a l u e o f w h i c h , o n t h e t h e r m o d y n a m i c s c a l e , is T.
T h e n let t h e b o d y b e k e p t a t t h e standard temperature and
brought t o the standard pressure, a n d let H be the number
of units o f h e a t g i v e n out during this p r o c e s s . Then the
e n t r o p y o f the b o d y i n its o r i g i n a l s t a t e is —.
W e shall use t h e s y m b o l c& t o d e n o t e t h e e n t r o p y .

I f the b o d y , i n order to arrive at the standard state,
requires to absorb h e a t , t h e n its original entropy must be
r e c k o n e d n e g a t i v e w i t h r e s p e c t t o t h e s t a n d a r d state.
W h e n heat enters a b o d y at the t e m p e r a t u r e 0 a n d causes
the e n t r o p y t o i n c r e a s e from ^ , t o (ji , t h e
z amount o f heat
w h i c h enters t h e b o d y is 6(<p — <f>i). 2
T h e entropy o f a b o d y in a given s t a t e is p r o p o r t i o n a l t o
the m a s s o f t h e b o d y , s o t h a t t h e entropy of two pounds of
water is d o u b l e t h a t o f o n e p o u n d i n t h e s a m e state.
W e often, h o w e v e r , s p e a k o f t h e e n t r o p y o f a substance,
by w h i c h w e m e a n t h e e n t r o p y o f unit o f mass o f that s u b
stance i n t h e g i v e n state.
T h e entropy of a system o f b o d i e s i n d i f f e r e n t s t a t e s is
the sum o f t h e e n t r o p i e s o f e a c h o f t h e b o d i e s .
W h e n a q u a n t i t y , H, o f h e a t p a s s e s f r o m a b o d y at t e m p e r a
ture 0, to a b o d y at t e m p e r a t u r e 6 , t h e e n t r o p y o f t h e first b o d y
2
is d i m i n i s h e d b y ^ i , w h i l e t h a t o f t h e s e c o n d is i n c r e a s e d b y
2
so t h a t t h e e n t r o p y o f t h e s y s t e m i n c r e a s e s b y H ^1~^ .
Now it is t h e condition o f the transfer o f heat that it

passes f r o m t h e h o t t e r t o t h e colder body, and t h e r e f o r e 9,
must b e g r e a t e r t h a n 0 - 2
T h e transference o f heat, therefore, from o n e b o d y o f the

system t o a n o t h e r a l w a y s i n c r e a s e s t h e e n t r o p y o f the s y s t e m .
Clausius e x p r e s s e s this b y s a y i n g t h a t the e n t r o p y o f the
system a l w a y s t e n d s t o w a r d s a m a x i m u m value.
M 2

164 Thermodynamics.
The heat w h i c h enters the b o d y during any very small

c h a n g e o f s t a t e is r e p r e s e n t e d , as w e h a v e s e e n , b y 8 (<P —<a 2 1),
w h e r e 9 is t h e mean temperature o f the b o d y during the

p r o c e s s , a n d 0, a n d 0 represent the e n t r o p y at the beginning
2
a n d the e n d o f the process.

If we suppose the t w o isentropic lines (PI a n d </> t o b e
2
continued in the direction o f decreasing temperatures down

to the temperature T , then the a r e a i n c l u d e d b e t w e e n the
t w o isentropic lines b e t w e e n the t e m p e r a t u r e s 0 a n d T will
be (8-T)(^-^,)-
I f w e could draw the i s e n t r o p i c a n d i s o t h e r m a l l i n e s cor
rectly for all temperatures d o w n t o t h e a b s o l u t e z e r o o f the
t h e r m o d y n a m i c scale, then the w h o l e area included between
the isentropic lines and the isothermals for 9 a n d zero would
be 9(I>I — <PI), a n d this area w o u l d r e p r e s e n t the heat whic
enters t h e b o d y during the process.
B u t t h o u g h i t is i m p o s s i b l e t o c o n j e c t u r e t h e p r o p e r t i e s
o f a b o d y a t a b s o l u t e z e r o o r t o d r a w o n a d i a g r a m t h e true
forms o f the thermal lines near that t e m p e r a t u r e , i t is easy,
after w e h a v e c o n s t r u c t e d the thermodynamic d i a g r a m for
that part o f the field w h i c h is known by observation,
t o d r a w l i n e s i n t h e u n k n o w n p a r t o f t h e field, b y m e a n s o f
w h i c h w e m a y still r e p r e s e n t q u a n t i t i e s o f h e a t b y areas.
I f the k n o w n p a r t o f t h e field is b o u n d e d b y t h e isother
mal T, and if w e draw from the extremities o f the k n o w n
parts o f the isentropic lines a series o f lines o f any form
which d o not intersect each other, and i f w e draw another
l i n e , zz', s o t h a t t h e s p a c e i n c l u d e d b e t w e e n this l i n e , t w o
n e i g h b o u r i n g i s e n t r o p i c s 0, a n d <j> a n d t h e
v isothermal line
T is T ( ^ 2 — w e m a y , i n c a l c u l a t i n g q u a n t i t i e s o f h e a t , treat
t h e l i n e zz' as t h e fictitious isothermal o f absolute zero, and
t h e series o f l i n e s as a fictitious isentropic series.
For the area b e t w e e n the t w o isentropic lines from tem
p e r a t u r e 0 t o t e m p e r a t u r e T is (9 — T ) ( 0 — T h i s 2 area is
within the k n o w n part o f the field. T h e continuation of
this a r e a i n t h e u n k n o w n p a r t o f t h e field d o w n t o t h e ficti
tious isothermal o f absolute z e r o is T ( < £ — 1 ^ ) .
2 T h e whole

Fictitious Thermal Lines. 165
area t h e r e f o r e is 0(p 2 —(h), and it therefore represents the
quantity o f h e a t absorbed in passing at the temperature 8
from the l i n e <j> t o t h e l i n e (p .
l 2
The whole heat a b s o r b e d b y a b o d y in passing from a

state A t o a s t a t e B t h r o u g h a d e f i n i t e s e r i e s o f i n t e r m e d i a t e
steps r e p r e s e n t e d b y F l G _ 2 3 a
the path A B , m a y b e
called the ' heat of
the path A B.' By
dividing A B into a
sufficient number of
small parts, a n d c o n
sidering t h e a r e a r e
presenting the heat
absorbed during the
passage o f t h e body
over e a c h o f t h e s e d i v i s i o n s , w e find t h a t t h e s u m o f t h e s e
areas is t h e a r e a i n c l u d e d b y t h e p a t h A B , the isentropics
through A a n d B i n c l u d i n g t h e i r fictitious parts, a n d the ficti
tious i s o t h e r m a l o f a b s o l u t e z e r o .
C H A P T E R IX.
O N T H E RELATIONS B E T W E E N T H E PHYSICAL
PROPERTIES O F A SUBSTANCE.
LET T, T! a n d T T 2 2 represent t w o isothermal lines corre
sponding to t w o c o n s e c u t i v e degrees o f temperature. Let
0i (j>i a n d <p <p r e p r e s e n t
2 2 t w o c o n s e c u t i v e adiabatic lines.
Let A p. c D be the q u a d r i l a t e r a l w h i c h lies b e t w e e n b o t h
these pairs o f l i n e s . I f the lines are drawn close enough to
each o t h e r w e m a y t r e a t this q u a d r i l a t e r a l as a p a r a l l e l o g r a m .
The a r e a o f this p a r a l l e l o g r a m is, as w e have already
shown, equal to unity.
D r a w h o r i z o n t a l l i n e s t h r o u g h A a n d r> t o m e e t t h e l i n e
B c produced in K and Q, t h e n , since the parallelograms
A B C D and A K Q D stand o n the same base and are b e t w e e n
the s a m e p a r a l l e l s , t h e y a r e e q u a l . N o w draw the vertical

166 Thermodynamics.
lines A k a n d K P to m e e t Q D , p r o d u c e d i f necessary. Then

t h e r e c t a n g l e A K P k is e q u a l t o t h e p a r a l l e l o g r a m A K Q D ,
because they stand o n the same base A K , and are between
the same parallels A K and k Q. H e n c e the r e c t a n g l e AKP h
FIG. 24.
is also equal to the original parallelogram A R C D . If,

therefore, we draw A K from A horizontally to meet the
i s o t h e r m a l T , and A k vertically t o m e e t a horizontal line
2
t h r o u g h D , w e shall h a v e t h e f o l l o w i n g r e l a t i o n :
A K. A k =A B C D.
I n t h e s a m e w a y , i f t h e h o r i z o n t a l l i n e t h r o u g h A cuts the
adiabatic line 0 2 in L and the verticals through D a n d B in
m a n d n, a n d i f t h e v e r t i c a l l i n e t h r o u g h A cuts t h e i s o t h e r m a l
l n N a n t t n e
line T 2 in M , the adiabatic line f 2 > ^ horizontal
l i n e t h r o u g h B i n /, w e shall g e t t h e f o l l o w i n g f o u r v a l u e s o f
the area o f A B C D , including that w h i c h w e h a v e already
investigated :
A B C D = A K . A / £ = A L . A / = A M . A W 2 = A N . A « = I .
We have next to interpret the physical m e a n i n g o f the

f o u r pairs o f l i n e s w h i c h e n t e r i n t o t h e s e p r o d u c t s .
We m u s t r e m e m b e r that t h e v o l u m e o f t h e s u b s t a n c e is
m e a s u r e d h o r i z o n t a l l y t o t h e r i g h t , a n d its p r e s s u r e v e r t i c a l l y

Four Thermodynamical Relations, 167
upwards ; that t h e i n t e r v a l b e t w e e n t h e i s o t h e r m a l lines

represents o n e d e g r e e o f t e m p e r a t u r e , t h e g r a d u a t i o n o f t h e
scale b e i n g as m u c h s u b d i v i d e d as w e p l e a s e ; a n d that the
interval b e t w e e n t h e a d i a b a t i c l i n e s r e p r e s e n t s t h e a d d i t i o n
of a quantity o f heat whose numerical value is T, the
absolute t e m p e r a t u r e .
(1) A K r e p r e s e n t s t h e i n c r e a s e o f v o l u m e f o r a rise o f
temperature e q u a l to o n e d e g r e e , the pressure b e i n g m a i n
tained constant. This is called the dilatability of the
substance p e r unit o f m a s s , a n d i f w e d e n o t e t h e d i l a t a b i l i t y
per unit o f v o l u m e b y A K w i l l b e d e n o t e d b y v a,
A k represents the d i m i n u t i o n o f pressure corresponding
to t h e a d d i t i o n o f a q u a n t i t y o f h e a t r e p r e s e n t e d n u m e r i c a l l y
b y T , the t e m p e r a t u r e b e i n g m a i n t a i n e d c o n s t a n t .
I f the p r e s s u r e is i n c r e a s e d b y u n i t y , the temperature
r e m a i n i n g c o n s t a n t , t h e q u a n t i t y o f h e a t w h i c h is e m i t t e d b y
the substance is ——. Since A K . A k = 1, —— = T . A K.

A k Ak
H e n c e the f o l l o w i n g relation b e t w e e n the dilatation under
constant p r e s s u r e a n d t h e h e a t d e v e l o p e d b y p r e s s u r e .
First Thermodyna7nu Relation.—If the pressure o f a sub
stance b e i n c r e a s e d b y u n i t y w h i l e t h e t e m p e r a t u r e is m a i n
tained c o n s t a n t , t h e q u a n t i t y o f h e a t emitted b y the sub
stance is e q u a l t o t h e p r o d u c t o f t h e a b s o l u t e temperature
into the dilatation for o n e degree o f temperature under
constant p r e s s u r e .
H e n c e , i f the t e m p e r a t u r e is m a i n t a i n e d constant, those
substances which increase in volume as t h e temperature
rises g i v e out heat w h e n the press,ure is increased, and
those w h i c h c o n t r a c t as t h e t e m p e r a t u r e rises a b s o r b heat
w h e n t h e p r e s s u r e is i n c r e a s e d .
(2) A L r e p r e s e n t s t h e i n c r e a s e o f v o l u m e u n d e r constant
pressure w h e n a q u a n t i t y o f h e a t n u m e r i c a l l y e q u a l t o T i s
communicated to the substance.
A / represents the increase o f pressure r e q u i r e d t o raise

TJiermodynamics.
the substance o n e degree o f temperature w h e n n o h e a t is
allowed to escape.
Secçnd Thermodynamic Relation.—The quantity — re

p r e s e n t s t h e h e a t w h i c h m u s t b e c o m m u n i c a t e d t o t h e sub
s t a n c e i n o r d e r t o i n c r e a s e its v o l u m e b y u n i t y , t h e pressure
being constant. T h i s is e q u a l t o t h e p r o d u c t o f t h e ab
solute t e m p e r a t u r e i n t o t h e increase o f pressure required
t o raise t h e t e m p e r a t u r e o n e d e g r e e w h e n n o h e a t is a l l o w e d
to escape.
(3) A M r e p r e s e n t s t h e i n c r e a s e o f p r e s s u r e c o r r e s p o n d i n g
to a rise o f o n e d e g r e e o f temperature, the v o l u m e being
constant. ( W e m a y suppose the substance e n c l o s e d in a
vessel the sides o f w h i c h are perfectly unyielding.)
A m r e p r e s e n t s t h e i n c r e a s e o f v o l u m e p r o d u c e d b y the
communication o f a quantity o f heat numerically equal to
T , the temperature being maintained constant.
T h e heat g i v e n out b y the substance w h e n t h e v o l u m e is
d i m i n i s h e d b y unity, the temperature b e i n g m a i n t a i n e d con
stant, is t h e r e f o r e — — . T h i s q u a n t i t y is c a l l e d t h e l a t e n t
Am
heat o f expansion.
Since A M . A m = 1, w e m a y e x p r e s s t h e r e l a t i o n b e t w e e n
t h e s e l i n e s thus : — — = T . A M , or, in w o r d s :
m A
Third Thermodynamic Relation.—The latent heat o f ex

p a n s i o n is e q u a l t o t h e p r o d u c t o f t h e a b s o l u t e t e m p e r a t u r e
a n d t h e i n c r e m e n t o f p r e s s u r e p e r d e g r e e o f t e m p e r a t u r e at
constant volume.
(4) A N r e p r e s e n t s t h e i n c r e a s e o f t h e p r e s s u r e w h e n a
q u a n t i t y , T , o f h e a t is c o m m u n i c a t e d t o t h e s u b s t a n c e , the
v o l u m e b e i n g constant.
A n r e p r e s e n t s t h e d i m i n u t i o n o f v o l u m e w h e n t h e sub
s t a n c e , b e i n g p r e v e n t e d f r o m l o s i n g h e a t , is c o m p r e s s e d till
t h e t e m p e r a t u r e rises o n e d e g r e e . Hence :

Specific Heat. l6g
Fourth Thermodynamic Relation. — represents the

A n
rise o f temperature due to a diminution o f the volume
b y unity, n o h e a t b e i n g a l l o w e d t o e s c a p e , a n d t h i s is e q u a l
to A N , t h e increase o f p r e s s u r e at c o n s t a n t v o l u m e d u e t o
a quantity o f heat, numerically equal t o T , c o m m u n i c a t e d t o
the s u b s t a n c e .
We h a v e thus o b t a i n e d f o u r r e l a t i o n s a m o n g t h e physical
properties o f the substance. T h e s e four relations are not
i n d e p e n d e n t o f e a c h o t h e r , s o as t o r a n k as separate truths.
Any one might be deduced from any other. The equality
of the p r o d u c t s A K, A k, & c , t o t h e p a r a l l e l o g r a m A B C D
a n d t o e a c h o t h e r is a m e r e l y g e o m e t r i c a l t r u t h , a n d d o e s
not depend upon thermodynamical principles. What we
learn f r o m thermodynamics is that the p a r a l l e l o g r a m and
the four p r o d u c t s are each equal to unity, w h a t e v e r b e the
nature o f t h e s u b s t a n c e o r its c o n d i t i o n as t o p r e s s u r e and
1
temperature.
O N T H E T W O M O D E S O F M E A S U R I N G SPECIFIC H E A T .
The quantity o f heat r e q u i r e d t o raise unit o f mass o f t h e

substance o n e d e g r e e o f t e m p e r a t u r e is c a l l e d t h e s p e c i f i c
heat o f the s u b s t a n c e .
1
These four relations may be concisely expressed in the language of
the Differential Calculus as follows:
D V _ D (P
, . (I)
D~e (P const.) ~~ DF, (fl const.) ' '
D V D fl • (2)
DIP (P const.) ~ ~DP (<f> const.) - -
DP _ D <f>
DH (V const.) D (fl const.)
V • 1
• (3)
P d D 9
D TP const.) D (<P const.)
V
1 1 • (4)
Here V denotes the volume.
p ,, pressure.
S „ absolute temperature.
$ ,, thermodynamic function, or ENTROPY.

Tliermodynamics.
A t p . 66 this q u a n t i t y o f h e a t is e x p r e s s e d i n t e r m s o f the
t h e r m a l unit, o r t h e h e a t r e q u i r e d t o r a i s e u n i t o f mass of
water o n e degree. T o r e d u c e this t o d y n a m i c a l m e a s u r e we
m u s t m u l t i p l y b y J o u l e ' s m e c h a n i c a l e q u i v a l e n t o f t h e thermal
unit. T h e q u a n t i t y thus f o u n d is n o l o n g e r a m e r e r a t i o , as
at p . 6 6 , b u t d e p e n d s o n t h e t h e r m o m e t r i c s c a l e w h i c h w e
select a n d also o n the unit o f w o r k .
B u t the s p e c i f i c h e a t o f a s u b s t a n c e d e p e n d s o n t h e m o d e
in w h i c h t h e pressure and v o l u m e o f the substance vary
d u r i n g t h e rise o f t e m p e r a t u r e .
T h e r e are, therefore, an indefinite n u m b e r o f m o d e s of
defining the specific heat. T w o o n l y o f these are o f any
practical importance. T h e first m e t h o d is t o s u p p o s e the
v o l u m e t o r e m a i n constant d u r i n g t h e rise o f temperature.
T h e s p e c i f i c h e a t u n d e r this c o n d i t i o n is c a l l e d t h e specific
h e a t at c o n s t a n t v o l u m e . W e s h a l l d e n o t e it b y K .
V
I n the diagram the line A M N represents the different

states o f t h e s u b s t a n c e w h e n t h e v o l u m e is c o n s t a n t , A M
represents the increase o f pressure d u e t o a rise o f one
d e g r e e o f temperature, a n d A N that d u e t o the application
o f a quantity of heat numerically equal to T . H e n c e t o find
the quantity o f heat, which must b e c o m m u n i c a t e d to
t h e s u b s t a n c e i n o r d e r t o r a i s e its t e m p e r a t u r e one degree,
a n d so increase the pressure b y A M , w e h a v e
A N : A M :: T : K T
T h e s e c o n d m e t h o d o f d e f i n i n g s p e c i f i c h e a t is t o s u p p o s e
the pressure constant. T h e specific heat under constant
p r e s s u r e is d e n o t e d b y K . P
T h e l i n e A L K in t h e d i a g r a m r e p r e s e n t s t h e d i f f e r e n t states
o f t h e s u b s t a n c e at c o n s t a n t p r e s s u r e , A K r e p r e s e n t s the in
crease o f v o l u m e d u e t o a rise o f o n e d e g r e e o f temperature,
a n d A L represents the increase o f v o l u m e due to a quantity
of h e a t n u m e r i c a l l y e q u a l t o T. N O W the quantity K „ of
h e a t r a i s e s the s u b s t a n c e o n e degree, a n d therefore increases
t h e v o l u m e b y A K.
Relations of Specific Heat and Elasticity. 171
Hence
A L :A K ;; T : K P
or
A K
K E = T .
A L
(A third mode of defining specific heat is sometimes
adopted in the case of saturated steam. I n this c a s e the
steam is s u p p o s e d t o r e m a i n at t h e p o i n t o f s a t u r a t i o n as
the t e m p e r a t u r e rises. I t appears, from the experiments o f
M. R e g n a u l t , as s h o w n in t h e d i a g r a m at p . 135, t h a t heat
leaves the saturated s t e a m as i t s t e m p e r a t u r e rises, so t h a t
its specific h e a t is negative, a result p o i n t e d o u t b y C l a u s i u s
and R a n k i n e . )
ON T H E TWO MODES O FMEASURING ELASTICITY.
The elasticity of a substance w a s d e f i n e d at p. 107 to

be the ratio of the increment of pressure to the com
pression p r o d u c e d b y it, the compression being defined
to b e t h e r a t i o of t h e d i m i n u t i o n o f v o l u m e t o t h e o r i g i n a l
volume.
But w e r e q u i r e to know something about the thermal
c o n d i t i o n s u n d e r w h i c h t h e s u b s t a n c e is p l a c e d b e f o r e w e
can assign a d e f i n i t e v a l u e t o t h e e l a s t i c i t y . T h e only two
conditions which are of practical importance are, first,
when the temperature remains constant, and, s e c o n d , w h e n
there is n o c o m m u n i c a t i o n of h e a t .
(1) T h e e l a s t i c i t y u n d e r t h e c o n d i t i o n t h a t t h e t e m p e r a t u r e
remains c o n s t a n t m a y b e d e n o t e d b y E«.
In this c a s e t h e r e l a t i o n b e t w e e n v o l u m e a n d p r e s s u r e is
defined b y the isothermal line D A. The increment of
pressure is k A, and the diminution o f v o l u m e is m A.
Calling the v o l u m e v , t h e e l a s t i c i t y at c o n s t a n t tempera
ture is
A k A M
E 9 = V - V .
A m A K.
(2) T h e elasticity under the c o n d i t i o n that heat neither
enters n o r l e a v e s t h e s u b s t a n c e is d e n o t e d b y E4,.
In this c a s e t h e r e l a t i o n b e t w e e n v o l u m e a n d p r e s s u r e is
172 TJiermodynamics.
d e n n e d b y trie a d i a b a t i c l i n e A B. T h e i n c r e m e n t o f pressure
is A / , and the decrement o f v o l u m e i s A n. Hence the
e l a s t i c i t y w h e n n o h e a t e s c a p e s is
A / AN
Ea = V . = V
A 71 A L
There are several important relations among these
quantities. In the first place, w e find f o r t h e r a t i o o f the
specific heats,
A K AN
T . — V .
A L
Kp _ AL_E^
_ _ E s
K
" ~ x . ±20: v . —
' A N A K
or t h e ratio o f the specific h e a t at c o n s t a n t p r e s s u r e t o that

at constant v o l u m e is e q u a l t o the ratio o f the elasticity
w h e n n o heat escapes to the elasticity at constant tempera
ture. T h i s r e l a t i o n is q u i t e i n d e p e n d e n t o f t h e p r i n c i p l e s o f
thermodynamics, being a direct consequence o f the defini
tions.
The r a t i o o f K t o K „ o r o f E^, t o E
p 9] is c o m m o n l y d e n o t e d
b y the s y m b o l y : thus K p = yK , a n d E^ =
v yE«.
Let us next determine the difference between thq two
elasticities
A /.A m — Kn.hk
Ej, — E« = v . -.
A m. A n
The numerator o f the fraction is e v i d e n t l y , b y t h e g e o
metry o f the figure, equal to the parallelogram A B c D.
M u l t i p l y i n g b y K „ w e find
M^-E,) = T V . ^ 1 . A B C D
= T . V . ^ ,
Am A N . A « AWi
since A « . A N = ABCD, as w e h a v e s h o w n .
Since K T E ^= K P E 9 > w e also find
/ \ A M
E (K„ — K ) = T v
6 T
Am
These relations are independent of the principles of
thermodynamics.
Latent Heat. 173
I f w e n o w apply the thermodynamical equation A M . A m
= 1, e a c h o f t h e s e q u a n t i t i e s b e c o m e s e q u a l t o
T v . (A M) . 2
Now A M is t h e i n c r e m e n t o f p r e s s u r e at c o n s t a n t v o l u m e
per degree o f temperature, a v e r y important quantity. The
results t h e r e f o r e may b e written
K T (E0 — Be) = T V A M » = Eg (K„ — K ) . Y
C H A P T E R X.
ON L A T E N T HEAT.
A V E R Y i m p o r t a n t c l a s s o f c a s e s is t h a t i n w h i c h t h e sub
s t a n c e is i n t w o d i f f e r e n t states a t t h e s a m e t e m p e r a t u r e a n d
pressure, as w h e n p a r t o f it is s o l i d a n d p a r t l i q u i d , or part
solid or l i q u i d and part gaseous.
In such c a s e s t h e v o l u m e o c c u p i e d b y t h e s u b s t a n c e m u s t
be c o n s i d e r e d as c o n s i s t i n g o f t w o parts, v 1 b e i n g that o f the
s u b s t a n c e i n t h e first state, a n d v 2 t h a t o f t h e s u b s t a n c e in
the s e c o n d state. T h e quantity o f heat necessary to convert
unit o f m a s s o f the substance from t h e first s t a t e to the
s e c o n d w i t h o u t a l t e r i n g its t e m p e r a t u r e is c a l l e d t h e L a t e n t
H e a t o f t h e s u b s t a n c e , a n d is d e n o t e d b y L.
D u r i n g this p r o c e s s t h e v o l u m e c h a n g e s f r o m v 1 t o z> at
3
the c o n s t a n t p r e s s u r e ^ .
Let p s be an isothermal
line, w h i c h i n this c a s e is h o r i
z o n t a l , a n d l e t i t c o r r e s p o n d to
the p r e s s u r e P a n d t h e t e m p e
rature s.
Let Q T be another iso
t h e r m a l l i n e c o r r e s p o n d i n g to
the pressure Q a n d the t e m p e
rature T.

174 Latent Heat.
L e t B A a n d c D b e adiabatic lines cutting the isothermals

ill A B C D.
Then t h e s u b s t a n c e , i n e x p a n d i n g at t h e t e m p e r a t u r e s
from the volume p B to the v o l u m e P C, w i l l a b s o r b a
q u a n t i t y o f h e a t e q u a l t o L — — — , w h e r e L is t h e latent
v — Vi 2
h e a t at t e m p e r a t u r e s.
When the substance is c o m p r e s s e d f r o m Q D t o Q A at
t e m p e r a t u r e T it w i l l g i v e o u t a q u a n t i t y o f h e a t e q u a l t o
w h e r e t h e a c c e n t e d q u a n t i t i e s refer t o t h e t e m p e r a t u r e T.
The q u a n t i t y o f w o r k d o n e b y a n e n g i n e w h e n the indi
c a t i n g p o i n t d e s c r i b e s t h e f i g u r e A E C D o n t h e d i a g r a m is
r e p r e s e n t e d b y t h e a r e a o f this figure, a n d i f the temperatures
s and T are so near e a c h other that w e m a y neglect the
c u r v a t u r e o f t h e l i n e s A B a n d c D , this a r e a is
£ (B C + A D ) P Q.
I f t h e d i f f e r e n c e o f p r e s s u r e s p Q is v e r y s m a l l , B C = A D
n e a r l y , so t h a t w e m a y w r i t e t h e a r e a thus :
B c ( p — Q).
But w e m a y calculate the w o r k in another way. It is
equal to the heat absorbed at the higher temperature,
multiplied b y the ratio o f the difference o f the temperatures
to t h e h i g h e r t e m p e r a t u r e . T h i s is
B c s — T
V 2 — Z>, S
E q u a t i n g the t w o v a l u e s o f t h e w o r k , w e find t h e l a t e n t
heat
/
L = {p - vj \s
t
P — Q
_ ^ ,
w h e r e it is t o b e r e m e m b e r e d t h a t i n c a l c u l a t i n g t h e frac
t i o n y ~~ ^ t h e d i f f e r e n c e o f t h e p r e s s u r e s P a n d Q a n d the
s — T
d i f f e r e n c e o f the t e m p e r a t u r e s s a n d T a r e t o b e supposed

Latent Heat. 175
very small. I n fact, t h i s f r a c t i o n is t h a t w h i c h i n t h e lan
guage o f the differential calculus w o u l d b e d e n o t e d b y ^~

ao
The student m a y d e d u c e the equation at o n c e from the
third t h e r m o d y n a m i c r e l a t i o n at p . 168.
T h e most important case o f a substance in t w o different
states is that i n w h i c h t h e s u b s t a n c e is p a r t l y w a t e r and
partly s t e a m at t h e s a m e temperature.
T h e p r e s s u r e o f s t e a m i n a v e s s e l c o n t a i n i n g w a t e r at t h e
same t e m p e r a t u r e is c a l l e d the p r e s s u r e o f s a t u r a t e d s t e a m
or a q u e o u s v a p o u r a t t h a t t e m p e r a t u r e .
T h e v a l u e o f this p r e s s u r e has b e e n d e t e r m i n e d f o r a g r e a t
n u m b e r o f t e m p e r a t u r e s as m e a s u r e d o n t h e o r d i n a r y s c a l e s .
T h e m o s t c o m p l e t e d e t e r m i n a t i o n s o f this k i n d a r e t h o s e o f
Regnault. R e g n a u l t h a s a l s o d e t e r m i n e d 1., t h e l a t e n t h e a t
o f unit o f m a s s o f s t e a m , f o r m a n y d i f f e r e n t temperatures.
Hence, if w e also k n e w the value of v 2 — w , or
v the
difference o f v o l u m e b e t w e e n u n i t o f m a s s o f w a t e r a n d the
same w h e n c o n v e r t e d into steam, w e should have all the
data for d e t e r m i n i n g s, t h e absolute temperature on the
t h e r m o d y n a m i c scale.
Unfortunately there is considerable difficulty in ascer
taining the v o l u m e o f s t e a m at t h e p o i n t o f s a t u r a t i o n . If
we place a k n o w n w e i g h t o f water in a vessel, the capacity
o f w h i c h w e c a n adjust, and determine either the capacity
corresponding t o a g i v e n temperature at w h i c h t h e w h o l e is
just c o n v e r t e d i n t o s t e a m , o r t h e t e m p e r a t u r e corresponding
to a given capacity, w e m a y obtain data for determining
the density o f saturated s t e a m , b u t it is e x c e e d i n g l y difficult
to o b s e r v e e i t h e r t h e c o m p l e t i o n o f t h e e v a p o r a t i o n or the
beginning o f the condensation, and at the same time to
avoid other causes o f error. I t is t o b e h o p e d that these
difficulties w i l l b e o v e r c o m e , a n d t h e n our k n o w l e d g e o f t h e
other p r o p e r t i e s o f s a t u r a t e d s t e a m w i l l e n a b l e us t o c o m p a r e
the o r d i n a r y s c a l e s o f t e m p e r a t u r e with the thermodynamic
0 0
scale t h r o u g h a r a n g e e x t e n d i n g f r o m — 3 0 F . to 4 3 2 F.
I n the m e a n t i m e Clausius a n d R a n k i n e h a v e m a d e use o f

176 Latent Heat.
the f o r m u l a in o r d e r t o calculate the density o f saturated

s t e a m , a s s u m i n g t h a t t h e a b s o l u t e t e m p e r a t u r e is e q u a l t o the
temperature r e c k o n e d from —460° o f Fahrenheit's scale.
The same principle enables us to establish relations
b e t w e e n t h e p h y s i c a l p r o p e r t i e s o f a s u b s t a n c e at t h e p o i n t
a t w h i c h i t c h a n g e s f r o m the s o l i d t o t h e l i q u i d state.
r
T h e temperature o f m e l t i n g i c e w a s alw ays supposed to b e
a b s o l u t e l y c o n s t a n t t i l l it w a s p o i n t e d o u t b y P r o f e s s o r J a m e s
1
Thomson that it follows from Carnot's p r i n c i p l e that the
m e l t i n g point must b e l o w e r e d w h e n the pressure increases;
for i f is t h e v o l u m e o f a p o u n d o f i c e , a n d v 2 that o f a
pound o f water, b o t h b e i n g at 32° F . , w e k n o w that the
v o l u m e o f t h e i c e is g r e a t e r t h a n t h a t o f t h e w a t e r . Hence
i f s b e t h e m e l t i n g p o i n t at p r e s s u r e P , a n d T t h e melting
p o i n t a t p r e s s u r e Q, w e h a v e , as at p . 174,
If we make p = o and s = 32° F . , then the m e l t i n g tem-

p e r a t u r e at p r e s s u r e Q is
T = 3 2 ° F . _ (vx - vt) Q £.
Now t h e v o l u m e o f a p o u n d o f i c e at 3 2 ° F . is 0^0174
cubic feet = vlt a n d t h a t o f a p o u n d o f w a t e r a t the same
t e m p e r a t u r e is 0-016 c u b i c f e e t = v.
2 s, t h e a b s o l u t e t e m p e -
r a t u r e , c o r r e s p o n d i n g t o 3 2 ° F . , is 4 9 2 ° . L , the latent heat
r e q u i r e d t o c o n v e r t a p o u n d o f i c e i n t o a p o u n d o f water,
= 142 t h e r m a l u n i t s = 142 x 772 f o o t - p o u n d s . H e n c e T,
the temperature o f m e l t i n g , c o r r e s p o n d i n g to a pressure o f
Q p o u n d s w e i g h t p e r s q u a r e f o o t , is
x = 3 2 ° — O ° 0 0 0 0 O Ó 3 x Q.
-
I f the pressure b e that o f n atmospheres, each atmosphere

b e i n g 2,116 p o u n d s w e i g h t p e r s q u a r e f o o t ,
T = 32° — o°-oi33 n.
1
Transactions of the Royal Society of Edinburgh, vol. xvi. p. 575»
January 2 , 1849.

Freezing Point altered by Pressure. 177
H e n c e t h e m e l t i n g p o i n t o f i c e is l o w e r e d b y a b o u t the
seventy-fifth part of a degree of Fahrenheit for every
additional atmosphere o f pressure. T h i s result o f theory
was v e r i f i e d b y t h e direct experiments of Professor W.
1
Thomson. '
P r o f e s s o r J. T h o m s o n has a l s o p o i n t e d o u t t h e i m p o r t a n c e
o f the u n i q u e c o n d i t i o n as t o t e m p e r a t u r e a n d p r e s s u r e u n d e r
which water or a n y other substance can p e r m a n e n t l y exist
in the s o l i d , l i q u i d , a n d g a s e o u s forms in the same vesseL
T h i s c a n o n l y b e at t h e f r e e z i n g t e m p e r a t u r e corresponding
to the pressure o f v a p o u r at t h i s f r e e z i n g p o i n t . He calls
this the t r i p l e p o i n t , b e c a u s e t h r e e t h e r m a l l i n e s m e e t i n i t —
(1) the s t e a m l i n e , w h i c h d i v i d e s t h e l i q u i d f r o m t h e g a s e o u s
state j (2) the i c e l i n e , w h i c h d i v i d e s t h e l i q u i d f r o m t h e s o l i d
s t a t e ; (3) t h e h o a r - f r o s t l i n e , w h i c h d i v i d e s t h e s o l i d f r o m t h e
gaseous state.
W h e n e v e r the v o l u m e o f the substance is, l i k e that o f

water, less i n t h e l i q u i d t h a n i n t h e s o l i d state, t h e effect o f
pressure o n a v e s s e l c o n t a i n i n g t h e substance partly in a
l i q u i d a n d p a r t l y in a s o l i d s t a t e is t o c a u s e s o m e o f t h e
solid p o r t i o n t o m e l t , a n d t o l o w e r t h e t e m p e r a t u r e o f t h e
whole t o the m e l t i n g p o i n t c o r r e s p o n d i n g to the pressure.
If, o n t h e c o n t r a r y , t h e v o l u m e o f t h e s u b s t a n c e is g r e a t e r i n
the l i q u i d t h a n i n t h e s o l i d s t a t e , t h e effect o f p r e s s u r e is t o
solidify s o m e o f t h e l i q u i d p a r t , a n d t o r a i s e t h e temperature
t o the m e l t i n g p o i n t corresponding to the pressure. To
d e t e r m i n e at o n c e w h e t h e r t h e v o l u m e o f t h e s u b s t a n c e is
greater i n t h e liquid or the s o l i d state, w e h a v e only to
o b s e r v e w h e t h e r s o l i d p o r t i o n s o f t h e s u b s t a n c e s i n k or s w i m
in the m e l t e d s u b s t a n c e . If, like i c e in water, they s w i m ,
the v o l u m e is g r e a t e r i n t h e s o l i d s t a t e , a n d p r e s s u r e causes
melting and lowers the m e l t i n g point. If, l i k e sulphur, w a x ,
and m o s t k i n d s o f s t o n e , t h e s o l i d s u b s t a n c e sinks in the
liquid, t h e n pressure causes solidification and raises the
melting point.
1
Proceedings of the Royal Society of Edi?iburgk, 1850.
N

178 Application of Thermodynamics to Gases.
W h e n t w o p i e c e s o f i c e at t h e m e l t i n g p o i n t a r e pressed
together, the pressure causes m e l t i n g t o t a k e p l a c e at the
p o r t i o n s o f t h e surface i n c o n t a c t . T h e water so formed
escapes out o f the way and the temperature is lowered.
H e n c e as s o o n as t h e p r e s s u r e d i m i n i s h e s t h e t w o parts are,
0
frozen together with ice at a temperature below 32 . This
p h e n o m e n o n is c a l l e d R e g e l a t i o n .
I t is w e l l k n o w n that t h e t e m p e r a t u r e o f the earth increases
as w e d e s c e n d , so that at t h e b o t t o m o f a d e e p b o r i n g it is
c o n s i d e r a b l y h o t t e r t h a n at t h e surface. W e shall see that,
unless w e s u p p o s e t h e p r e s e n t state o f t h i n g s t o b e o f n o
g r e a t a n t i q u i t y , this i n c r e a s e o f t e m p e r a t u r e m u s t g o o n to
m u c h g r e a t e r d e p t h s t h a n a n y o f our b o r i n g s . I t is easy on
this s u p p o s i t i o n t o c a l c u l a t e at w h a t d e p t h t h e temperature
w o u l d b e e q u a l to t h a t a t w h i c h m o s t k i n d s o f s t o n e m e l t in
o u r furnaces, a n d it has b e e n s o m e t i m e s a s s e r t e d that at this
d e p t h w e s h o u l d find e v e r y t h i n g i n a state o f fusion. But
w e m u s t r e c o l l e c t that a t such d e p t h s t h e r e is an enormous
pressure, a n d t h e r e f o r e r o c k s w h i c h i n o u r furnaces would
b e m e l t e d at a c e r t a i n t e m p e r a t u r e m a y r e m a i n s o l i d e v e n at
m u c h g r e a t e r t e m p e r a t u r e s i n t h e h e a r t o f t h e earth.
CHAPTER X I .
ON THE APPLICATION OF T H E PRINCIPLES OF
THERMODYNAMICS TO GASES.
THE p h y s i c a l p r o p e r t i e s o f b o d i e s i n t h e g a s e o u s state are

more s i m p l e t h a n w h e n t h e y a r e i n a n y o t h e r state. The
relations o f the volume, pressure, and temperature are
then more or less a c c u r a t e l y r e p r e s e n t e d by the laws of
B o y l e a n d C h a r l e s , w h i c h w e shall s p e a k of, for b r e v i t y , as

Thermodynamics of Gases. 179
the ' g a s e o u s l a w s . ' W e m a y express them in the following
form :
L e t v d e n o t e t h e v o l u m e o f u n i t o f mass, p t h e pressure,
/ the t e m p e r a t u r e measured b y an air thermometer and
reckoned from the absolute zero o f that instrument, then
the q u a n t i t y - ^ - r e m a i n s c o n s t a n t f o r t h e s a m e g a s .
W e h e r e use the s y m b o l / t o d e n o t e t h e a b s o l u t e t e m p e r a
ture as measured b y the air thermometer, reserving the
symbol 6 to denote the temperature according to the
absolute t h e r m o d y n a m i c s c a l e .
W e have n o right t o assume w i t h o u t p r o o f that these t w o
quantities a r e t h e s a m e , a l t h o u g h w e shall b e a b l e t o s h o w
by e x p e r i m e n t that t h e o n e is n e a r l y e q u a l t o t h e o t h e r .
I t is p r o b a b l e t h a t w h e n t h e v o l u m e a n d the temperature
are sufficiently g r e a t a l l g a s e s fulfil with great accuracy the
gaseous l a w s ; b u t when, b y compression and cooling, the
i;as is b r o u g h t near t o its p o i n t of condensation into the
liquid form, the quantity b e c o m e s less than it is f o r
the p e r f e c t l y g a s e o u s state, a n d the substance, though still

apparently gaseous, no longer fulfils with accuracy the
gaseous l a w s . (See pp. i r 6 , 119.)
T h e specific heat o f a gas can b e d e t e r m i n e d only b y a
course o f e x p e r i m e n t s i n v o l v i n g c o n s i d e r a b l e d i f f i c u l t y and
requiring great d e l i c a c y in the measurements. The gas
must be enclosed in a vessel, and the density of the
gas itself is s o s m a l l t h a t its c a p a c i t y f o r h e a t forms but
a small p a r t o f t h e t o t a l c a p a c i t y o f the apparatus. Any
error, t h e r e f o r e , i n t h e d e t e r m i n a t i o n o f t h e c a p a c i t y e i t h e r
o f the v e s s e l i t s e l f o r o f t h e vessel with the g a s i n i t w i l l
produce a m u c h larger error in the calculated specific heat o f
the gas.
H e n c e the determinations o f the specific heat o f gases
were generally v e r y inaccurate, till M . Regnault brought
all the r e s o u r c e s o f his e x p e r i m e n t a l skill to bear on the
N 2

180 Application of Thermodynamics to Gase*.
i n v e s t i g a t i o n , a n d , by m a k i n g t h e g a s p a s s i n a continuous
c u r r e n t a n d i n l a r g e q u a n t i t i e s t h r o u g h t h e t u b e o f his calori
m e t e r , d e d u c e d results w h i c h c a n n o t b e far f r o m t h e truth.
T h e s e results, h o w e v e r , w e r e n o t p u b l i s h e d till 1853, but in
t h e m e a n t i m e R a n k i n e , b y t h e a p p l i c a t i o n o f t h e principles
of thermodynamics to facts already known, determined
theoretically a value o f the specific heat o f air, w h i c h he
published in 1850. T h e v a l u e w h i c h h e o b t a i n e d differed
f r o m t h a t w h i c h w a s t h e n r e c e i v e d as t h e b e s t result o f direct
experiment, but when Regnault's result was published it
a g r e e d exactly with R a n k i n e ' s calculation.
We must now explain the principle which Rankine
applied. W h e n a g a s is c o m p r e s s e d w h i l e t h e temperature
remains constant, the product o f the v o l u m e and pressure
remains constant. H e n c e , as w e h a v e s h o w n , t h e elasticity
o f t h e g a s at c o n s t a n t t e m p e r a t u r e is n u m e r i c a l l y e q u a l to its
pressure.
B u t i f t h e v e s s e l in w h i c h t h e g a s is c o n t a i n e d is i n c a p a b l e
o f r e c e i v i n g h e a t f r o m t h e g a s , o r o f c o m m u n i c a t i n g heat t o
it, t h e n w h e n c o m p r e s s i o n t a k e s p l a c e the temperature will
rise, a n d the pressure will be greater than it w a s in the
f o r m e r case. T h e e l a s t i c i t y , t h e r e f o r e , w i l l b e g r e a t e r in tire
case of no thermal communication than in the case o f
constant temperature.
T o determine the elasticity under these circumstances in
this w a y w o u l d b e i m p o s s i b l e , b e c a u s e w e cannot obtain a
vessel which will not allow heat to escape from the gas
w i t h i n it. If, h o w e v e r , t h e c o m p r e s s i o n is effected rapidly,
there will be very little t i m e for the heat to escape, but
then there will b e v e r y little t i m e to measure t h e pressure
in the ordinary way. I t is p o s s i b l e , h o w e v e r , after com
p r e s s i n g air i n t o a l a r g e v e s s e l a t a k n o w n t e m p e r a t u r e , to
open an aperture o f considerable s i z e f o r a t i m e w h i c h is
sufficient t o a l l o w t h e air t o rush o u t t i l l t h e p r e s s u r e is the
same within and without the vessel, but n o t sufficient to
a l l o w m u c h h e a t t o be a b s o r b e d b y t h e air f r o m t h e s i d e s of

Cooling of A ir by Expansion. 181
the vessel. W h e n t h e a p e r t u r e is c l o s e d t h e air is s o m e w h a t

cooler than before, a n d though it receives heat from the
sides o f t h e v e s s e l so fast t h a t its t e m p e r a t u r e i n t h e cooled
state c a n n o t b e a c c u r a t e l y o b s e r v e d w i t h a t h e r m o m e t e r , the
amount of cooling may be calculated by observing the
pressure o f t h e air w i t h i n t h e v e s s e l after its t e m p e r a t u r e has
become equal to that o f the atmosphere. S i n c e at the
m o m e n t o f c l o s i n g t h e a p e r t u r e t h e air w i t h i n w a s c o o l e r t h a n
the air w i t h o u t , w h i l e its pressure was the same, it f o l l o w s
that w h e n t h e temperature within has risen so as to be
equal t o that o f t h e a t m o s p h e r e its p r e s s u r e w i l l b e g r e a t e r .
Letp x b e the original pressure o f the air c o m p r e s s e d in a

vessel w h o s e v o l u m e is v ; l e t its t e m p e r a t u r e b e T, e q u a l t o
that o f t h e a t m o s p h e r e .
P a r t o f t h e air is t h e n a l l o w e d t o e s c a p e , till t h e p r e s s u r e
within the v e s s e l is p , e q u a l t o that o f t h e a t m o s p h e r e ; l e t
the t e m p e r a t u r e o f t h e air r e m a i n i n g w i t h i n t h e v e s s e l b e / .
N o w let t h e a p e r t u r e b e c l o s e d , a n d l e t t h e t e m p e r a t u r e o f
the air w i t h i n b e c o m e a g a i n T , e q u a l t o t h a t o f t h e a t m o s p h e r e ,
and l e t its p r e s s u r e b e t h e n p^.
T o d e t e r m i n e t, t h e a b s o l u t e t e m p e r a t u r e o f t h e air w h e n
cooled, we have, since the v o l u m e o f the enclosed air
is constant, t h e p r o p o r t i o n
p : p ::':
2 T,
or
^ PT
This gives the cooling effect of expansion from the

pressure p t to the pressure p . .To determine the corre
sponding change o f v o l u m e w e must calculate the v o l u m e
o r i g i n a l l y o c c u p i e d b y t h e air w h i c h r e m a i n s i n t h e v e s s e l .
A t the e n d o f t h e e x p e r i m e n t it o c c u p i e s a v o l u m e v , at a
pressure p 2 a n d a t e m p e r a t u r e T. A t the b e g i n n i n g o f the
experiment its pressure was p l and its temperature T:
hence the v o l u m e w h i c h it t h e n o c c u p i e d was ytx=zv, and

Pi

Application of Tliermodynanties to Gases.
a s u d d e n i n c r e a s e o f v o l u m e i n t h e r a t i o o f p% t o p l corre
sponds to a diminution o f pressure from p l t o P. Since/,
is g r e a t e r than>p, t h e r a t i o o f t h e p r e s s u r e s is g r e a t e r than
the ratio o f the v o l u m e s .
T h e e l a s t i c i t y o f t h e air u n d e r t h e c o n d i t i o n o f n o thermal
c o m m u n i c a t i o n is t h e v a l u e o f t h e quantity
v + V PI — P
or \{PI + PÎ)
2 v — V t\ - A
when the expansion is v e r y s m a l l , o r w h e n p 1 is v e r y little
greater than p.
B u t w e k n o w that t h e e l a s t i c i t y at c o n s t a n t temperature
is n u m e r i c a l l y e q u a l t o t h e p r e s s u r e ( s e e p . i n ) . H e n c e we
f i n d f o r t h e v a l u e o f y , t h e r a t i o o f t h e t w o elasticities,
__ PL — F
7
>i - A
or, m o r e exactly,
log/, - log P
7
l°g/i - log/ " 2
A l t h o u g h this m e t h o d o f d e t e r m i n i n g t h e e l a s t i c i t y in the
case o f n o thermal c o m m u n i c a t i o n i s a p r a c t i c a b l e o n e , it is
by no means the most perfect method. I t is difficult, for
instance, to arrange the experiment so that the pressure
may be completely equalised at the t i m e the a p e r t u r e is
c l o s e d , w h i l e at t h e s a m e t i m e n o s e n s i b l e p o r t i o n o f heat
has b e e n communicated to the air from the sides o f the
vessel. I t is a l s o n e c e s s a r y to ensure t h a t n o air has en
t e r e d f r o m w i t h o u t , a n d t h a t t h e m o t i o n w i t h i n t h e v e s s e l has
s u b s i d e d b e f o r e t h e a p e r t u r e is c l o s e d .
B u t t h e v e l o c i t y o f s o u n d i n air d e p e n d s , as w e shall after
wards s h o w , o n t h e r e l a t i o n b e t w e e n t h e v a r i a t i o n s o f its
d e n s i t y a n d its p r e s s u r e d u r i n g t h e r a p i d c o n d e n s a t i o n s a n d
r a r e f a c t i o n s w h i c h o c c u r d u r i n g t h e p r o p a g a t i o n o f sound. As
these changes o f pressure and density succeed one another
several hundred, or e v e n several thousand, times in a second,
t h e h e a t d e v e l o p e d b y c o m p r e s s i o n i n o n e p a r t o f t h e air has n d

Ratio of Elasticities. i§3
time to travel b y c o n d u c t i o n to parts c o o l e d b y expansion,

e v e n i f air w e r e as g o o d a c o n d u c t o r o f h e a t as c o p p e r is.
But w e k n o w t h a t a i r is r e a l l y a v e r y b a d c o n d u c t o r o f h e a t ,
so that i n t h e p r o p a g a t i o n o f s o u n d w e m a y b e q u i t e c e r t a i n
that the c h a n g e s o f v o l u m e t a k e place without any appreci
able c o m m u n i c a t i o n o f h e a t , a n d t h e r e f o r e t h e e l a s t i c i t y , as
deduced from measurements o f the velocity o f s o u n d , is
that c o r r e s p o n d i n g t o t h e c o n d i t i o n o f n o t h e r m a l communi
cation.
T h e r a t i o o f t h e e l a s t i c i t i e s o f air, as d e d u c e d from e x p e r i
ments o n t h e v e l o c i t y o f sound, is
y = I'408.
T h i s is a l s o , as w e h a v e s h o w n , t h e r a t i o o f t h e specific
heat at constant pressure to the specific heat at constant
volume.
T h e s e relations w e r e p o i n t e d ouj b y L a p l a c e , l o n g before
the r e c e n t d e v e l o p m e n t o f t h e r m o d y n a m i c s .
W e n o w proceed, following Rankine, to apply the thermo-
dynamical equation o f p. 173:
S
E 9 (K„ — K ) = T V (A M ) .
V
In the case of a fluid fulfilling t h e gaseous laws, and

also such t h a t t h e a b s o l u t e z e r o o f its t h e r m o m e t r i c scale
coincides w i t h the absolute z e r o o f the t h e r m o d y n a m i c scale,
we have
p
A M= —
a
and
Efl = p.
Hence
p v
K„ K — -_— — R ,
T
a constant quantity.
Now at the freezing temperature, which is 49<2°'6
on F a h r e n h e i t ' s scale from absolute zero, p v — 26,214
184 Application of Thermodynamics to Gases.
foot-pounds b y Regnault's experiments on air, so that »

is 53'2i foot-pounds per degree of Fahrenheit.
This is the work done by one pound o f air in expanding
under constant pressure while the temperature is raised one
degree Fahrenheit
N o w K is the mechanical equivalent of the heat required
y
to raise one pound o f air one degree Fahrenheit without

any change of volume, and K is the mechanical equivalent
b
of the heat required to produce the same change of tempera

ture when the gas expands under constant pressure, so that
Kp — represents the additional heat required for the ex
pansion. T h e equation, therefore, shows that this additional
heat is mechanically equivalent to the work done by the
air during its expansion. This, it must be remembered,
is not a self-evident truth, because the air is in a different
condition at the end o f the operation from that in which
it was at the beginning. I t is a consequence of the fact,
discovered experimentally b y Joule (p. 216), that no change
of temperature occurs when air expands without doing
external work.
W e have now obtained, in dynamical measure, the differ
ence between the two specific heats of air.
W e also know the ratio of K to K to be 1 -408.
P t Hence
K = Y 53_iL = 130-4 foot-pounds per degree Fahrenheit,

•408
and
K p — K -f- 53"2i =
T 183-6 foot-pounds per degree Fah.
N o w the specific heat of water at its maximum density is
Joule's equivalent of h e a t : for one pound it is 772 foot
pounds per degree Fahrenheit
H e n c e if Cp is the specific heat of air at constant pressure
referred to that of water as unity,
C p = ^£ = 0-2378.
T h i s calculation was published by Rankine in 1850.

Energy.
T h e v a l u e o f t h e s p e c i f i c h e a t o f air, d e t e r m i n e d directly
from e x p e r i m e n t b y M . R e g n a u l t and published in 1853, is
Cp — 0-2379.
C H A P T E R XII.
O N T H E INTRINSIC E N E R G Y O F A S Y S T E M O F BODIES.
T H E e n e r g y o f a b o d y is its c a p a c i t y for d o i n g w o r k , and

is m e a s u r e d b y t h e a m o u n t o f w o r k w h i c h it c a n b e made
to do. T h e I n t r i n s i c e n e r g y o f a b o d y is t h e w o r k w h i c h it
can d o in v i r t u e o f its a c t u a l c o n d i t i o n , w i t h o u t any supply
of e n e r g y f r o m w i t h o u t .
Thus a b o d y may do work b y expanding and overcoming
pressure, o r it m a y give out heat, a n d this h e a t m a y be
c o n v e r t e d i n t o w o r k i n w h o l e o r in p a r t . I f w e possessed a
perfect r e v e r s i b l e e n g i n e , a n d a refrigerator at t h e absolute
zero o f temperature, w e m i g h t convert the w h o l e o f the heat
which escapes from the b o d y into mechanical work. As we
c a n n o t o b t a i n a r e f r i g e r a t o r a b s o l u t e l y c o l d , i t is i m p o s s i b l e ,
even b y means o f perfect engines, to c o n v e r t all the heat
into mechanical work. W e know, however, from Joule's
experiments, the m e c h a n i c a l v a l u e o f a n y q u a n t i t y o f heat,
so that i f w e k n o w t h e w o r k done b y expansion, and the
quantity o f heat g i v e n out b y the b o d y during any alteration
of its c o n d i t i o n , w e c a n c a l c u l a t e t h e e n e r g y w h i c h has been
e x p e n d e d b y the b o d y d u r i n g the alteration.
A s w e c a n n o t i n a n y c a s e d e p r i v e a b o d y o f a l l its h e a t ,
a n d as w e c a n n o t , i n t h e case o f bodies which assume the
gaseous form, increase the v o l u m e o f the containing vessel
sufficiently t o o b t a i n all the mechanical energy o f the ex
p a n s i v e f o r c e , w e c a n n o t d e t e r m i n e e x p e r i m e n t a l l y the w h o l e
energy of the body. It is sufficient, however, for all
practical purposes to k n o w h o w m u c h the energy exceeds
or falls s h o r t o f t h e e n e r g y o f t h e b o d y in a certain definite

186 Energy, Entropy, and Dissipation.
condition—for instance, at a standard temperature and a

standard pressure.
I n a l l q u e s t i o n s a b o u t t h e m u t u a l a c t i o n o f b o d i e s w e are
c o n c e r n e d w i t h the difference b e t w e e n the e n e r g y o f each
b o d y in different states, a n d n o t w i t h its a b s o l u t e v a l u e , so
that the method o f comparing the e n e r g y o f the b o d y at
any t i m e w i t h its e n e r g y a t t h e s t a n d a r d t e m p e r a t u r e and
pressure is sufficient for our purpose. I f the b o d y in its
a c t u a l s t a t e has l e s s e n e r g y t h a n w h e n it is i n t h e standard
state, the expression for the relative e n e r g y will b e nega
tive. This, however, does not i m p l y that the energy of
a b o d y can e v e r b e r e a l l y n e g a t i v e , f o r t h i s is i m p o s s i b l e .
I t o n l y shows that in the standard state it has more energy
than in the a c t u a l state.
L e t us c o m p a r e t h e e n e r g y o f a s u b s t a n c e i n t w o different
states. L e t the two states b e i n d i c a t e d in the diagram by
the points A and B, a n d l e t t h e i n t e r m e d i a t e states through
w h i c h it p a s s e s b e i n d i c a t e d b y the line, straight or curved,
w h i c h is d r a w n f r o m A t o B.
T h e w o r k o f the path, or the w o r k w h i c h the b o d y does
while passing from the s t a t e A t o t h e s t a t e B a l o n g t h e path,
F A 6 A B, i s r e p r e s e n t e d , as w e
have s h o w n a t p. 103, by
the area included between
the path A B, the line o f
e q u a l v o l u m e , BO, the line
of z e r o p r e s s u r e , 6 a, and
the line o f equal volume,
a A, a n d i t is t o b e r e c k o n e d
positive when t h i s area is
described in the direction
o f the hands o f a watch.
T h e h e a t o f t h e p a t h , or
the heat absorbed by the
body during its passage
a l o n g A B , is r e p r e s e n t e d b y the area i n c l u d e d between the

Available Energy. 187
path A B, the i s e n t r o p i c B the fictitious z e r o i s o t h e r m a l /3 a,
a n d the i s e n t r o p i c a A. (See page 164.)
T h i s a r e a is t o b e r e c k o n e d positive w h e n it lies on the
right h a n d o f A B. I n the figure, i n w h i c h it l i e s o n t h e left
h a n d o f AB, it m u s t b e r e c k o n e d n e g a t i v e , or, in o t h e r w o r d s ,
it r e p r e s e n t s h e a t g i v e n o u t b y t h e b o d y .
The sum o f the w o r k d o n e and o f heat g i v e n out b y the
b o d y , b o t h i n d y n a m i c a l m e a s u r e , is t h e w h o l e e n e r g y g i v e n
out b y t h e body d u r i n g its p a s s a g e f r o m t h e s t a t e A t o t h e
state B. I t is r e p r e s e n t e d b y t h e w h o l e a r e a aAafiBia, and
this area, t h e r e f o r e , r e p r e s e n t s t h e d i m i n u t i o n o f the energy
o f the b o d y , w h i c h is e v i d e n t l y i n d e p e n d e n t o f t h e f o r m o f
the p a t h b e t w e e n A a n d B. N O W this a r e a is the difference
between the areas AOZUA and B/3ZI$B, w h i c h are b o u n d e d
b y the l i n e o f z e r o p r e s s u r e , t h e fictitious line o f zero tempe
rature, a n d the l i n e s o f e q u a l v o l u m e a n d o f e q u a l entropy.
I f w e suppose the fictitious line o f z e r o temperature j o i n e d
t o the l i n e o f zero pressure b y a line o f any form, f3z, w e
may consider the area b o u n d e d b y these lines and b y the
lines o f e q u a l v o l u m e a n d o f equal entropy through A as
representing that part o f the energy o f the body in the
state A t h e v a r i a t i o n s o f w h i c h w e are dealing with, for if
the b o d y p a s s e s i n t o t h e s t a t e B, b y d o i n g w o r k a n d g i v i n g
out heat, the e n e r g y g i v e n out is r e p r e s e n t e d b y t h e excess
o f the area AOZUA a b o v e Bpzbs, and this, t h e r e f o r e , re
presents the excess o f t h e e n e r g y i n t h e s t a t e A a b o v e that
in t h e state B.
H e n c e , i n d i s c u s s i n g t h e v a r i a t i o n s o f tire e n e r g y , w e m a y
consider them represented by the variations o f the area
AQZCA, o r , w h a t is t h e s a m e t h i n g , w e m a y s u p p o s e the
energy to be represented by this a r e a t o g e t h e r with an
unknown constant.
AVAILABLE ENERGY.
The sum o f the w o r k d o n e b y the b o d y a n d the d y n a m i c a l
e q u i v a l e n t o f the h e a t w h i c h it g i v e s o u t d u r i n g its passage

188 Energyi Entropy, and Dissipation.
from the state A to the s t a t e B is, as w e h a v e s e e n , the

s a m e w h a t e v e r b e t h e p a t h b y w h i c h t h e b o d y p a s s e s from
the state A t o the state B . If, h o w e v e r , w e s u p p o s e that
the b o d y is s u r r o u n d e d b y a medium, the temperature of
which is maintained con-
FIG. 260.
A stant, s o t h a t t h e b o c i y can
g i v e o u t h e a t o n l y w h e n its
t e m p e r a t u r e is h i g h e r t h a n
that o f the medium, and
can take in heat only when
its temperature is lower
than that o f t h e medium,
then these conditions will
confine the path within
certain limits.
D r a w the isothermal I T ,
representing the constant temperature o f the surrounding
medium. T h e n s i n c e t h e t e m p e r a t u r e o f t h e b o d y at A a n d
at a l l p o i n t s a b o v e t h e l i n e T T ' is h i g h e r t h a n t h a t o f the
m e d i u m , the b o d y cannot receive heat from the medium.
H e n c e its e n t r o p y c a n n o t i n c r e a s e , a n d t h e p a t h c a n n o t rise
a b o v e t h e a d i a b a t i c o r i s e n t r o p i c A a, d r a w n t h r o u g h A.
A g a i n , w h e n the b o d y gives out heat t o t h e m e d i u m , its
temperature must be higher than that of the medium.
H e n c e t h e p a t h m u s t b e a b o v e t h e i s o t h e r m a l T T'.
T h e p a t h f o r m e d b y the isentropic A T and t h e isothermal
T B is t h e r e f o r e the limiting form o f the p a t h , a n d is that
w h e r e i n t h e w o r k d o n e b y t h e b o d y is a m a x i m u m , a n d the
h e a t g i v e n o u t b y it a m i n i m u m .
I f w e d e n o t e the e n e r g y o f the b o d y in the state A b y e,
a n d its e n t r o p y b y a), a n d the energy and entropy of the
body at the temperature and pressure o f the surrounding
medium (represented by B ) by e0 and <pa, t h e n the total
e n e r g y g i v e n o u t as w o r k a n d h e a t d u r i n g t h e p a s s a g e from
the state A t o t h e s t a t e B is e—e . 0

Available Energy,
T h e amount o f heat w h i c h the b o d y gives out during the

process c a n n o t b e less t h a n t h a t c o r r e s p o n d i n g t o t h e p a t h
A T B, which is
(<t> ~ <Po) T
where T is t h e absolute temperature o f the surrounding
medium.
T h e amount o f w o r k d o n e b y the b o d y during the process
cannot, t h e r e f o r e , b e g r e a t e r t h a n
e — e — (<p — <p ) T.
0 0
T h i s , t h e r e f o r e , is t h e p a r t o f t h e e n e r g y w h i c h is a v a i l a b l e
for m e c h a n i c a l p u r p o s e s under the circumstances in which
the b o d y is p l a c e d , n a m e l y , w h e n s u r r o u n d e d by a medium
at t e m p e r a t u r e T a n d p r e s s u r e P.
I t appears, therefore, that t h e greater the original e n t r o p y ,
1
the smaller is t h e a v a i l a b l e e n e r g y o f t h e b o d y .
I f the s y s t e m u n d e r c o n s i d e r a t i o n c o n s i s t s o f a n u m b e r o f
bodies at different pressures and temperatures contained
within a vessel from which neither matter nor heat can
escape, t h e n t h e a m o u n t o f e n e r g y c o n v e r t e d i n t o w o r k w i l l
be greatest when the system is reduced to thermal and
mechanical equilibrium b y the f o l l o w i n g process.
ist. L e t e a c h o f t h e b o d i e s b e b r o u g h t t o t h e same tem
perature b y e x p a n s i o n o r c o m p r e s s i o n w i t h o u t communica
tion o f h e a t .
2nd. T h e b o d i e s b e i n g n o w at t h e same temperature, let
those w h i c h e x e r t t h e g r e a t e s t p r e s s u r e b e a l l o w e d t o e x p a n d
1
In former editions of this book the meaning of the term Entropy,
as introduced by Clausius, was erroneously stated to be that part of the
energy which cannot be converted into work. T h e book then proceeded
to use the term, as equivalent to the available energy ; thus introducing
great confusion into the language of thermodynamics. In this edition
1 have endeavoured to use the word Entropy according to its original
definition by Clausius.

igo Energy, Entropy, and Dissipation.
and to compress t h o s e w h i c h e x e r t less p r e s s u r e , till the
p r e s s u r e s o f a l l t h e b o d i e s i n the v e s s e l a r e e q u a l , t h e p r o c e s s
being conducted so s l o w l y that t h e t e m p e r a t u r e s o f a l l the
bodies remain sensibly equal to each other throughout the
process.
D u r i n g t h e first p a r t o f t h i s p r o c e s s , i n w h i c h t h e r e is n o
c o m m u n i c a t i o n o f heat b e t w e e n the bodies, the entropy o f
each b o d y remains constant. D u r i n g the s e c o n d p a r t , the
b o d i e s a r e a l l at t h e s a m e t e m p e r a t u r e , a n d t h e r e f o r e t h e c o m
munication o f heat from o n e b o d y to another diminishes
t h e e n t r o p y o f t h e o n e b o d y as m u c h as it i n c r e a s e s that o f
the o t h e r , s o t h a t t h e s u m o f t h e entropy remains constant.
H e n c e the total entropy o f the system remains the same
from the b e g i n n i n g t o the e n d o f the process. The work
d o n e against m e c h a n i c a l resistances during the establishment
o f t h e r m a l a n d m e c h a n i c a l e q u i l i b r i u m is g r e a t e r w h e n the
p r o c e s s is c o n d u c t e d i n this w a y t h a n w h e n c o n d u c t i o n o f
heat is a l l o w e d to take p l a c e b e t w e e n b o d i e s at s e n s i b l y
different temperatures.
H e n c e t h e final state o f t h e s y s t e m is d e t e r m i n e d b y the

following conditions :
L e t n b e the n u m b e r o f b o d i e s f o r m i n g the system.

Let m .. v . m n b e the masses o f these b o d i e s ,
v
\ • . . v n the v o l u m e o f unit o f mass o f each,
<?! • . . <p t h e e n t r o p y o f u n i t o f m a s s o f e a c h ,
u
. . e the e n e r g y o f unit o f mass o f each,

a
P\ • . .p n the pressure o f each,

81 · . . 0 n the temperature o f each.
T h e v o l u m e o f t h e w h o l e is
«,»! + . . . + », rv = S(JWW),
a n d s i n c e t h e s y s t e m is c o n t a i n e d i n a v e s s e l o f v o l u m e v ,
S.{mv) = v
during the w h o l e process.

Available Energy. 191
T h e e n t r o p y o f t h e w h o l e is
«1 01 + · . • + * » „ rV = 2(«f>) = *·
W h e n there is n o c o m m u n i c a t i o n o f h e a t e x c e p t b e t w e e n
todies o f equal temperature, * remains constant. When
there is c o m m u n i c a t i o n o f h e a t b e t w e e n b o d i e s o f d i f f e r e n t
temperature, * increases.
I n the final state o f t h e s y s t e m
P\ =/s •· • = A = v
= = e
There are
e, = e,...
therefore « — 1 conditions with respect to
pressure, a n d n — 1 c o n d i t i o n s w i t h r e s p e c t t o temperature,
together with o n e c o n d i t i o n w i t h r e s p e c t t o v o l u m e a n d o n e
with respect t o e n t r o p y , o r , i n a l l , 2 n c o n d i t i o n s t o b e satis
fied b y the n b o d i e s ; a n d s i n c e t h e s t a t e o f e a c h b o d y is a
function o f t w o v a r i a b l e s , t h e c o n d i t i o n s a r e n e c e s s a r y and
sufficient t o d e t e r m i n e t h e final state o f e a c h o f t h e n b o d i e s .
T h e w o r k d o n e against resistances external to the system
may b e d e t e r m i n e d b y comparing the total e n e r g y at the
beginning o f t h e p r o c e s s w i t h t h e final e n e r g y ; f o r , s i n c e n o
heat is a l l o w e d t o escape, any diminution o f energy must
arise from w o r k b e i n g d o n e .
T h e t o t a l e n e r g y is
S.(me) = E.
I f E b e t h e o r i g i n a l a n d E ' t h e final v a l u e o f this q u a n t i t y ,

the e n e r g y a v a i l a b l e t o p r o d u c e m e c h a n i c a l w o r k is
E —
I f during any part o f the process b y which the system

reaches its final s t a t e o f t h e r m a l a n d m e c h a n i c a l e q u i l i b r i u m
there takes p l a c e a c o m m u n i c a t i o n o f a q u a n t i t y H o f h e a t
from a b o d y at t e m p e r a t u r e (9j t o a b o d y at t e m p e r a t u r e 0,
2
the increase o f t h e t o t a l e n t r o p y o f t h e s y s t e m a r i s i n g f r o m
the c o m m u n i c a t i o n i s , as w e h a v e s h o w n ( a t p . 163),

192 Energy, Entropy, and Dissipation.
a n d t h e final e n t r o p y , i n s t e a d o f b e i n g e q u a l t o t h e original
entropy becomes
T h i s i n c r e a s e o f t h e final e n t r o p y i n v o l v e s a c o r r e s p o n d i n g
i n c r e a s e i n t h e f i n a l t e m p e r a t u r e a n d t h e final e n e r g y .
I f t h e rise o f t h e final t e m p e r a t u r e is s m a l l , t h e n , since the
v o l u m e is c o n s t a n t , t h e i n c r e a s e o f t h e final e n e r g y is
e (*' — *) = H e
and the a v a i l a b l e e n e r g y is t h e r e f o r e d i m i n i s h e d b y this

quantity on account o f the passage o f the quantity H of
heat from a b o d y at temperature Ö, t o a b o d y at tem
perature 0 . 2
P r o c e s s e s o f this k i n d , b y w h i c h , w h i l e the total energy

remains the s a m e , t h e a v a i l a b l e e n e r g y is d i m i n i s h e d , are
i n s t a n c e s o f w h a t Sir W . T h o m s o n has called the Dissipa
tion o f Energy. T h e doctrine o f the dissipation o f energy
is c l o s e l y c o n n e c t e d w i t h t h a t o f t h e g r o w t h o f e n t r o p y , but
i s b y n o m e a n s i d e n t i c a l w i t h it.
T h e increment o f the total entropy of a system arising
f r o m t h e c o m m u n i c a t i o n o f a g i v e n a m o u n t o f h e a t , H , from
a b o d y at o n e g i v e n t e m p e r a t u r e , 61, t o a n o t h e r g i v e n t e m
p e r a t u r e , 02, i s , as w e h a v e s e e n ,
a q u a n t i t y c o m p l e t e l y d e t e r m i n e d b y t h e s t a t e o f t h e system
w h e n this c o m m u n i c a t i o n takes p l a c e .
T h e e n e r g y d i s s i p a t e d o r r e n d e r e d u n a v a i l a b l e as a source
o f m e c h a n i c a l w o r k is
into w h i c h a n e w factor, 6 , enters, and this factor denotes

Dissipation of Energy. 193
the final t e m p e r a t u r e o f t h e s y s t e m w h e n it has r e a c h e d the
state o f t h e r m a l a n d mechanical equilibrium. G, therefore,
since it depends on the final state of the system, can
only b e c a l c u l a t e d when we know not only the relations
between the t h e r m o d y n a m i c v a r i a b l e s f o r a l l t h e b o d i e s , b u t
the v o l u m e w h i c h t h e y o c c u p y i n their final state.
The calculation o f the a m o u n t o f e n e r g y dissipated during
any process is t h e r e f o r e m u c h m o r e d i f f i c u l t t h a n t h a t o f t h e
increase o f the t o t a l e n t r o p y .
I f the s y s t e m is a l l o w e d t o r e a c h its final s t a t e o f t h e r m a l
and m e c h a n i c a l e q u i l i b r i u m , i n s u c h a m a n n e r t h a t n o e x
ternal w o r k is d o n e , a n d n o h e a t is a l l o w e d t o l e a v e o r e n t e r
the system, the c o n d i t i o n is t h a t t h e final e n e r g y is e q u a l t o
the original e n e r g y .
C o m b i n i n g this w i t h t h e o t h e r c o n d i t i o n s , t h a t t h e v o l u m e is
unchanged, a n d that t h e final state with respect to pressure
and t e m p e r a t u r e is c o m m o n t o a l l t h e b o d i e s , w e m a y d e t e r
mine the final v a l u e o f the temperature, pressure, a n d total
entropy.
T h e total e n t r o p y w i l l n o w h a v e t h e m a x i m u m v a l u e c o n
sistent w i t h t h e o r i g i n a l s t a t e o f the s y s t e m . T h e dissipation
of the a v a i l a b l e e n e r g y w i l l b e c o m p l e t e .
MECHANICAL AND THERMAL ANALOGIES.
In studying thermodynamics we may find considerable

assistance f r o m a c o m p a r i s o n b e t w e e n the thermal and the
mechanical phenomena.
W e have to d o w i t h e n e r g y in t w o forms, w o r k a n d heat.
W h e n e n e r g y is b e i n g t r a n s f e r r e d f r o m o n e b o d y t o another
we can a l w a y s t e l l w h e t h e r t h e first b o d y is d o i n g m e c h a n i c a l
w o r k on t h e s e c o n d o r c o m m u n i c a t i n g h e a t t o it. W o r k is
done by m o t i o n against resistance. H e a t is communicated
from a h o t t e r t o a c o l d e r b o d y .
B u t as s o o n as t h e e n e r g y has e n t e r e d t h e s e c o n d body,
o
194 Mechanical and Thermal Analogies.
we can no longer distinguish by any legitimate process

w h e t h e r i t is i n t h e f o r m o f w o r k o r o f h e a t . I n fact w e m a y
r e m o v e it f r o m t h e b o d y u n d e r e i t h e r o f t h e s e f o r m s .
I f a f l u i d at a p r e s s u r e p i n c r e a s e s i n v o l u m e f r o m v t o
it performs w o r k against external resistance, the amount of
w h i c h w o r k is
p (v' — V) = w.
I f a b o d y at t e m p e r a t u r e fl i n c r e a s e s i n e n t r o p y f r o m cj> to
<j>\ a n a m o u n t o f h e a t m u s t h a v e e n t e r e d it r e p r e s e n t e d b y
6 («,' - = H.
I f b o t h these processes t a k e place, a n d if the energy of

t h e b o d y is t h e r e b y c h a n g e d f r o m E t o E', then
E' — E = H — w = 0 (</>' — <f) — p (»' — »).
H e r e t h e n w e h a v e t w o sets o f q u a n t i t i e s , o n e r e l a t i n g to
work, the other t o heat.
w v p
H (j> 8
O f these quantities W o r k and H e a t a r e s i m p l y t w o forms

of Energy.
T h e v o l u m e is a q u a n t i t y s u c h t h a t w i t h o u t a c h a n g e o f
its v a l u e n o w o r k c a n b e d o n e . T h e amount o f work done,
h o w e v e r , is m e a s u r e d , n o t b y t h e c h a n g e o f v o l u m e a l o n e ,
but b y that c h a n g e m u l t i p l i e d b y another quantity—the
pressure.
In the s a m e ^ w a y t h e e n t r o p y is a q u a n t i t y such that
w i t h o u t a c h a n g e i n its v a l u e n o h e a t c a n e n t e r or l e a v e the
body. T h e a m o u n t o f this h e a t , h o w e v e r , is n o t m e a s u r e d
b y t h e c h a n g e o f e n t r o p y , b u t b y that c h a n g e m u l t i p l i e d b y
another quantity—the absolute temperature.
A g a i n , t h e p r e s s u r e is a q u a n t i t y s u c h t h a t its e q u a l i t y in
two communicating vessels determines their mechanical

Mechanical and Thermal Analogies. 195
equilibrium, w h i l e its e x c e s s i n e i t h e r d e t e r m i n e s a flow of

fluid from that v e s s e l t o t h e o t h e r .
I n like m a n n e r t h e t e m p e r a t u r e is a q u a n t i t y s u c h t h a t its
equality in t w o b o d i e s i n c o n t a c t determines their thermal
equilibrium, w h i l e its e x c e s s i n e i t h e r d e t e r m i n e s a flow of
heat from that b o d y t o t h e o t h e r .
I f w e r e g a r d the e n e r g y o f a b o d y as d e t e r m i n e d b y its
v o l u m e a n d its e n t r o p y , t h e n t h e p r e s s u r e m a y b e d e f i n e d as
the rate at w h i c h t h e e n e r g y d i m i n i s h e s with increase of
volume, while the e n t r o p y remains constant.
T h e temperature m a y in like m a n n e r b e d e f i n e d as t h e
rate at w h i c h t h e e n e r g y i n c r e a s e s w i t h i n c r e a s e o f e n t r o p y ,
the v o l u m e r e m a i n i n g constant.
REPRESENTATION OF T H E P R O P E R T I E S OF A SUBSTANCE BY
MEANS OF A SURFACE.
P r o f e s s o r J. W i l l a r d G i b b s , o f Y a l e C o l l e g e , U . S . , t o w h o m
w e are indebted for a careful examination o f the different
methods o f representing t h e r m o d y n a m i c relations b y plane
diagrams, has i n t r o d u c e d a n e x c e e d i n g l y v a l u a b l e m e t h o d o f
1
studying t h e p r o p e r t i e s o f a s u b s t a n c e b y m e a n s o f a s u r f a c e .
According to this method, the volume, entropy, and
energy o f the b o d y in a g i v e n state are r e p r e s e n t e d b y the
three r e c t a n g u l a r c o o r d i n a t e s o f a p o i n t i n t h e surface, and
this p o i n t o n t h e surface is s a i d t o c o r r e s p o n d t o t h e given
state o f t h e b o d y . W e shall s u p p o s e t h e v o l u m e m e a s u r e d
towards t h e east f r o m t h e m e r i d i a n p l a n e c o r r e s p o n d i n g to
no v o l u m e , t h e e n t r o p y m e a s u r e d t o w a r d s the north from a
vertical p l a n e p e r p e n d i c u l a r t o t h e m e r i d i a n , w h o s e p o s i t i o n
is e n t i r e l y a r b i t r a r y , a n d the energy measured downwards
from the h o r i z o n t a l p l a n e o f n o e n e r g y , t h e p o s i t i o n o f w h i c h
m a y b e c o n s i d e r e d as a r b i t r a r y , b e c a u s e w e cannot measure
the w h o l e e n e r g y e x i s t i n g i n a b o d y .
1
Transactions of the Academy of Sciences of Connecticut, vol. ii.
O 3

Thermodynamic Surface.
T h e s e c t i o n o f this surface b y a vertical plane perpen

dicular to the meridian represents the relation between
volume and energy when the entropy is c o n s t a n t , that is,
w h e n n o heat enters or leaves the b o d y .
I f t h e p r e s s u r e is p o s i t i v e , t h e n t h e b o d y , b y expanding,
w o u l d d o w o r k against external resistance, a n d its intrinsic
energy would diminish. The rate at which the energy
diminishes as t h e volume increases is r e p r e s e n t e d by the
tangent o f t h e a n g l e w h i c h t h e c u r v e o f s e c t i o n m a k e s with
the h o r i z o n .
The p r e s s u r e is t h e r e f o r e r e p r e s e n t e d b y t h e t a n g e n t of
the angle o f s l o p e o f the curve o f section. T h e pressure is
p o s i t i v e w h e n t h e c u r v e s l o p e s d o w n w a r d s t o w a r d s the west.
W h e n t h e s l o p e o f t h e c u r v e is t o w a r d s t h e east t h e corre
s p o n d i n g p r e s s u r e is n e g a t i v e .
A t e n s i o n o r n e g a t i v e p r e s s u r e c a n n o t e x i s t i n a gas. It
m a y , h o w e v e r , e x i s t i n a l i q u i d , s u c h as m e r c u r y . T h u s , if
a barometer tube is w e l l filled with clean mercury, and
then placed in a vertical position, with its closed end
uppermost, the mercury sometimes does not fall in the
tube t o the p o i n t corresponding to the atmospheric pres
sure, b u t remains suspended in the tube, so as t o fill it
completely.
T h e pressure in this case is n e g a t i v e i n t h a t p a r t o f the
m e r c u r y w h i c h is a b o v e t h e l e v e l o f t h e o r d i n a r y b a r o m e t r i c
column.
In solid bodies, as w e k n o w , tensions of considerable
m a g n i t u d e m a y exist.
H e n c e in our t h e r m o d y n a m i c m o d e l t h e p r e s s u r e o f the
s u b s t a n c e is i n d i c a t e d b y the tangent o f the s l o p e o f the
curve o f constant entropy, and is r e c k o n e d p o s i t i v e w h e n
t h e e n e r g y d i m i n i s h e s as t h e v o l u m e i n c r e a s e s .
T h e s e c t i o n o f t h e surface b y a v e r t i c a l p l a n e p a r a l l e l t o
t h e m e r i d i a n is a c u r v e o f c o n s t a n t v o l u m e . In this c u r v e
the temperature is represented b y the rate at which the

Representation of Pressure and Temperature. 197
energy increases as t h e e n t r o p y i n c r e a s e s , t h a t is t o say, b y

the tangent o f t h e s l o p e o f t h e c u r v e .
S i n c e the t e m p e r a t u r e , r e c k o n e d f r o m a b s o l u t e z e r o , is a n
essentially p o s i t i v e q u a n t i t y , the curve o f constant volume
must b e such that t h e e n t r o p y and energy always increase
together.
T o ascertain the p r e s s u r e a n d t e m p e r a t u r e o f t h e s u b s t a n c e
in a g i v e n state, w e m a y draw a tangent plane t o the cor
responding p o i n t o f t h e s u r f a c e . T h e n o r m a l t o this plane
through the o r i g i n w i l l cut a h o r i z o n t a l p l a n e at u n i t o f d i s
tance a b o v e t h e o r i g i n at a p o i n t w h o s e c o o r d i n a t e s represent
the pressure a n d t e m p e r a t u r e , t h e p r e s s u r e b e i n g r e p r e s e n t e d
by the c o o r d i n a t e d r a w n t o w a r d s t h e w e s t , a n d t h e t e m p e r a
ture b y the c o o r d i n a t e d r a w n t o w a r d s t h e n o r t h .
The pressure a n d temperature a r e thus represented by

the d i r e c t i o n o f t h i s n o r m a l , and if, at any two points
of the surface, t h e d i r e c t i o n s o f t h e n o r m a l s a r e parallel,
then in t h e t w o states o f t h e s u b s t a n c e c o r r e s p o n d i n g to
these t w o p o i n t s t h e p r e s s u r e a n d t e m p e r a t u r e m u s t b e t h e
same.
I f w e wish t o t r a c e o u t o n a m o d e l o f t h e surface a s e r i e s
of lines o f e q u a l p r e s s u r e , w e h a v e o n l y t o p l a c e it i n the
sunshine a n d t o turn it s o t h a t t h e sun's rays are parallel to
the p l a n e o f v o l u m e a n d e n e r g y , a n d m a k e a n a n g l e w i t h t h e
line o f v o l u m e w h o s e t a n g e n t is p r o p o r t i o n a l t o t h e p r e s s u r e .
Then, if w e trace o n t h e surface the boundary o f light and
shadow, t h e p r e s s u r e at a l l p o i n t s o f t h i s l i n e w i l l b e the
same.
In like manner, if w e p l a c e the m o d e l so t h a t t h e sun's
rays are p a r a l l e l t o t h e plane of entropy and energy, the
boundary of light and s h a d o w will b e a line such that the
temperature is t h e s a m e at e v e r y p o i n t , a n d p r o p o r t i o n a l t o
the t a n g e n t o f t h e a n g l e w h i c h t h e sun's rays m a k e w i t h the
line o f e n t r o p y .
I n this w a y w e m a y t r a c e o u t o n t h e m o d e l t w o series o f

Thermodynamic Model.
l i n e s : l i n e s o f e q u a l p r e s s u r e , w h i c h P r o f e s s o r G i b b s calls
Isopiestics ; and lines o f equal temperature, or Isothermals.
B e s i d e s t h e s e , w e m a y t r a c e t h e t h r e e s y s t e m s o f p l a n e sec
t i o n s p a r a l l e l t o t h e c o o r d i n a t e p l a n e s , t h e i s o m e t r i c s or lines
of equal v o l u m e , the isentropics or lines o f equal entropy,
which we f o r m e r l y c a l l e d , after R a n k i n e , adiabatics, and
the isenergics or lines o f equal e n e r g y .
The network f o r m e d b y these five systems o f l i n e s will
f o r m a c o m p l e t e r e p r e s e n t a t i o n o f t h e r e l a t i o n s b e t w e e n the
five quantities, v o l u m e , e n t r o p y , e n e r g y , p r e s s u r e , a n d tem
p e r a t u r e , f o r a l l states o f t h e b o d y .
The body itself need not be homogeneous either in
c h e m i c a l nature or in physical state. A l l t h a t is n e c e s s a r y
is t h a t t h e w h o l e s h o u l d b e a t t h e same pressure and the
same temperature.
B y m e a n s o f this m o d e l P r o f e s s o r G i b b s h a s s o l v e d several
i m p o r t a n t p r o b l e m s r e l a t i n g t o t h e t h e r m o d y n a m i c relations
between two portions o f a substance, in different physical
states, b u t at t h e s a m e p r e s s u r e a n d temperature.
Let a s u b s t a n c e b e c a p a b l e o f e x i s t i n g i n t w o different
states, s a y l i q u i d a n d g a s e o u s , at t h e same temperature and
pressure. W e w i s h t o d e t e r m i n e w h e t h e r t h e s u b s t a n c e will
t e n d o f i t s e l f t o pass f r o m o n e o f t h e s e states t o t h e other.
L e t t h e s u b s t a n c e b e p l a c e d i n a c y l i n d e r , u n d e r a piston,
a n d s u r r o u n d e d b y a m e d i u m at t h e g i v e n t e m p e r a t u r e and
pressure, the extent o f this m e d i u m b e i n g s o g r e a t that its
pressure and temperature are not sensibly altered by the
changes o f v o l u m e o f the w o r k i n g substance, or by the
h e a t w h i c h t h a t b o d y g i v e s o u t o r t a k e s in.
T h e t w o p h y s i c a l states w h i c h a r e t o b e c o m p a r e d are re
presented b y t w o points o n the surface o f the m o d e l ; and
since the pressure a n d t e m p e r a t u r e are the same, the tangent
p l a n e s at t h e s e p o i n t s a r e e i t h e r c o i n c i d e n t o r p a r a l l e l .
T h e surface r e p r e s e n t i n g t h e t h e r m o d y n a m i c p r o p e r t i e s o f
the surrounding m e d i u m must b e supposed to b e constructed

Equilibrium between Two Physical States. 199
on a scale p r o p o r t i o n a l t o t h e a m o u n t o f this m e d i u m ; a n d
gs w e assume that t h e r e is a v e r y g r e a t m a s s o f this m e d i u m ,
the scale o f t h e surface w i l l b e so g r e a t t h a t w e m a y r e g a r d
the p o r t i o n o f t h e surface with which we have to do as
sensibly p l a n e ; a n d s i n c e its p r e s s u r e a n d t e m p e r a t u r e are
those o f the w o r k i n g s u b s t a n c e in t h e g i v e n s t a t e , t h i s p l a n e
surface is p a r a l l e l t o t h e
tangent plane at the
given p o i n t o f t h e sur
face o f the m o d e l .
Let A B C be three,
points o f t h e m o d e l a t
which the t a n g e n t p l a n e s
are parallel, t h e e n e r g y
being r e c k o n e d d o w n
wards.
L e t A a a b e t h e t a n g e n t p l a n e at A , a n d l e t us c o n s i d e r it
as part o f t h e m o d e l r e p r e s e n t i n g t h e e x t e r n a l m e d i u m , t h i s
model being so p l a c e d that v o l u m e , e n t r o p y , a n d energy
are r e c k o n e d in t h e o p p o s i t e d i r e c t i o n s from those in the
model o f the w o r k i n g substance.
N o w let us s u p p o s e t h e s u b s t a n c e t o p a s s f r o m t h e s t a t e A
to the state B, p a s s i n g through the series o f states r e p r e
sented b y the p o i n t s o n t h e i s o t h e r m a l l i n e j o i n i n g t h e p o i n t s
of equal t e m p e r a t u r e A a n d B.
T h e n since t h e w o r k i n g s u b s t a n c e a n d t h e e x t e r n a l m e d i u m
are a l w a y s at t h e s a m e t e m p e r a t u r e , t h e e n t r o p y lost b y the
one is e q u a l t o t h a t g a i n e d b y t h e o t h e r .
A l s o the o n e g a i n s i n v o l u m e w h a t is l o s t b y t h e o t h e r .
H e n c e , during the passage o f the w o r k i n g substance from
the state A t o t h e s t a t e n, t h e state o f t h e e x t e r n a l m e d i u m
is a l w a y s r e p r e s e n t e d b y a p o i n t i n t h e t a n g e n t p l a n e i n t h e
same v e r t i c a l l i n e as t h e p o i n t r e p r e s e n t i n g t h e s t a t e o f t h e
working substance.
F o r the s a m e h o r i z o n t a l m o t i o n w h i c h r e p r e s e n t s a g a i n o f

200 Tìiermodynamic Model.
volume o r entropy o f the one substance represents a n equal

loss of vojume o r entropy in the other. ,
H e n c e , when t h e state of the working substance is repre-
sented by the point B , that o f t h e external medium will b e
represented by the point a, where the vertical line through
B meets t h e tangent plane through A.
N o w the energy is reckoned downwards for the working
substance and upwards for the external medium. Hence,
drawing A K horizontal, K B represents the gain in energy of
the working substance, and K a the loss of energy of the
external medium.
T h e line B a, or the vertical height o f t h e tangent plane
above the point B , represents the gain o f energy i n the whole
system, consisting o f the working substance and the external
medium, during the passage from the state A to the state B .
B u t the energy of the system can be increased only by doing
work on it.
B u t if the system can o f itself pass from one state to
another, the work required t o produce the corresponding
changes of configuration must be drawn from the energy of
the system, and the energy must therefore diminish.
T h e fact, therefore, that in the case before us the energy
increases, shows that the passage from the state A to the
State B i n presence of a medium of constant temperature
and pressure, cannot be effected without the expenditure of
work b y some external agent.
T h e working substance, therefore, cannot o f itself pass
from the state A to the state B , if B lies below the plane
which touches the surface at A.
W e h a v e supposed t h e substance to pass from A to B by a
process during which it is always at the same temperature
as the external medium. I n this case the entropy of the
system remains constant.
If, however, the communication of heat between the sub-
stances occurs when they are not at t h e same temperature,

Condition of Stability. 201
the e n t r o p y o f t h e s y s t e m w i l l i n c r e a s e ; a n d i f i n t h e f i g u r e
the g a i n o f e n t r o p y o f t h e w o r k i n g s u b s t a n c e is r e p r e s e n t e d
b y the h o r i z o n t a l c o m p o n e n t o f A B, the loss o f entropy o f
the external medium will be represented by a smaller
quantity, such as t h e h o r i z o n t a l c o m p o n e n t o f A a'. Hence
a' will b e t o t h e left o f a, a n d t h e r e f o r e h i g h e r . T h e gain
of e n t r o p y o f t h e s y s t e m w i l l t h e r e f o r e b e r e p r e s e n t e d b y t h e
h o r i z o n t a l p a r t o f a a'.
N o w since temperature is e s s e n t i a l l y p o s i t i v e , a g a i n o f
e n t r o p y at a g i v e n v o l u m e a l w a y s i m p l i e s a g a i n o f e n e r g y .
H e n c e the g a i n o f e n e r g y is g r e a t e r w h e n t h e r e is a g a i n o f
entropy than w h e n the e n t r o p y remains constant.
T h e r e is, t h e r e f o r e , n o m e t h o d b y w h i c h t h e c h a n g e from
A to B c a n b e e f f e c t e d without a gain o f energy, and this
implies t h e e x p e n d i t u r e o f w o r k b y a n e x t e r n a l a g e n t
If, t h e r e f o r e , t h e t a n g e n t p l a n e at A is e v e r y w h e r e a b o v e
the t h e r m o d y n a m i c surface, the c o n d i t i o n o f the working
substance r e p r e s e n t e d b y t h e p o i n t A is e s s e n t i a l l y stable,
and the s u b s t a n c e c a n n o t o f i t s e l f pass i n t o a n y o t h e r s t a t e
while e x p o s e d to the same external influences o f pressure
and temperature.
This will be the case if t h e surface is c o n v e x o - c o n v e x
upwards.
If, on t h e o t h e r h a n d , t h e surface, as a t the point B, is
either concave upwards in all directions, or c o n c a v e in
one d i r e c t i o n a n d c o n v e x in a n o t h e r , it w i l l b e p o s s i b l e to
draw o n t h e surface a line from the point o f contact lying
entirely a b o v e t h e t a n g e n t p l a n e , a n d therefore representing
a series o f states t h r o u g h w h i c h the substance can pass o f
itself.
I n this c a s e t h e p o i n t o f c o n t a c t r e p r e s e n t s a state o f t h e
substance w h i c h , if physically possible for an instant, is
essentially u n s t a b l e , a n d c a n n o t b e permanent
T h e r e is a t h i r d case, h o w e v e r , in w h i c h the surface, as
at the p o i n t c , is c o n v e x o - c o n v e x , so t h a t a l i n e d r a w n on

202 Thermodynamic Model.
the surface from the point o f contact must lie b e l o w the
t a n g e n t p l a n e ; b u t t h e t a n g e n t p l a n e , i f p r o d u c e d far e n o u g h ,
c u t s t h e surface at c, so t h a t the p o i n t A l i e s a b o v e the
tangent plane. In this case the substance cannot pass
t h r o u g h a n y c o n t i n u o u s series o f s t a t e s f r o m c t o A , b e c a u s e
a n y l i n e d r a w n o n t h e surface f r o m c t o A b e g i n s b y d i p p i n g
b e l o w the tangent plane. B u t i f a q u a n t i t y , h o w e v e r small,
o f t h e s u b s t a n c e i n t h e s t a t e A is i n p h y s i c a l c o n t a c t w i t h
t h e rest o f t h e s u b s t a n c e i n t h e s t a t e c , m i n u t e p o r t i o n s will
p a s s at o n c e f r o m t h e state c t o t h e state A w i t h o u t passing
t h r o u g h t h e i n t e r m e d i a t e states.
The e n e r g y set at liberty by this transformation will
a c c e l e r a t e t h e s u b s e q u e n t r a t e o f t r a n s f o r m a t i o n , so that the
p r o c e s s will b e o f the nature o f an e x p l o s i o n .
Instances o f s u c h a p r o c e s s o c c u r w h e n a l i q u i d n o t in
p r e s e n c e o f its v a p o u r is h e a t e d a b o v e its b o i l i n g p o i n t , a n d
a l s o w h e n a l i q u i d is c o o l e d b e l o w its f r e e z i n g p o i n t , or w h e n
a s o l u t i o n o f a salt, o r o f a g a s , b e c o m e s s u p e r s a t u r a t e d .
In the first o f t h e s e cases the contact o f the smallest
quantity o f vapour will produce an explosive evaporation;
in the s e c o n d , the contact o f ice will produce explosive
f r e e z i n g ; i n t h e t h i r d , a c r y s t a l o f t h e salt w i l l p r o d u c e e x
plosive crystallization; and in the fourth, a b u b b l e o f any
gas will p r o d u c e e x p l o s i v e effervescence.
Finally, when the tangent plane touches the surface at
t w o or m o r e points, and is a b o v e t h e surface everywhere
e l s e , p o r t i o n s o f t h e s u b s t a n c e i n states c o r r e s p o n d i n g t o the
points o f contact can exist in p r e s e n c e o f each other, and
t h e s u b s t a n c e c a n pass f r e e l y f r o m o n e s t a t e t o a n o t h e r in
either direction.
T h e s t a t e o f t h e w h o l e b o d y w h e n p a r t is in o n e p h y s i c a l
state a n d part in a n o t h e r is r e p r e s e n t e d b y a p o i n t in the
straight line j o i n i n g the c e n t r e o f g r a v i t y o f t w o masses equal
r e s p e c t i v e l y t o t h e m a s s e s o f t h e s u b s t a n c e i n t h e t w o states,
a n d p l a c e d at t h e p o i n t s o f t h e m o d e l c o r r e s p o n d i n g t o these
states.

Primitive and Secondary Surfaces. 203
H e n c e , in a d d i t i o n t o t h e surface a l r e a d y c o n s i d e r e d , w h i c h
w e ma.y c a l l t h e p r i m i t i v e , surface, a n d w h i c h r e p r e s e n t s the
properties o f the substance w h e n h o m o g e n e o u s , all the points
o f the l i n e j o i n i n g t h e t w o points o f contact o f the same
tangent p l a n e b e l o n g t o a s e c o n d a r y surface, w h i c h r e p r e
sents t h e p r o p e r t i e s o f t h e s u b s t a n c e w h e n p a r t is i n o n e
state a n d part i n a n o t h e r .
T o t r a c e o u t this s e c o n d a r y surface w e m a y s u p p o s e the
doubly tangent plane t o b e m a d e to roll u p o n the surface,
always t o u c h i n g it a t t w o p o i n t s c a l l e d t h e n o d e - c o u p l e .
T h e t w o p o i n t s o f c o n t a c t w i l l thus t r a c e o u t t w o c u r v e s
such that a p o i n t in t h e o n e c o r r e s p o n d s t o a p o i n t i n the
other. T h e s e t w o c u r v e s are c a l l e d in g e o m e t r y the node-
couple c u r v e s .
The s e c o n d a r y s u r f a c e is g e n e r a t e d b y a l i n e w h i c h m o v e s
so as a l w a y s t o j o i n c o r r e s p o n d i n g p o i n t s o f c o n t a c t . I t is
a d e v e l o p a b l e surface, being the e n v e l o p e o f the rolling
tangent plane.
T o c o n s t r u c t it, s p r e a d a film o f g r e a s e o n a s h e e t o f g l a s s
and cause t h e s h e e t o f g l a s s t o r o l l w i t h o u t s l i p p i n g o n t h e
m o d e l , a l w a y s t o u c h i n g it in t w o p o i n t s a t l e a s t .
T h e grease w ' l l b e partly transferred from the glass t o the
m o d e l at the p o i n t s o f c o n t a c t , a n d there will b e traces on
the m o d e l o f t h e n o d e - c o u p l e c u r v e s , a n d on the glass o f
corresponding plane curves.
If we now copy o n paper the curve traced out on the
glass a n d cut it out, w e m a y b e n d t h e p a p e r s o t h a t t h e cut
edges shall c o i n c i d e w i t h t h e t w o n o d e - c o u p l e c u r v e s , a n d
the p a p e r b e t w e e n t h e s e c u r v e s w i l l f o r m t h e d e r i v e d sur
face r e p r e s e n t i n g t h e s t a t e o f t h e b o d y w h e n p a r t is i n o n e
physical state a n d p a r t i n a n o t h e r ,
T h e r e is o n e p o s i t i o n o f t h e t a n g e n t p l a n e in w h i c h it
touches t h e p r i m i t i v e surface in t h r e e p o i n t s . T h e s e points
r e p r e s e n t the s o l i d , l i q u i d , a n d g a s e o u s states o f t h e sub
stance w h e n t h e t e m p e r a t u r e a n d t h e p r e s s u r e a r e s u c h that
the t h r e e states c a n e x i s t t o g e t h e r i n e q u i l i b r i u m .

T h e p l a n e triangle, o f w h i c h these p o i n t s are the angles,

r e p r e s e n t s a l l p o s s i b l e m i x t u r e s o f t h e s e t h r e e states. For
i n s t a n c e , i f t h e r e a r e s g r a m m e s i n t h e s o l i d state, L g r a m m e s
i n t h e l i q u i d state, and v grammes in the state o f vapour,
this c o n d i t i o n o f t h e substance will be represented by a
p o i n t i n t h e t r i a n g l e w h i c h is t h e c e n t r e o f g r a v i t y o f masses
s, L , a n d v p l a c e d at t h e c o r r e s p o n d i n g a n g u l a r p o i n t s .
F r o m this p o s i t i o n o f t h e t a n g e n t p l a n e it m a y r o l l o n the
p r i m i t i v e surface in t h r e e d i r e c t i o n s so as i n e a c h c a s e t o t o u c h
it at t w o p o i n t s . W e thus o b t a i n t h r e e s h e e t s o f the d e r i v e d
surface, t h e first c o n n e c t i n g t h e s o l i d a n d l i q u i d states, the
s e c o n d t h e l i q u i d a n d g a s e o u s states, a n d t h e t h i r d t h e gas
eous and s o l i d states. T h e s e t h r e e d e v e l o p a b l e surfaces,
1 ogether with the plane triangle S L V , constitute what Pro
fessor G i b b s calls the Surface o f D i s s i p a t e d E n e r g y .
O f t h e t h r e e d e v e l o p a b l e surfaces t h e first a n d third, those
w h i c h c o n n e c t the solid state w i t h the liquid and gaseous,
h a v e b e e n e x p e r i m e n t a l l y i n v e s t i g a t e d o n l y t o a short dis
tance from the triangle s L v ; but the sheet w h i c h connects
t h e l i q u i d a n d g a s e o u s states has b e e n t h o r o u g h l y e x p l o r e d .
T h e experiments o f C a g n i a r d de la T o u r a n d the numeri
cal d e t e r m i n a t i o n s o f A n d r e w s s h o w t h a t t h e c u r v e s traced
out b y the t w o points o f contact o f the d o u b l y tangent plane
unite in a point w h i c h represents w h a t A n d r e w s calls t h e
c r i t i c a l state. A t this p o i n t t h e t w o p o i n t s o f c o n t a c t o f the
r o l l i n g t a n g e n t p l a n e c o a l e s c e , a n d i f t h e p l a n e c o n t i n u e s to
r o l l o n t h e surface it w i l l t o u c h i t at o n e p o i n t o n l y .
I f t h e p r i m i t i v e surface f o r m s a c o n t i n u o u s s h e e t beneath
t h e surface o f d i s s i p a t e d e n e r g y , it c a n n o t b e at all points
convexo-convex upwards. For
Fici. s6c.
let A D b e the line j o i n i n g two
corresponding points o f contact
of the d o u b l y tangent plane, and
H l e t A B c D b e the s e c t i o n o f the
p r i m i t i v e surface b y a v e r t i c a l p l a n e t h r o u g h A D , t h e n it is

Condition of Instability. 205
manifest that t h e curve A B C D must in s o m e part o f its
course b e c o n c a v e u p w a r d s .
N o w a p o i n t o n t h e p r i m i t i v e surface at w h i c h e i t h e r o f its
principal c u r v a t u r e s is c o n c a v e u p w a r d s , represents a state
o f the b o d y w h i c h is e s s e n t i a l l y unstable. Part of the
p r i m i t i v e surface, t h e r e f o r e , i f it is c o n t i n u o u s , must repre
sent states o f t h e b o d y e s s e n t i a l l y u n s t a b l e . If, therefore,
the p r i m i t i v e surface is c o n t i n u o u s , there must b e a region
representing states e s s e n t i a l l y u n s t a b l e , b e c a u s e o n e o r b o t h
of the p r i n c i p a l c u r v a t u r e s is c o n c a v e u p w a r d s . This region
is b o u n d e d b y w h a t is c a l l e d i n g e o m e t r y t h e spinode c u r v e .
B e y o n d this c u r v e t h e surface is c o n v e x o - c o n v e x , b u t the
tangent plane still cuts t h e surface at s o m e m o r e o r less
distant p o i n t till w e c o m e t o t h e c u r v e o f t h e node-couple,
at w h i c h t h e t a n g e n t p l a n e t o u c h e s t h e surface at t w o p o i n t s .
B e y o n d this t h e t a n g e n t p l a n e l i e s e n t i r e l y a b o v e t h e surface,
and t h e c o r r e s p o n d i n g state o f t h e b o d y is e s s e n t i a l l y s t a b l e .
The region b e t w e e n the spinode curve and the node-

couple c u r v e r e p r e s e n t s s t a t e s o f t h e b o d y w h i c h , though
stable w h e n t h e w h o l e s u b s t a n c e is h o m o g e n e o u s , are l i a b l e
to sudden change if a portion o f the same substance in
another state is p r e s e n t .
Since e v e r y v e r t i c a l s e c t i o n t h r o u g h two corresponding
points o f c o n t a c t m u s t c u t t h e s p i n o d e c u r v e at t h e points
o f i n f l e x i o n B a n d c, t h e c h o r d A D o f t h e n o d e - c o u p l e c u r v e
and the c h o r d B c o f t h e s p i n o d e c u r v e m u s t c o i n c i d e at t h e
critical p o i n t , so t h a t at this p o i n t t h e s p i n o d e c u r v e a n d t h e
two b r a n c h e s o f t h e n o d e - c o u p l e c u r v e c o a l e s c e a n d h a v e a
c o m m o n tangent. This point is called in geometry the
tacnodal p o i n t .
Note.—For these geometrical names I am indebted to Professor

Cayley.

T H E R M A L LINES O N T H E T H E R M O D Y N A M I C SURFACE.
(FIG. xtd.)
o Origin.
O v Axis of volume.
O 0 A x i s o f entropy,
o e A x i s o f energy.
P] . . . p 6 I s o p i e s t i c s o r lines o f equal pressure.
Of t h e s e P ] r e p r e s e n t s a n e g a t i v e p r e s s u r e , or, i n other
w o r d s , a t e n s i o n , s u c h as m a y e x i s t in s o l i d s a n d in some
liquids. •
T, . . . T 6 I s o t h e r m a l s , or lines o f equal temperature.
The curves T 3 a n d T h a v e b r a n c h e s i n tire f o r m o f c l o s e d
4
loops.
F G H c. T o t h e right o f t h i s l i n e t h e s u b s t a n c e is gaseous
and absolutely stable. T o t h e l e f t o f F G it m a y c o n d e n s e
i n t o t h e s o l i d s t a t e , a n d t o the left o f G H c it m a y c o n d e n s e
i n t o t h e l i q u i d state.
c K. L M N . B e l o w this l i n e t h e substance is liquid and
absolutely stable. T o t h e right o f L K C it m a y e v a p o r a t e , to
t h e left o f L M N i t m a y s o l i d i f y .
Q R s E. T o t h e left o f this l i n e t h e s u b s t a n c e is s o l i d and
absolutely stable. T o the right o f SRQ it m a y m e l t , and
a b o v e s E it m a y e v a p o r a t e .
c is t h e c r i t i c a l p o i n t o f t h e l i q u i d a n d g a s e o u s states.
B e l o w t h i s p o i n t t h e r e is n o d i s c o n t i n u i t y o f states.
C is c a l l e d in g e o m e t r y t h e t a c n o d a l p o i n t .
The curves F G, G H C K I., I. M N , Q R S, a n d s E are
branches o f what is c a l l e d i n g e o m e t r y t h e node-couple
curve.
The curves x c x and Y Y are branches o f the spinode
curve.
Above this c u r v e the substance is absolutely unstable.
B e t w e e n i t a n d t h e n o d e - c o u p l e c u r v e t h e s u b s t a n c e is stable,
but o n l y if h o m o g e n e o u s .

T h e p l a n e t r i a n g l e SLC represents that state o f uniform

pressure and temperature at which the substance can be
partly solid, partly liquid, and partly gaseous.
T h e s t r a i g h t l i n e s r e p r e s e n t states o f u n i f o r m p r e s s u r e and
t e m p e r a t u r e in w h i c h t w o d i f f e r e n t s t a t e s a r e i n e q u i l i b r i u m .
s G and E F b e t w e e n solid and gaseous.

G L and K H b e t w e e n liquid and gaseous,
s i , R M , and Q N b e t w e e n solid and liquid.
The surface o f dissipated e n e r g y consists o f the plane

triangle SLG and the three d e v e l o p a b l e surfaces o f which
the generating lines are those above mentioned. T h i s sur
face lies a b o v e the primitive thermodynamic surface and
touches it a l o n g the n o d e - c o u p l e curve.

Free Expansion. 209
C H A P T E R XIII.
ON FREE EXPANSION.
Theory of a Fluid in which no External Work is done

during a Change of Pressure.
LET a fluid b e f o r c e d t h r o u g h a s m a l l h o l e , o r o n e o r m o r e
narrow tubes, or a p o r o u s plug, and let the work d o n e b y
the pressure from behind be entirely employed in over
coming the resistance o f the fluid, so that w h e n t h e fluid,
after passing t h r o u g h t h e p l u g , has a r r i v e d at a c e r t a i n p o i n t
its v e l o c i t y is v e r y s m a l l . L e t us a l s o s u p p o s e that n o heat
enters or leaves the fluid, and that no sound or other
vibration, the energy o f w h i c h is c o m p a r a b l e with that
which w o u l d sensibly alter the temperature o f the fluid,
escapes f r o m t h e apparatus.
We a l s o s u p p o s e t h a t t h e m o t i o n is s t e a d y — t h a t is, t h a t
the s a m e q u a n t i t y o f the fluid enters and issues from the
apparatus i n e v e r y s e c o n d .
During the passage o f unit o f mass through the apparatus,
if p a n d v a r e its p r e s s u r e a n d v o l u m e a t t h e
section A b e f o r e r e a c h i n g t h e p l u g , a n d p, v
the s a m e at t h e s e c t i o n B after p a s s i n g t h r o u g h
it, the w o r k d o n e i n f o r c i n g t h e fluid through
the s e c t i o n A is p v , a n d t h e w o r k d o n e b y t h e
fluid in issuing t h r o u g h t h e s e c t i o n B is p v, s o
that the a m o u n t o f w o r k c o m m u n i c a t e d t o t h e
fluid in p a s s i n g t h r o u g h t h e p l u g is P v — p v.
H e n c e , i f E is t h e e n e r g y o f u n i t o f m a s s o f
the fluid w h i l e e n t e r i n g at t h e s e c t i o n A, a n d e the energy of
unit o f m a s s i s s u i n g at t h e s e c t i o n B,
e — E = PV — pv,
or
% + VY =z e+ p V . . . ( i )
P
2IO Free Expansion.
T h a t is t o say, t h e sum o f the intrinsic e n e r g y and the

product o f the v o l u m e and the pressure remains the same
after p a s s i n g t h r o u g h t h e p l u g , p r o v i d e d n o h e a t is l o s t or
g a i n e d from external sources.
N o w t h e i n t r i n s i c e n e r g y E is i n d i c a t e d o n the diagram
b y the area between A a an
F I G . 28.
adiabatic line, A a a vertical
l i n e , a n d ab v the line o f no
p r e s s u r e , a n d P v is represent
ed b y t h e r e c t a n g l e A p 0 a.
Hence the area included by
a A p o v, t h e l i n e s A a a n d o v
b e i n g p r o d u c e d till t h e y m e e t ,
represents the quantity which
ce r e m a i n s t h e s a m e after passing
through the plug. H e n c e in
o the figure the a r e a Ap g R is

equal to the area contained
b e t w e e n B R a n d t h e t w o a d i a b a t i c . l i n e s R a a n d B (1.
W e s h a l l n e x t e x a m i n e t h e r e l a t i o n s b e t w e e n t h e different
p r o p e r t i e s o f t h e s u b s t a n c e , i n o r d e r t o d e t e r m i n e t h e rise o f
temperature c o r r e s p o n d i n g to a passage through the plug
f r o m a p r e s s u r e P t o a p r e s s u r e p, a n d w e s h a l l first s u p p o s e
t h a t p is n o t m u c h g r e a t e r t h a n p.
L e t A c b e a n i s o t h e r m a l l i n e t h r o u g h A , c u t t i n g q B in c,
and l e t us suppose that the passage o f the substance from
t h e state r e p r e s e n t e d b y A to the s t a t e r e p r e s e n t e d b y B is
effected b y a passage a l o n g the i s o t h e r m a l l i n e A C, followed
b y an increase of v o l u m e from c t o B. T h e smaller the
d i s t a n c e A B , t h e less w i l l t h e r e s u l t s o f this p r o c e s s differ
from t h o s e o f t h e a c t u a l p a s s a g e f r o m A t o B, i n w h a t e v e r
m a n n e r t h i s is r e a l l y e f f e c t e d .
I n p a s s i n g f r o m A t o c , at t h e c o n s t a n t t e m p e r a t u r e 0, the
p r e s s u r e d i m i n i s h e s f r o m p t o p. T h e heat a b s o r b e d during
this p r o c e s s is, b y t h e first t h e r m o d y n a m i c r e l a t i o n ( p . 167),
f p - / ) V 8 a,
Free Expansion. 211
w h e r e a is t h e d i l a t a t i o n o f u n i t o f v o l u m e at c o n s t a n t p r e s
sure p e r d e g r e e o f t e m p e r a t u r e .
I n p a s s i n g f r o m c t o B t h e s u b s t a n c e e x p a n d s at c o n s t a n t
pressure, a n d its t e m p e r a t u r e rises f r o m 8 t o 6 + T.
The h e a t r e q u i r e d t o p r o d u c e this r i s e o f t e m p e r a t u r e is
Kp T,
where K p d e n o t e s t h e s p e c i f i c h e a t o f t h e s u b s t a n c e at c o n
stant pressure.
The whole heat absorbed b y the substance during the
passage f r o m A t o B is t h e r e f o r e
(P — / ) V 0 a 4- K D T,
and this is t h e v a l u e o f t h e a r e a b e t w e e n A B a n d t h e t w o
adiabatic l i n e s A a, B /3.
N o w this is e q u a l t o t h e a r e a Ap q B or (p — / ) v .
H e n c e w e h a v e the equation
K,T = (p-/)v(l-6a) . . . (2)

where K p d e n o t e s t h e s p e c i f i c h e a t o f u n i t o f m a s s at con
stant pressure, e x p r e s s e d in d y n a m i c a l m e a s u r e ;
T, the rise o f t e m p e r a t u r e after p a s s i n g t h r o u g h t h e p l u g ;
p — / , t h e small difference o f pressure o n the t w o sides o f
the p l u g ;
v , the v o l u m e o f u n i t o f m a s s ( w h e n P — p is s o g r e a t as
to cause c o n s i d e r a b l e a l t e r a t i o n o f v o l u m e , this quantity
must b e t r e a t e d d i f f e r e n t l y ) ;
8, the t e m p e r a t u r e o n t h e a b s o l u t e d y n a m i c a l s c a l e ;
a, the d i l a t a t i o n o f u n i t o f v o l u m e at c o n s t a n t pressure
per d e g r e e o f t e m p e r a t u r e .
T h e r e are t w o cases in w h i c h o b s e r v a t i o n s o f the rise ( o r
fall) of t e m p e r a t u r e m a y b e a p p l i e d t o d e t e r m i n e q u a n t i t i e s
of g r e a t i m p o r t a n c e i n t h e s c i e n c e o f h e a t .
1. To Determine the Dynamical Equivalent of Heat.—The
first case is t h a t i n w h i c h t h e s u b s t a n c e is a l i q u i d such as
water or m e r c u r y , t h e v o l u m e o f w h i c h is b u t s l i g h t l y a f f e c t e d
either b y p r e s s u r e o r b y t e m p e r a t u r e . I n this c a s e v w i l l
p 2
212 Free Expansion.
v a r y so l i t t l e t h a t t h e effect o f its v a r i a t i o n m a y b e taken

i n t o a c c o u n t as a c o r r e c t i o n r e q u i r e d o n l y i n c a l c u l a t i o n s o f
great accuracy. T h e d i l a t a t i o n a is a l s o v e r y s m a l l , s o much
s o t h a t t h e p r o d u c t 6 a, t h o u g h , n o t t o b e a b s o l u t e l y n e g l e c t e d ,
m a y b e f o u n d w i t h sufficient a c c u r a c y w i t h o u t a v e r y a c c u r a t e
k n o w l e d g e o f t h e a b s o l u t e v a l u e o f fl.
I f w e s u p p o s e t h e p r e s s u r e t o b e d u e t o a d e p t h o f fluid
e q u a l t o H o n o n e s i d e o f t h e p l u g a n d h o n t h e o t h e r , then
(p - p) = (H - h) p g,
w h e r e p is t h e d e n s i t y , a n d g is t h e n u m e r i c a l m e a s u r e o f the
force of gravity. Now
v p = I,
s o t h a t e q u a t i o n (2) b e c o m e s
H h l 6 a
k
p r
= S( - ) ( - ),
an equation from w h i c h w e can determine K p when w e know
r t h e rise o f t e m p e r a t u r e , a n d H — h the difference of level
of the l i q u i d , a its c o e f f i c i e n t o f dilatation b y heat, and
( w i t h i n a m o d e r a t e d e g r e e o f e x a c t n e s s ) 6 the absolute tem
p e r a t u r e in terms o f the d e g r e e s o f the same thermometer
w h i c h i s u s e d t o d e t e r m i n e r.
T h e quantity K p is t h e s p e c i f i c h e a t at c o n s t a n t pressure,
t h a t is t h e q u a n t i t y o f h e a t w h i c h w i l l r a i s e u n i t o f m a s s o f
the substance o n e d e g r e e o f the thermometer. It is e x
pressed here in dynamical measure or foot-poundals.
If the specific heat is to be expressed in gravitation
m e a s u r e , as i n f o o t - p o u n d s , w e m u s t d i v i d e b y g, t h e i n t e n s i t y
of gravity. I f the s p e c i f i c h e a t is t o b e e x p r e s s e d i n terms
o f t h e s p e c i f i c h e a t o f a s t a n d a r d s u b s t a n c e , as, f o r instance,
w a t e r at its m a x i m u m density, w e must d i v i d e b y j , the
specific heat o f this substance.
We have already shown h o w b y a direct experiment to
compare the specific heat o f any s u b s t a n c e w i t h that o f
water. I f t h e s p e c i f i c h e a t e x p r e s s e d i n this w a y is d e n o t e d
by c , while K
p p is t h e s a m e q u a n t i t y e x p r e s s e d i n dynamical

Dynamical Equivalent of Heat. 213
measure, then the dynamical equivalent o f the thermal
unit is
T h e q u a n t i t y J is c a l l e d J o u l e ' s Mechanical Equivalent

o f H e a t , b e c a u s e J o u l e w a s t h e first t o d e t e r m i n e its v a l u e
by a n a c c u r a t e method. I t m a y b e d e f i n e d as t h e s p e c i f i c
heat, i n dynamical measure, of water at its maximum
density.
I t is e q u a l t o 772 f o o t - p o u n d s at M a n c h e s t e r p e r pound
of w a t e r . I f w e a l t e r t h e s t a n d a r d o f m a s s , w e at t h e s a m e
time alter t h e u n i t o f w o r k i n t h e s a m e p r o p o r t i o n , so t h a t
w e m u s t still e x p r e s s J b y t h e same number. Hence we
may express Joule's result b y s a y i n g t h a t t h e w o r k d o n e b y
any q u a n t i t y o f w a t e r in f a l l i n g 772 f e e t a t M a n c h e s t e r is
capable o f raising that w a t e r o n e d e g r e e F a h r e n h e i t . If we
wish t o r e n d e r t h e d e f i n i t i o n i n d e p e n d e n t o f the value o f
gravity at a p a r t i c u l a r place, w e h a v e only to calculate the
velocity o f a b o d y after f a l l i n g 772 f e e t at M a n c h e s t e r . The
e n e r g y c o r r e s p o n d i n g t o this v e l o c i t y i n a n y m a s s o f w a t e r
is c a p a b l e w h e n c o n v e r t e d i n t o h e a t o f r a i s i n g t h e w a t e r o n e
degree Fahrenheit.
T h e r e are c o n s i d e r a b l e difficulties in o b t a i n i n g the v a l u e o f

j b y this m e t h o d , e v e n w i t h m e r c u r y , f o r w h i c h a p r e s s u r e
of 25 feet g i v e s a rise o f o n e d e g r e e F a h r e n h e i t .
2. To reduce Temperatures to the Thermodynamic Scale.

7'he most important application o f the method is tc
ascertain the temperature, 0, o n t h e t h e r m o d y n a m i c s c a l e ,
which c o r r e s p o n d s to the reading, /, registered b y any ordi
nary t h e r m o m e t e r , e.g. a c e n t i g r a d e t h e r m o m e t e r .
The s u b s t a n c e e m p l o y e d is air, o r a n y o t h e r g a s w h i c h
satisfies a p p r o x i m a t e l y t h e gaseous l a w s e x p r e s s e d in the
equation
vp = v p (1 + a t),
0 0 0
where v , Pa> a r e t h e v o l u m e a n d
6 p r e s s u r e a t t h e z e r o o f the

214 Free Expansion.
thermometer, and a 0 is t h e v o l u m i n a l d i l a t a t i o n p e r d e g r e e
at t h a t temperature.
T h e v o l u m i n a l d i l a t a t i o n , A , at t h e t e m p e r a t u r e t is therefore
I + at
a
s o that t h e e x p r e s s i o n f o r K R b e c o m e s
P
K R = V p —~ f ( I + A r - A 0 ) .
P 0 0 0 0
This expression is s t r i c t l y true only for a very small

v a r i a t i o n o f t h e pressure. W h e n , as i n t h e e x p e r i m e n t s of
J o u l e a n d T h o m s o n , p is s e v e r a l t i m e s p, w e m u s t ascertain
t h e e f f e c t o f t h e g r a d u a l d i m i n u t i o n o f p r e s s u r e b y the process
d e s c r i b e d at p . 221, w h i c h is a p p l i c a b l e i n t h i s c a s e , b e c a u s e
the variation o f temperature is f o u n d to be small. The
result is t h a t i n s t e a d o f F- w e m u s t w r i t e l o g , —, w h e r e
P p
P
t h e l o g a r i t h m is N a p i e r i a n , o r 2-3026 l o g - , w h e r e the l o g -
/
a r i t h m is t a k e n f r o m t h e c o m m o n t a b l e s . Hence we find
'0
K
,v p0
r
0 log P — l o g /
e = t + ! " °'4343
a n e x p r e s s i o n w h i c h g i v e s t h e t e m p e r a t u r e , 6, o n t h e t h e r m o
d y n a m i c s c a l e c o r r e s p o n d i n g t o t h e r e a d i n g , /, o f a n o r d i n a r y
t h e r m o m e t e r , t h e d e g r e e s o f t h e t h e r m o d y n a m i c scale b e i n g
equal t o those o f the t h e r m o m e t e r near the temperature of
the experiment.
I n the case of most of the gases examined by Joule
and T h o m s o n t h e r e w a s a slight c o o l i n g effect o n t h e gas
passing through the plug. I n other words, r was negative,
and the absolute temperature was therefore higher than
that i n d i c a t e d by the gaseous thermometer. T h e ratio,
therefore, in which the gas e x p a n d e d b e t w e e n t w o standard

Determination of Absolute Temperature. 215
temperatures w a s g r e a t e r t h a n the true ratio o f these tem

peratures o n t h e t h e r m o d y n a m i c s c a l e . T h e c o o l i n g effect
was m u c h greater with carbonic acid than with oxygen,
n i t r o g e n , o r air, as w a s to b e e x p e c t e d , because w e k n o w
from t h e e x p e r i m e n t s o f Regnault that the dilatation of
c a r b o n i c a c i d is g r e a t e r t h a n t h a t o f air o r its constituents.
I t was a l s o f o u n d , f o r a l l t h e s e g a s e s , t h a t t h e c o o l i n g effect
was less a t h i g h temperatures, which shows that as the
temperature rises the dilatation of the gas is m o r e and
more accurately proportional t o the absolute temperature
o f the t h e r m o d y n a m i c s c a l e .
The only gas which exhibited a contrary effect was

hydrogen, in which there was a slight heating effect after
passing t h e p l u g .
T h e result o f the experiments o f Joule and Thomson
was to show that the temperature of melting ice is
273°'7 on the thermodynamic scale, the degrees being
such that t h e r e a r e 100 of them b e t w e e n this temperature
and that o f the v a p o u r o f b o i l i n g w a t e r at the standard
pressure.
The absolute z e r o o f the t h e r m o d y n a m i c s c a l e is t h e r e
fore — z 7 3 ° 7 C e n t i g r a d e , o r —46o°'66 F a h r e n h e i t .
I t a p p e a r s , t h e r e f o r e , that, i n t h e m o r e perfect gases, the
c o o l i n g effect d u e t o e x p a n s i o n is a l m o s t e x a c t l y balanced
b y the h e a t i n g e f f e c t d u e t o t h e w o r k d o n e b y t h e e x p a n s i o n
w h e n this w o r k is w h o l l y s p e n t in generating heat in the
gas. T h i s result h a d b e e n already obtained, although b y a
1
method not admitting o f such great accuracy, b y Joule, who
showed that the intrinsic e n e r g y o f a g a s is t h e s a m e at
the s a m e temperature, whatever b e the volume which it
occupies.
T o test this, h e c o m p r e s s e d air i n t o a v e s s e l till i t c o n
tained about 2 2 atmospheres, and exhausted t h e air from
another vessel. These vessels w e r e then connected by
1
Phil. Mag. M a y 1845.

2IÖ Free Expansion.
means o f a p i p e c l o s e d by a s t o p c o c k , a n d the w h o l e placed

m a vessel o f water.
A f t e r a sufficient time the w a t e r w a s t h o r o u g h l y stirred,
a n d its t e m p e r a t u r e taken b y means o f a delicate thermo
meter. T h e s t o p c o c k was t h e n o p e n e d b y m e a n s o f a proper
k e y , a n d t h e air a l l o w e d t o p a s s f r o m t h e full i n t o the e m p t y
vessel till equilibrium was established between the two.
Lastly the water was again stirred and its temperature
carefully n o t e d .
From a number of experiments o f this k i n d , carefully
corrected for all sources of error, J o u l e was l e d to the
conclusion thatno change of temperature occurs when air
is allowed to expand in such a manner as not to develop
mechanical power.
This result, as h a s been shown b y the more accurate
e x p e r i m e n t s a f t e r w a r d s m a d e b y J o u l e a n d W . T h o m s o n , is
not q u i t e c o r r e c t , f o r t h e r e is a s l i g h t c o o l i n g effect. This
e f f e c t , h o w e v e r , is v e r y s m a l l i n t h e c a s e o f p e r m a n e n t gases,
and diminishes when the gas, b y rise o f temperature or
d i m i n u t i o n o f pressure, approaches nearer to the condition
o f a perfect gas.
W e m a y h o w e v e r a s s e r t , as t h e r e s u l t o f t h e s e e x p e r i m e n t s ,
that the amount o f heat absorbed by a g a s e x p a n d i n g at
u n i f o r m t e m p e r a t u r e is n e a r l y , t h o u g h n o t e x a c t l y , t h e t h e r m a l
e q u i v a l e n t o f the m e c h a n i c a l w o r k d o n e b y the gas during
the expansion. I n fact, w e k n o w t h a t i n t h e c a s e o f air the
h e a t a b s o r b e d is a l i t t l e grea.ter a n d i n h y d r o g e n a v e r y l i t t l e
less than this quantity.
T h i s is a v e r y i m p o r t a n t p r o p e r t y o f g a s e s . I f w e reverse
t h e p r o c e s s , w e find t h a t t h e h e a t d e v e l o p e d b y c o m p r e s s i n g
air at constant t e m p e r a t u r e is t h e t h e r m a l e q u i v a l e n t o f t h e
w o r k d o n e i n c o m p r e s s i n g it.
T h i s is b y n o m e a n s a self-evident proposition. In fact,
it is n o t t r u e i n t h e c a s e o f s u b s t a n c e s w h i c h a r e n o t i n the
g a s e o u s state, a n d e v e n i n t h e case o f the m o r e imperfect
g a s e s it d e v i a t e s from t h e truth. H e n c e the calculation of

Measurement of Heights by Üie Barometer. 217
the d y n a m i c a l e q u i v a l e n t o f h e a t , w h i c h M a y e r f o u n d e d on
this p r o p o s i t i o n , a t a time when its truth h a d not been
e x p e r i m e n t a l l y p r o v e d , c a n n o t b e r e g a r d e d as l e g i t i m a t e .
C H A P T E R X I V .
OX T H E D E T E R M I N A T I O N OF H E I G H T S BY T H E BAROMETER.
THE barometer is a n instrument b y means o f which the

pressure o f t h e air a t a p a r t i c u l a r place m a y b e measured.
I n the m e r c u r i a l b a r o m e t e r , w h i c h is t h e m o s t p e r f e c t f o r m o f
the i n s t r u m e n t , t h e p r e s s u r e o f t h e a i r o n t h e free s u r f a c e o f
the m e r c u r y i n t h e c i s t e r n is e q u a l t o t h a t o f a c o l u m n o f
m e r c u r y w h o s e h e i g h t is t h e d i f f e r e n c e b e t w e e n t h e l e v e l o f
the m e r c u r y i n t h e c i s t e r n , w h i c h sustains t h e p r e s s u r e o f t h e
air, a n d t h a t o f t h e m e r c u r y i n the tube, w h i c h has no air
a b o v e it. T h e p r e s s u r e o f t h e air is o f t e n e x p r e s s e d i n t e r m s
o f the h e i g h t o f this c o l u m n . T h u s w e speak o f a pressure
o f 30 i n c h e s o f m e r c u r y , o r o f a p r e s s u r e o f 760 m i l l i m e t r e s o f
mercury.
To express a pressure in absolute measure we must

consider the force e x e r t e d against unit o f area. F o r this
purpose w e m u s t find t h e w e i g h t o f a c o l u m n o f m e r c u r y o f
the g i v e n h e i g h t s t a n d i n g o n u n i t o f a r e a a s b a s e .
I f h is t h e h e i g h t o f t h e c o l u m n , t h e n , s i n c e its s e c t i o n is
unity, its v o l u m e is e x p r e s s e d b y h.
T o find t h e m a s s o f m e r c u r y c o n t a i n e d i n this v o l u m e w e
must m u l t i p l y t h e v o l u m e b y t h e d e n s i t y o f m e r c u r y . I f this
density is d e n o t e d b y 0, the m a s s o f t h e c o l u m n is a h. The
pressure, w h i c h w e h a v e t o find, is t h e f o r c e w i t h w h i c h t h i s
mass is d r a w n d o w n w a r d s b y t h e earth's attraction. If g
denotes the f o r c e o f the earth's attraction o n unit o f mass,
then t h e f o r c e o n t h e c o l u m n w i l l b e gfi h. The pressure

2i8 Measurement of Heights by the Barometer.
t h e r e f o r e of a c o l u m n o f m e r c u r y o f h e i g h t h is e x p r e s s e d
by
gph,
w h e r e h is t h e h e i g h t of t h e c o l u m n , p t h e d e n s i t y o f m e r c u r y ,
a n d ^ t h e i n t e n s i t y o f g r a v i t y at t h e p l a c e . T h e density of
m e r c u r y d i m i n i s h e s as t h e t e m p e r a t u r e i n c r e a s e s . I t is usual
t o r e d u c e a l l p r e s s u r e s m e a s u r e d i n this w a y t o t h e h e i g h t o f
a c o l u m n o f m e r c u r y at t h e f r e e z i n g t e m p e r a t u r e o f w a t e r .
I f t w o b a r o m e t e r s at t h e s a m e p l a c e a r e k e p t at different
temperatures, the heights o f the b a r o m e t e r s are in the pro
p o r t i o n o f t h e v o l u m e s o f m e r c u r y at t h e t w o t e m p e r a t u r e s .
., T h e i n t e n s i t y o f g r a v i t a t i o n v a r i e s at d i f f e r e n t p l a c e s , b e i n g
l e s s at t h e e q u a t o r t h a n at t h e p o l e s , a n d less at t h e t o p o f a
m o u n t a i n t h a n at t h e l e v e l o f t h e sea.
I t is u s u a l t o r e d u c e o b s e r v e d b a r o m e t r i c h e i g h t s t o the
h e i g h t o f a c o l u m n o f m e r c u r y at t h e f r e e z i n g p o i n t a n d at
t h e l e v e l o f t h e s e a i n l a t i t u d e 45°, w h i c h w o u l d p r o d u c e the
same pressure.
I f t h e r e w e r e n o t i d e s o r w i n d s , a n d i f t h e s e a a n d t h e air
w e r e ' p e r f e c t l y c a l m in the w h o l e r e g i o n b e t w e e n t w o places,
then the actual pressure o f the air at the level o f the sea
m u s t b e t h e s a m e in t h e s e t w o p l a c e s ; f o r t h e surface o f
t h e s e a is e v e r y w h e r e p e r p e n d i c u l a r t o t h e f o r c e o f g r a v i t y .
If, t h e r e f o r e , t h e p r e s s u r e o n its surface w e r e d i f f e r e n t in
t w o p l a c e s , w a t e r w o u l d f l o w f r o m t h e p l a c e o f g r e a t e r pres
s u r e t o t h e p l a c e o f l e s s p r e s s u r e till e q u i l i b r i u m e n s u e d .
H e n c e , i f in c a l m w e a t h e r t h e b a r o m e t e r is f o u n d t o stand
at a d i f f e r e n t h e i g h t i n t w o d i f f e r e n t p l a c e s at t h e l e v e l o f
t h e sea, t h e r e a s o n m u s t b e t h a t g r a v i t y i s m o r e i n t e f i s e at
t h e p l a c e w h e r e t h e b a r o m e t e r is l o w .
Let us n e x t c o n s i d e r t h e m e t h o d o f finding the depth
b e l o w t h e l e v e l o f t h e sea b y m e a n s o f a b a r o m e t e r c a r r i e d
d o w n in a d i v i n g bell.
I f D is t h e d e p t h o f t h e surface o f t h e w a t e r i n t h e d i v i n g
b e l l b e l o w t h e surface o f t h e s e a , a n d i f p is t h e p r e s s u r e o f
the a t m o s p h e r e o n the surface o f the sea, t h e n the pressure

Barometer in a Diving Bell. 219
of the air i n t h e d i v i n g b e l l m u s t e x c e e d that o n t h e surface
o f the sea b y t h e p r e s s u r e d u e t o a c o l u m n o f w a t e r o f d e p t h
D. I f o- is t h e d e n s i t y o f s e a - w a t e r , t h e p r e s s u r e d u e to a
c o l u m n o f d e p t h D is g a D .
L e t t h e h e i g h t o f t h e b a r o m e t e r at t h e surface o f t h e sea
b e o b s e r v e d , a n d l e t us s u p p o s e t h a t i n t h e d i v i n g b e l l i t is
found t o b e h i g h e r b y a h e i g h t h, t h e n t h e a d d i t i o n a l p r e s
sure i n d i c a t e d b y t h i s r i s e is g p h, w h e r e p is t h e d e n s i t y o f
mercury. Hence
g " D = g p h,
or
D = ^ h — s k,
, p density o f mercury .,- ., ,

where s = —= —= .- - -- - = specific g r a v i t y o f
rj density o f water
mercury.
T h e d e p t h b e l o w t h e surface o f t h e s e a is t h e r e f o r e e q u a l
to the p r o d u c t o f t h e r i s e o f t h e b a r o m e t e r m u l t i p l i e d b y t h e
specific g r a v i t y o f m e r c u r y . I f the w a t e r is salt w e m u s t
d i v i d e this result b y t h e s p e c i f i c g r a v i t y o f t h e salt w a t e r at
the p l a c e o f o b s e r v a t i o n .
T h e calculation o f d e p t h s u n d e r w a t e r b y this m e t h o d is
comparatively easy, because the density o f t h e w a t e r is n o t
v e r y d i f f e r e n t at d i f f e r e n t d e p t h s . I t is o n l y at g r e a t d e p t h s
that t h e c o m p r e s s i o n o f t h e w a t e r w o u l d s e n s i b l y affect the
result.
I f the d e n s i t y o f air h a d b e e n as u n i f o r m as t h a t o f w a t e r ,
the m e a s u r e m e n t o f h e i g h t s i n t h e a t m o s p h e r e w o u l d h a v e
b e e n as e a s y . F o r i n s t a n c e , i f t h e d e n s i t y o f air h a d b e e n
equal t o a a t a l l p r e s s u r e s , t h e n , n e g l e c t i n g t h e v a r i a t i o n o f
gravity with h e i g h t a b o v e the earth, w e should find the
height >§ o f t h e a t m o s p h e r e thus : L e t h b e t h e h e i g h t o f
the b a r o m e t e r , a n d p t h e d e n s i t y o f m e r c u r y , t h e n t h e p r e s s u r e
i n d i c a t e d b y t h e b a r o m e t e r is
/ = g P »·

220 Measurement of Heights by tJie Barometer.
If •§ is t h e height o f an atmosphere o f density A, it

produces a pressure
p —g A ft.
Hence
A
T h i s is t h e h e i g h t o f t h e a t m o s p h e r e a b o v e t h e p l a c e on
XHZ FALSE s u p p o s i t i o n t h a t its d e n s i t y is t h e s a m e at all heights
as it is at t h a t p l a c e . T h i s h e i g h t is g e n e r a l l y r e f e r r e d t o as
the HEIGHT OF THE ATMOSPHERE SUPPOSED OF U
m o r e b r i e f l y a n d t e c h n i c a l l y as t h e h e i g h t o f t h e HOMOGENEOUS
ATMOSPHERE.
L e t us f o r a m o m e n t c o n s i d e r w h a t this height (which
e v i d e n t l y has nothing to do with the real height o f the
a t m o s p h e r e ) really represents. F r o m the equation
f> =g°%,
r e m e m b e r i n g that A the d e n s i t y o f air is t h e s a m e t h i n g as
the r e c i p r o c a l o f v the v o l u m e o f unit o f mass, w e get
o r . § is simply the product / v expressed in gravitation

measure instead o f absolute measure.
Now, by Boyle's l a w the product o f the pressure and
the v o l u m e at a constant t e m p e r a t u r e is c o n s t a n t , a n d by
Charles's l a w this p r o d u c t is p r o p o r t i o n a l to the absolute
temperature. F o r d r y air a t t h e t e m p e r a t u r e o f m e l t i n g i c e ,
and when g = 32-2,
v
>§ = ^ • = 26,214 f e e t ,
S
o r s o m e w h a t l e s s t h a n five statute m i l e s .
It is w e l l k n o w n that M r . G l a i s h e r has ascended in a
balloon to the height o f seven miles. T h i s b a l l o o n was
s u p p o r t e d b y t h e air, a n d t h o u g h t h e a i r a t this g r e a t h e i g h t
w a s m o r e t h a n t h r e e t i m e s r a r e r t h a n at t h e earth's surface, it
was p o s s i b l e t o b r e a t h e i n it. H e n c e i t is c e r t a i n that the

Height of a Mountain. 221
a t m o s p h e r e m u s t e x t e n d a b o v e t h e h e i g h t <§, w h i c h w e h a v e
deduced from our false assumption that the density is
uniform.
But t h o u g h the d e n s i t y o f t h e a t m o s p h e r e is b y n o means
uniform t h r o u g h great ranges o f height, y e t i f w e confine
ourselves t o a v e r y s m a l l r a n g e , s a y t h e m i l l i o n t h p a r t o f > § —
that is, a b o u t o"026 f e e t , o r l e s s t h a n t h e t h i r d o f a n inch—the
density w i l l o n l y v a r y o n e - m i l l i o n t h p a r t o f i t s e l f f r o m the
top to the b o t t o m o f this range, so that w e m a y s u p p o s e the
pressure at t h e b o t t o m t o e x c e e d t h a t a t t h e t o p b y e x a c t l y
one-millionth.
L e t us n o w a p p l y t h i s m e t h o d t o d e t e r m i n e t h e h e i g h t o f
a mountain b y the f o l l o w i n g i m a g i n a r y process, t o o laborious
to b e r e c o m m e n d e d , e x c e p t f o r t h e p u r p o s e o f explaining
the p r a c t i c a l m e t h o d :
W e shall s u p p o s e t h a t w e b e g i n a t t h e t o p o f t h e m o u n t a i n ,
a n d that, b e s i d e s o u r b a r o m e t e r , w e have one thermometer
t o d e t e r m i n e the t e m p e r a t u r e o f t h e m e r c u r y , a n d a n o t h e r t o
d e t e r m i n e t h e t e m p e r a t u r e o f t h e air. W e are a l s o p r o v i d e d
with a h y g r o m e t e r , to determine the quantity of aqueous
v a p o u r in t h e air, so t h a t b y t h e t h e r m o m e t e r a n d h y g r o m e t e r
w e can c a l c u l a t e Jq, t h e h e i g h t o f the homogeneous atmo
sphere, at e v e r y s t a t i o n o f o u r p a t h .
O n the t o p o f t h e m o u n t a i n , t h e n , w e o b s e r v e t h e h e i g h t o f
the b a r o m e t e r t o b e W e n o w d e s c e n d the m o u n t a i n till
we observe the mercury in the b a r o m e t e r to rise b y one-
m i l l i o n t h p a r t o f its o w n h e i g h t T h e height o f the baro
m e t e r at this first s t a t i o n is
J> =
i ( r o o o o o i ) p.
T h e d i s t a n c e w e h a v e d e s c e n d e d is o n e - m i l l i o n t h o f >§,
the h e i g h t o f t h e h o m o g e n e o u s a t m o s p h e r e f o r t h e observed
temperature at t h e first s t a g e o f t h e d e s c e n t . S i n c e i t is
at p r e s e n t impossible to measure pressures, & c , to one-
m i l l i o n t h o f t h e i r v a l u e , it d o e s not matter whether .§ b e

222 Measurement of Heights by the Barometer.
m e a s u r e d a t t h e t o p o f t h e m o u n t a i n o r o n e - t h i r d o f an inch
lower down.
N o w l e t us d e s c e n d a n o t h e r s t a g e , till t h e p r e s s u r e again
increases o n e - m i l l i o n t h o f itself, s o t h a t i f p 2 is the n e w
pressure,
p = (i/OOQOOl) Pi,
t
and the s e c o n d d e s c e n t is t h r o u g h a h e i g h t e q u a l t o the

m i l l i o n t h o f «E> , t h e h e i g h t o f t h e h o m o g e n e o u s a t m o s p h e r e
2
in the s e c o n d stage.
I f w e g o o n i n t h i s w a y « t i m e s , t i l l w e at last r e a c h the
bottom o f the mountain, and i f / „ is the p r e s s u r e at the
bottom,
A = (I'OOOOOI) A.-1
a
= (l-OOOOOl) /„_ 2
= (fOOOOOl)"/,
and the w h o l e vertical height will b e
h _ £1 + £ 2 + &c + &
1,000,000
I f w e assume that the temperature and h u m i d i t y are the
s a m e at all heights b e t w e e n the top and t h e b o t t o m , then
= JQ =
2 &c.= •£>„ = >§, a n d t h e h e i g h t o f t h e mountain
will be
= —?
1,000,000
if w e k n o w n, t h e number o f stages, w e can determine
the height o f the m o u n t a i n in this w a y . B u t it is easy t o
find n without going through the laborious process of
descending b y distances o f the third o f a n i n c h , for since
/„ = P is t h e p r e s s u r e a t t h e b o t t o m , a n d / t h a t at the top,
w e h a v e the equation
p = (i-oooooi)"/.
Taking t h e l o g a r i t h m o f b o t h s i d e s o f this e q u a t i o n , w e
get

2 2
Waves. 3
log P = « log ( i ' o o o o o i ) 4- l o g / ,

or
n = log P — l o g /
log ( r o o o o o i )
N o w log r o o o o o i = 0-0000004342942648.
Substituting this value in the expression for h, we get
h = ^ * _ log *
434294 P
where the logarithms are the common logarithms to base 10,
or
h = 2-302585 $ log ?.
For dry air at the temperature of melting ice<§ = 26,214

feet: hence
0
h = log J x J 60360 + ( 0 - 3 2 ) (123-68) J
gives the height in feet for a temperature 0 on Fahrenheit's
scale.
For rough purposes, the difference of the logarithms of the
heights of the barometer multiplied by 10,000 gives the
difference of the heights in fathoms of six feet.
CHAPTER XV.
O N T H E PROPAGATION O F WAVES.
THE following method o f investigating the conditions o f the

1
propagation o f waves is due to Prof. R a n k i n e . I t involves
only elementary principles and operations, but leads to
results which have been hitherto obtained only by opera
tions involving the higher branches o f mathematics.
1 1
Phil. Trans. 1869 : On the Thermodynamic Theory of Waves of
Finite Longitudinal Disturbance.'

224 Waves.
T h e k i n d o f w a v e s t o w h i c h t h e i n v e s t i g a t i o n a p p l i e s are
t h o s e i n w h i c h t h e m o t i o n o f t h e p a r t s o f t h e substance is
a l o n g straight lines parallel t o the d i r e c t i o n in w h i c h the
wave is p r o p a g a t e d , a n d the w a v e is d e f i n e d t o b e one
w h i c h is p r o p a g a t e d w i t h c o n s t a n t v e l o c i t y , a n d t h e t y p e of
w h i c h d o e s n o t a l t e r d u r i n g its p r o p a g a t i o n .
In other words, if we observe what goes on in the
s u b s t a n c e at a g i v e n p l a c e w h e n t h e w a v e p a s s e s that place,
and if w e s u d d e n l y transport o u r s e l v e s a c e r t a i n distance
forward in the direction o f propagation o f the wave, then
a f t e r a c e r t a i n t i m e w e s h a l l o b s e r v e e x a c t l y t h e s a m e things
o c c u r r i n g i n t h e s a m e o r d e r i n t h e n e w p l a c e , w h e n the w a v e
r e a c h e s it. I f w e t r a v e l w i t h the v e l o c i t y o f the wave, we
shall therefore o b s e r v e n o c h a n g e i n the appearance pre
s e n t e d b y t h e w a v e as i t t r a v e l s a l o n g w i t h us. T h i s is the
characteristic o f a w a v e o f p e r m a n e n t type.
We shall first consider the quantity o f the substance

w h i c h passes i n u n i t o f t i m e t h r o u g h u n i t o f a r e a o f a plane
which w e shall suppose fixed, and perpendicular to the
direction o f motion.
Let u b e the velocity o f t h e s u b s t a n c e , w h i c h w e shall
s u p p o s e t o b e u n i f o r m , t h e n i n u n i t o f t i m e a p o r t i o n o f the
substance w h o s e l e n g t h is u passes t h r o u g h a n y section
of a plane perpendicular to the direction o f motion. Hence
t h e v o l u m e w h i c h p a s s e s t h r o u g h u n i t o f a r e a is r e p r e s e n t e d
by u.
N o w l e t Q b e t h e q u a n t i t y o f t h e s u b s t a n c e w h i c h passes
through, and let v b e the v o l u m e o f unit o f m a s s o f the
s u b s t a n c e , t h e n t h e w h o l e v o l u m e is Q v, a n d this, b y what
w e h a v e said, is e q u a l t o u, t h e v e l o c i t y o f t h e substance.
I f t h e p l a n e , i n s t e a d o f b e i n g fixed, is m o v i n g f o r w a r d s with
a velocity u, the quantity w h i c h passes t h r o u g h it will
d e p e n d , n o t o n t h e a b s o l u t e v e l o c i t y , u, o f t h e substance,
b u t o n t h e r e l a t i v e v e l o c i t y , u — u , a n d i f Q is t h e quantity
w h i c h passes through the p l a n e from right t o left,
Qv = u — u (i)

Waves of Longitudinal Displacement. 225
Let A b e an i m a g i n a r y p l a n e m o v i n g f r o m left t o right

with v e l o c i t y u, a n d l e t this b e t h e v e l o c i t y o f p r o p a g a t i o n
Fic. 39.
o f the w a v e , t h e n , as t h e p l a n e A t r a v e l s a l o n g , t h e v a l u e s o f
u and all o t h e r q u a n t i t i e s b e l o n g i n g t o the wave at the
plane A remain t h e same. If u Y is t h e a b s o l u t e v e l o c i t y o f
the substance at A , Z / , t h e v o l u m e o f u n i t o f m a s s , a n d p x the
pressure, a l l t h e s e q u a n t i t i e s w i l l b e c o n s t a n t , a n d
Q i »1 = u - «1 (2)
If B be another plane, travelling with the same velo

v
city U, and if Q 2 »2 % Pi he the corresponding values
at B,
0.2 v 2 = U - « 2 (3)
The distance b e t w e e n the planes A and B remains in
variable, b e c a u s e t h e y t r a v e l w i t h t h e s a m e v e l o c i t y . Also
the quantity o f the substance intercepted between them
remains t h e s a m e , b e c a u s e t h e d e n s i t y o f t h e s u b s t a n c e at
corresponding parts o f the wave remains the s a m e as the
wave travels a l o n g . Hence the quantity o f matter which
enters t h e s p a c e b e t w e e n A a n d B at A m u s t b e equal to
that w h i c h l e a v e s i t at B , o r
Qi = Qa = Q (say) (4)
Hence
» 1 = " - Q t , « 2 = U - Q » 2 . . (5)
so that w h e n w e k n o w u a n d Q a n d the v o l u m e o f unit o f

mass, w e c a n f i n d u 1 and « . 2
L e t us n e x t c o n s i d e r t h e f o r c e s a c t i n g o n t h e m a t t e r con
tained b e t w e e n A a n d B. If p y is t h e p r e s s u r e at A , a n d / > ,
Q
226 Waves.
t h a t at B, t h e f a r c e a r i s i n g f r o m t h e s e p r e s s u r e s t e n d i n g to
i n c r e a s e t h e m o m e n t u m f r o m l e f t t o right i s p 2 — p v
T h i s is t h e m o m e n t u m g e n e r a t e d i n u n i t o f t i m e b y the
external pressures o n the p o r t i o n o f the substance between
A a n d B.
N o w w e m u s t r e c o l l e c t that, t h o u g h c o r r e s p o n d i n g points
o f t h e s u b s t a n c e i n t h i s i n t e r v a l a r e a l w a y s m o v i n g in the
s a m e w a y , the matter i t s e l f b e t w e e n A ' a n d B is c o n t i n u a l l y
c h a n g i n g , a q u a n t i t y Q e n t e r i n g a t A, a n d a n e q u a l quantity
Q l e a v i n g a t B.
N o w the portion Q w h i c h enters at A has a velocity u u
and therefore a m o m e n t u m Q u¡, a n d t h a t w h i c h issues at

B has a v e l o c i t y u , 2 and therefore a m o m e n t u m Q « . 2
H e n c e the m o m e n t u m o f the entering fluid e x c e e d s that

o f t h e i s s u i n g fluid b y
Q(*i — « 2 ) -
T h e o n l y w a y i n w h i c h this m o m e n t u m c a n b e p r o d u c e d
is b y the action o f the external pressures p l and/ ; 2 for the
m u t u a l a c t i o n s o f t h e p a r t s o f t h e s u b s t a n c e c a n n o t alter the
m o m e n t u m o f the whole. H e n c e w e find
6
A —A =Q(*i — « 2 ) ( )
S u b s t i t u t i n g t h e v a l u e s o f K, a n d a a f r o m e q u a t i o n (5), w e
find
A - / i = Q > i -v )
2 (7)
Hence
2 2
A +Q »1 = A +Q *i (8)
N o w t h e o n l y r e s t r i c t i o n o n t h e p o s i t i o n o f t h e p l a n e B is
t h a t it m u s t remain at a c o n s t a n t distance b e h i n d A, and
whatever be the distance between A and B, t h e above
e q u a t i o n is a l w a y s true.
s
Hence the quantity p + 0 v must continue constant
during the whole process i n v o l v e d in the passage o f the
wave. C a l l i n g t h i s q u a n t i t y p, w e h a v e
p = P_ ri (9)

Waves of Permanent Type. 227
or the p r e s s u r e is e q u a l t o a c o n s t a n t p r e s s u r e , P, d i m i n i s h e d
b y a q u a n t i t y p r o p o r t i o n a l t o t h e v o l u m e v.
T h i s r e l a t i o n b e t w e e n p r e s s u r e a n d v o l u m e is n o t fulfilled
in the c a s e o f a n y a c t u a l s u b s t a n c e . I n a l l s u b s t a n c e s i t is
true that as t h e v o l u m e d i m i n i s h e s t h e p r e s s u r e i n c r e a s e s ,
but the i n c r e a s e o f p r e s s u r e is n e v e r strictly p r o p o r t i o n a l to
the diminution o f v o l u m e . A s s o o n as t h e d i m i n u t i o n o f
volume becomes considerable, the pressure b e g i n s to in
crease in a g r e a t e r r a t i o t h a n t h e v o l u m e d i m i n i s h e s .
But if w e c o n s i d e r o n l y small changes of volume and
pressure, w e m a y m a k e use o f o u r f o r m e r d e f i n i t i o n o f e l a s
ticity at p . 1 0 7 — n a m e l y , t h e r a t i o o f t h e n u m b e r expressing
the i n c r e m e n t o f p r e s s u r e t o t h a t e x p r e s s i n g t h e v o l u m i n a l
compression, or, c a l l i n g the elasticity E ,
P2 — Pi
E = v v — v — v Q b y equation (7) s
(10)
x %
w h e r e v is the v o l u m e o f u n i t o f m a s s , and since v x and v%
are v e r y n e a r l y e q u a l , w e m a y t a k e e i t h e r f o r t h e v a l u e o f v.
A g a i n , if v is t h e v o l u m e o f u n i t o f m a s s i n t h o s e p a r t s o f t h e
substance w h i c h a r e n o t disturbed by the wave, and for
which, t h e r e f o r e , u = o,
H = Q!) (il)
H e n c e w e find
8 J
u =Q = Ev (12)
which s h o w s t h a t t h e s q u a r e o f t h e v e l o c i t y o f p r o p a g a t i o n
o f a w a v e o f l o n g i t u d i n a l d i s p l a c e m e n t in a n y s u b s t a n c e is
equal t o t h e p r o d u c t o f t h e e l a s t i c i t y a n d t h e v o l u m e o f u n i t
of mass.
In calculating the elasticity w e must take into account the
conditions u n d e r which the compression of the substance
actually t a k e s p l a c e . I f , as i n t h e c a s e o f s o u n d - w a v e s , it is
very s u d d e n , so that a n y h e a t w h i c h is d e v e l o p e d c a n n o t b e
conducted away, then w e must calculate the elasticity o n the
supposition t h a t n o h e a t is a l l o w e d t o e s c a p e .
I n the c a s e o f air o r a n y o t h e r gas the e l a s t i c i t y at constant

228 Waves.
temperature is n u m e r i c a l l y e q u a l to t h e pressure, I f we
d e n o t e , as u s u a l , t h e r a t i o o f t h e s p e c i f i c h e a t at constant
pressure to that at constant v o l u m e b y t h e s y m b o l y, the
e l a s t i c i t y w h e n n o h e a t e s c a p e s is
E* = yp (13)
H e n c e , i f u is t h e v e l o c i t y o f s o u n d ,
u = yp v
a
(14)
We k n o w that when the temperature is t h e s a m e the

product p v remains constant. H e n c e , t h e v e l o c i t y o f sound
is t h e same for the same temperature, whatever be the
pressure o f the air.
If is t h e h e i g h t o f t h e atmosphere supposed homo
geneous—that is to say, the h e i g h t o f a column o f the
same d e n s i t y as the actual density, the w e i g h t o f which
w o u l d p r o d u c e a p r e s s u r e e q u a l t o t h e a c t u a l pressure—then,
i f t h e s e c t i o n o f t h e c o l u m n i s u n i t y , its v o l u m e is · § , and i f
m is its m a s s , = m v.
A l s o t h e w e i g h t o f this c o l u m n is p = m g, w h e r e g is the
force o f gravity.
Hence
p v = g%
and
u 2
= g y&
T h e velocity o f sound m a y b e c o m p a r e d w i t h that o f a
b o d y f a l l i n g a c e r t a i n d i s t a n c e u n d e r t h e a c t i o n o f gravity.
F o r i f v is t h e v e l o c i t y o f a b o d y f a l l i n g t h r o u g h a h e i g h t s,
v 2
= 2g s.
I f we make v = u, t h e n s = £ y >£>.
e e t
A t t h e t e m p e r a t u r e o f m e l t i n g i c e 4? = 26,214 f if ™ e
-
f o r c e o f g r a v i t y is 3 2 2 .
A t the same temperature t h e v e l o c i t y o f s o u n d in air is
1,090 f e e t p e r s e c o n d b y e x p e r i m e n t .
The square o f this is 1,188,100, w h e r e a s t h e square of
the velocity due to half the height o f the homogeneous

Velocity of Sound. 229
a t m o s p h e r e is 843,821. Hence by means o f the known
v e l o c i t y o f s o u n d w e c a n d e t e r m i n e 7, t h e r a t i o o f 1,188,100
t o 843,821, to b e 1-408.
T h e h e i g h t o f t h e h o m o g e n e o u s a t m o s p h e r e is p r o p o r t i o n a l
to the t e m p e r a t u r e r e c k o n e d f r o m a b s o l u t e z e r o . H e n c e the
v e l o c i t y o f s o u n d is p r o p o r t i o n a l t o t h e square r o o t o f the
absolute temperature. I n several o f the m o r e perfect gases
the v a l u e o f y s e e m s t o b e n e a r l y t h e s a m e as i n air. Hence
in t h o s e g a s e s t h e v e l o c i t y o f s o u n d is i n v e r s e l y as t h e s q u a r e
r o o t o f t h e i r s p e c i f i c g r a v i t y c o m p a r e d w i t h air.
This investigation w o u l d b e perfectly accurate, howevet
great the c h a n g e s o f pressure a n d d e n s i t y due t o the passage
o f the s o u n d - w a v e , p r o v i d e d t h e s u b s t a n c e is s u c h t h a t i n t h e
actual c h a n g e s o f p r e s s u r e a n d v o l u m e t h e q u a n t i t y
p + Q v 2
remains constant, Q b e i n g the v e l o c i t y o f p r o p a g a t i o n . In

all substances, as w e h a v e s e e n , w e m a y , w h e n t h e v a l u e s o f
/ and v are always v e r y near their m e a n values, assume a
v a l u e o f Q w h i c h s h a l l a p p r o x i m a t e l y satisfy this c o n d i t i o n ;
but in t h e c a s e o f v e r y v i o l e n t s o u n d s a n d o t h e r d i s t u r b a n c e s
o f the air t h e c h a n g e s o f p a n d v m a y b e s o g r e a t t h a t this
a p p r o x i m a t i o n c e a s e s t o b e n e a r t h e truth. To understand
what t a k e s p l a c e i n t h e s e c a s e s w e m u s t r e m e m b e r t h a t t h e
c h a n g e s ofp a n d v are n o t p r o p o r t i o n a l t o e a c h other, for in
a l m o s t all s u b s t a n c e s p i n c r e a s e s faster f o r a g i v e n d i m i n u t i o n
o f v as p i n c r e a s e s a n d v d i m i n i s h e s .
Hence Q, which represents the mass o f the substance
traversed b y the w a v e , will b e greater in those parts o f the
w a v e w h e r e t h e p r e s s u r e is g r e a t t h a n i n t h o s e p a r t s w h e r e
the p r e s s u r e is s m a l l ; t h a t is, t h e c o n d e n s e d p o r t i o n s o f t h e
w a v e will t r a v e l faster than the rarefied p o r t i o n s . T h e result
of this w i l l b e t h a t i f t h e w a v e o r i g i n a l l y c o n s i s t s o f a g r a d u a l
c o n d e n s a t i o n f o l l o w e d b y a g r a d u a l r a r e f a c t i o n , the c o n d e n
sation w i l l b e c o m e m o r e s u d d e n a n d the rarefaction m o r e
gradual as t h e w a v e a d v a n c e s t h r o u g h t h e air, i n t h e same

230 Radiation.
w a y a n d f o r n e a r l y t h e s a m e r e a s o n as t h e w a v e s o f the sea
on coming into shallow water b e c o m e steeper in front and
m o r e g e n t l y s l o p i n g b e h i n d , t i l l at l a s t t h e y c u r l o v e r o n the
shore.
F I G . 30.
C H A P T E R X V I .
ON RADIATION.
W E have already noticed some o f the p h e n o m e n a o f radia

t i o n , a n d h a v e s h o w n t h a t t h e y d o n o t p r o p e r l y b e l o n g t o the
science o f H e a t , and that t h e y should rather b e treated,
a l o n g w i t h s o u n d a n d l i g h t , as a b r a n c h o f t h e g r e a t s c i e n c e
of Radiation.
The phenomenon o f radiation consists i n t h e transmis
sion o f energy from o n e b o d y to another by propagation
through the intervening medium, in s u c h a w a y that the
p r o g r e s s o f t h e r a d i a t i o n m a y b e t r a c e d , after it has left the
first b o d y a n d b e f o r e it r e a c h e s t h e s e c o n d , t r a v e l l i n g through
the m e d i u m w i t h a certain v e l o c i t y , and l e a v i n g the medium
b e h i n d i t i n t h e c o n d i t i o n i n w h i c h i t f o u n d it.
W e h a v e already c o n s i d e r e d o n e instance o f radiation in
the case o f w a v e s o f sound. I n this c a s e t h e energy com
municated to the air b y a v i b r a t i n g body is propagated
7
through t h e air, a n d m a y finally set s o m e o t h e r b o d ) , as the
d r u m o f t h e ear, in m o t i o n . D u r i n g t h e p r o p a g a t i o n o f the
sound this e n e r g y e x i s t s in t h e p o r t i o n o f air t h r o u g h w h i c h
it is t r a v e l l i n g , p a r t l y i n t h e f o r m o f m o t i o n o f t h e air t o a n d

Radiation.
fro, a n d p a r t l y i n t h e f o r m o f c o n d e n s a t i o n and rarefaction.

T h e e n e r g y d u e t o s o u n d in t h e a i r is d i s t i n c t f r o m h e a t , b e -
cause it is p r o p a g a t e d i n a d e f i n i t e d i r e c t i o n , so that in a
certain t i m e i t w i l l h a v e e n t i r e l y left t h e p o r t i o n o f air u n d e r
consideration, and w i l l b e f o u n d i n a n o t h e r p o r t i o n o f air t o
w h i c h it has t r a v e l l e d . N o w h e a t n e v e r passes out o f a h o t
b o d y e x c e p t t o e n t e r a c o l d e r b o d y , s o that t h e energy o f
sound-waves, or any other f o r m o f e n e r g y w h i c h is p r o p a
g a t e d s o as t o p a s s w h o l l y o u t o f o n e p o r t i o n o f t h e m e d i u m
a n d i n t o a n o t h e r , c a n n o t b e c a l l e d heat.
There are, h o w e v e r , i m p o r t a n t thermal effects produced
b y r a d i a t i o n , so t h a t w e c a n n o t u n d e r s t a n d t h e s c i e n c e o f h e a t
without studying s o m e o f the p h e n o m e n a o f radiation.
When a b o d y is r a i s e d to a very high temperature it
b e c o m e s v i s i b l e i n t h e d a r k , a n d is s a i d t o shine, o r t o e m i t
light. T h e velocity o f propagation o f the light emitted b y
the sun a n d b y v e r y h o t b o d i e s h a s b e e n a p p r o x i m a t e l y m e a
sured, a n d is e s t i m a t e d t o b e b e t w e e n 180.000 a n d 192,000
miles p e r s e c o n d , o r a b o u t 900,000 t i m e s faster than sound
i n air.
T h e t i m e t a k e n b y t h e l i g h t in p a s s i n g f r o m o n e p l a c e to
a n o t h e r w i t h i n t h e l i m i t e d r a n g e w h i c h w e h a v e at o u r c o m
m a n d i n a l a b o r a t o r y is e x c e e d i n g l y s h o r t , a n d it is o n l y b y
m e a n s o f t h e m o s t r e f i n e d e x p e r i m e n t a l m e t h o d s t h a t it has
been measured. I t is certain, h o w e v e r , that there is an
interval o f time b e t w e e n the emission o f light b y one b o d y
a n d its r e c e p t i o n b y a n o t h e r , a n d that d u r i n g this t i m e t h e
energy transmitted from the one body to the other has
e x i s t e d in s o m e f o r m i n t h e i n t e r v e n i n g m e d i u m .
T h e opinions with regard to the relation between light
and heat h a v e suffered several alternations, according as
these a g e n t s w e r e r e g a r d e d as s u b s t a n c e s o r as accidents.
At one t i m e l i g h t w a s r e g a r d e d as a substance projected
from the luminous body, which, if the luminous body
were hot, m i g h t itself b e c o m e h o t l i k e a n y other substance.
H e a t w a s thus r e g a r d e d as a n a c c i d e n t o f t h e s u b s t a n c e l i g h t .

232 Radiation.
When the progress o f science had rendered the measure

m e n t o f q u a n t i t i e s o f h e a t as a c c u r a t e as t h e measurement
o f quantities o f gases, heat, under the n a m e o f c a l o r i c , was
p l a c e d i n t h e list o f s u b s t a n c e s . Afterwards, the independent
progress of optics l e d t o the rejection o f the corpuscular
t h e o r y o f light, and the establishment o f the undulatory
t h e o r y , a c c o r d i n g t o w h i c h l i g h t is a w a v e - l i k e m o t i o n o f a
m e d i u m already existing. T h e c a l o r i c t h e o r y o f heat, how
ever, still prevailed e v e n after the corpuscular theory of
light was rejected, s o t h a t h e a t a n d l i g h t s e e m e d a l m o s t to
have exchanged places.
W h e n the caloric theory o f heat w a s at l e n g t h demon
s t r a t e d t o b e false, t h e g r o u n d s o f t h e a r g u m e n t w e r e quite
i n d e p e n d e n t o f t h o s e w h i c h h a d b e e n u s e d i n t h e case o f
light.
We shall therefore consider the nature of radiation,
w h e t h e r o f light o r heat, in an independent m a n n e r , and
s h o w w h y w e b e l i e v e t h a t w h a t is c a l l e d r a d i a n t h e a t is the
same thing as w h a t is c a l l e d l i g h t , o n l y p e r c e i v e d b y us
through a different channel. The same radiation which
w h e n w e b e c o m e a w a r e o f it b y t h e e y e w e c a l l l i g h t , w h e n
we detect it b y a t h e r m o m e t e r o r b y t h e s e n s a t i o n o f heat
w e call radiant heat.
I n t h e first p l a c e , r a d i a n t h e a t a g r e e s w i t h l i g h t in always
m o v i n g in straight lines through a n y uniform m e d i u m . I t is
n o t , t h e r e f o r e , p r o p a g a t e d b y d i f f u s i o n , as i n t h e case o f the
c o n d u c t i o n o f h e a t , w h e r e t h e h e a t a l w a y s t r a v e l s f r o m hotter
to c o l d e r parts o f t h e m e d i u m in whatever d i r e c t i o n this
c o n d i t i o n m a y l e a d it.
The medium through which radiant heat passes is not
heated if perfectly diathermanous, any m o r e than a per
fectly transparent m e d i u m through which light passes is
rendered luminous. B u t i f a n y i m p u r i t y o r d e f e c t o f trans
p a r e n c y causes the m e d i u m to b e c o m e v i s i b l e w h e n light
passes through it, it w i l l a l s o c a u s e it t o b e c o m e h o t a n d to
s t o p p a r t o f t h e h e a t w h e n t r a v e r s e d b y r a d i a n t heat.

Light and Heat. 233
In the next place, radiant heat is reflected from the

p o l i s h e d surfaces o f b o d i e s a c c o r d i n g t o t h e s a m e l a w s as
light. A c o n c a v e m i r r o r c o l l e c t s t h e r a y s o f t h e sun i n t o a
brilliantly l u m i n o u s f o c u s . I f these c o l l e c t e d r a y s fall o n a
p i e c e o f w o o d , t h e y w i l l set i t o n fire. I f the luminous rays
are c o l l e c t e d b y m e a n s of a c o n v e x lens, similar heating
effects a r e p r o d u c e d , s h o w i n g t h a t r a d i a n t h e a t is r e f r a c t e d
w h e n it p a s s e s f r o m o n e t r a n s p a r e n t m e d i u m t o a n o t h e r .
W h e n l i g h t is r e f r a c t e d t h r o u g h a p r i s m , so as t o c h a n g e
its d i r e c t i o n t h r o u g h a c o n s i d e r a b l e a n g l e o f d e v i a t i o n , i t is
separated i n t o a series o f k i n d s o f light w h i c h are easily
distinguished from each other by their various colours.
T h e r a d i a n t h e a t w h i c h is r e f r a c t e d t h r o u g h t h e p r i s m is a l s o
spread out t h r o u g h a c o n s i d e r a b l e a n g u l a r r a n g e , w h i c h s h o w s
that i t a l s o c o n s i s t s o f radiations o f various kinds. The
luminosity o f the different radiations is e v i d e n t l y n o t i n t h e
s a m e p r o p o r t i o n as t h e i r h e a t i n g effects. F o r the b l u e a n d
g r e e n rays h a v e v e r y l i t t l e h e a t i n g p o w e r c o m p a r e d w i t h t h e
e x t r e m e r e d , w h i c h a r e m u c h less l u m i n o u s , a n d t h e h e a t i n g
rays a r e f o u n d far b e y o n d t h e e n d o f t h e r e d , w h e r e n o l i g h t
at all is v i s i b l e .
T h e r e are other m e t h o d s o f separating the different k i n d s
of light, w h i c h are s o m e t i m e s m o r e c o n v e n i e n t than the use
of a prism. Many substances are more transparent to
one kind o f light than another, and are therefore called
coloured media. Such media absorb certain rays and
transmit others. I f the light transmitted b y a stratum o f a
coloured m e d i u m afterwards passes through a n o t h e r stratum
o f the s a m e m e d i u m , it w i l l b e much less diminished in
intensity t h a n at first. F o r t h e k i n d o f l i g h t w h i c h is m o s t
absorbed b y the m e d i u m has b e e n already r e m o v e d , and
what is t r a n s m i t t e d b y t h e first s t r a t u m is t h a t w h i c h c a n p a s s
most r e a d i l y through t h e second. T h u s a v e r y thin stratum
of a solution o f b i c h r o m a t e o f potash cuts off the w h o l e o f
the s p e c t r u m f r o m t h e m i d d l e o f t h e g r e e n t o t h e v i o l e t , b u t
the r e m a i n d e r o f t h e light, consisting o f the red, orange,

234 Radiation.
y e l l o w , a n d p a r t o f t h e g r e e n , i s v e r y s l i g h t l y d i m i n i s h e d in
intensity b y passing through another s t r a t u m o f the same
medium.
If, h o w e v e r , the s e c o n d stratum b e c f a different m e d i u m ,
w h i c h absorbs m o s t o f the r a y s w h i c h t h e first t r a n s m i t s , it
w i l l cut off nearly the w h o l e l i g h t , t h o u g h it m a y b e itself
v e r y t r a n s p a r e n t f o r o t h e r r a y s a b s o r b e d b y t h e first m e d i u m .
T h u s a s t r a t u m o f s u l p h a t e o f c o p p e r a b s o r b s n e a r l y all t h e
rays transmitted b y the b i c h r o m a t e o f potash, e x c e p t a few
o f the g r e e n rays.
M e l l o n i found that different substances a b s o r b different
kinds o f radiant heat, and that the heat sifted b y a screen
of any substance will pass in greater proportion through
a screen o f the s a m e substance than unsifted heat, w h i l e it
m a y b e s t o p p e d i n g r e a t e r p r o p o r t i o n than unsifted heat b y
a screen o f a different substance.
T h e s e remarks m a y illustrate t h e g e n e r a l similarity b e t w e e n
light and radiant heat. W e must next consider the reasons
w h i c h i n d u c e us t o r e g a r d l i g h t as d e p e n d i n g o n a p a r t i c u l a r
kind of motion in the medium through which i t is pro
pagated. T h e s e reasons are principally d e r i v e d from the
p h e n o m e n a o f the interference o f light. T h e y are explained
m o r e a t l a r g e i n t r e a t i s e s o n l i g h t , b e c a u s e i t is m u c h easier
to o b s e r v e these p h e n o m e n a b y the e y e than b y a n y kind
of thermometer. W e shall t h e r e f o r e b e as b r i e f as p o s s i b l e .
T h e r e are various m e t h o d s b y w h i c h a b e a m o f light from
a small luminous object m a y b e divided into t w o portions,
w h i c h , after t r a v e l l i n g b y s l i g h t l y d i f f e r e n t p a t h s , finally fall
o n a w h i t e screen. W h e r e the t w o portions o f light overlap
e a c h other o n the screen, a series o f l o n g n a r r o w stripes m a y
be seen, alternately lighter and darker than the average
b r i g h t n e s s o f t h e s c r e e n n e a r t h e m , a n d w h e n w h i t e l i g h t is
used, these stripes are b o r d e r e d w i t h c o l o u r s . B y using light
o f o n e k i n d o n l y , s u c h as t h a t o b t a i n e d f r o m t h e s a l t e d w i c k
o f a spirit-lamp, a greater n u m b e r o f b a n d s or fringes may
b e seen, and a greater difference o f brightness b e t w e e n the

Interference. 235
light and the d a r k b a n d s . I f w e stop either o f the portions
of light into w h i c h t h e o r i g i n a l b e a m w a s d i v i d e d , t h e w h o l e ,
system o f bands disappears, s h o w i n g that t h e y are due,
not t o either o f t h e p o r t i o n s a l o n e , b u t t o b o t h u n i t e d .
I f w e n o w fix our attention o n o n e o f the dark bands, a n d
then cut o f f o n e o f t h e partial beams o f light, we shall
o b s e r v e that i n s t e a d o f a p p e a r i n g d a r k e r i t b e c o m e s a c t u a l l y
brighter, a n d i f w e a g a i n a l l o w t h e l i g h t t o fall o n t h e s c r e e n
it b e c o m e s d a r k a g a i n . H e n c e i t is p o s s i b l e to produce
darkness b y t h e a d d i t i o n o f t w o p o r t i o n s o f l i g h t I f light
is a substance, there cannot be another substance which
when a d d e d t o it shall p r o d u c e d a r k n e s s . W e are therefore
c o m p e l l e d t o a d m i t t h a t l i g h t is n o t a s u b s t a n c e .
N o w is t h e r e a n y o t h e r i n s t a n c e i n w h i c h t h e a d d i t i o n o f
two a p p a r e n t l y similar things diminishes t h e result ? We
know b y e x p e r i m e n t s w i t h m u s i c a l instruments that a c o m
bination o f t w o s o u n d s m a y p r o d u c e l e s s a u d i b l e effect t h a n
either s e p a r a t e l y , a n d it c a n b e s h o w n t h a t t h i s t a k e s p l a c e
when the o n e is h a l f a w a v e - l e n g t h i n a d v a n c e o f t h e other.
H e r e the m u t u a l a n n i h i l a t i o n o f t h e s o u n d s arises f r o m the
fact that a m o t i o n o f t h e air towards t h e e a r is t h e exact
opposite o f a m o t i o n a w a y f r o m t h e ear, a n d if the t w o in
struments a r e s o a r r a n g e d t h a t t h e m o t i o n s w h i c h t h e y tend
to p r o d u c e in t h e air near the ear are in o p p o s i t e d i r e c
tions a n d o f e q u a l m a g n i t u d e , t h e result w i l l b e n o m o t i o n
at all. N o w t h e r e is n o t h i n g absurd in o n e m o t i o n being
the e x a c t o p p o s i t e o f a n o t h e r , t h o u g h the supposition that
one s u b s t a n c e is t h e e x a c t o p p o s i t e o f a n o t h e r s u b s t a n c e , as
in s o m e f o r m s o f t h e T w o - F l u i d t h e o r y o f E l e c t r i c i t y , is a n
absurdity.
We may show the interference o f waves in a visible
manner b y d i p p i n g a t w o - p r o n g e d f o r k i n t o w a t e r o r m e r c u r y .
T h e waves which d i v e r g e from the t w o centres where the
prongs enter or leave the fluid are seen to produce a
greater d i s t u r b a n c e when they exactly coincide than w h e n
one gets a h e a d o f t h e o t h e r .

6 Radiation,
23
N o w i t is f o u n d , b y m e a s u r i n g t h e p o s i t i o n s o f t h e b r i g h t
and dark b a n d s o n the screen, that the difference of the
distances t r a v e l l e d b y the t w o portions o f l i g h t is f o r the
bright bands always an exact multiple o f a certain very
small distance w h i c h w e shall call a wave-length, whereas
for the dark bands i t is i n t e r m e d i a t e between two multi
ples o f the wave-length, being i ^ , z\, & c . , times that
length.
We therefore conclude that whatever exists or takes
p l a c e at a certain p o i n t i n a r a y o f light, then, at the same
i n s t a n t , a t a p o i n t at \ o r r^- o f t h e w a v e - l e n g t h i n a d v a n c e ,
s o m e t h i n g e x a c t l y t h e o p p o s i t e exists o r t a k e s p l a c e , s o that
in g o i n g a l o n g a ray w e find an alternation o f conditions
w h i c h w e m a y call positive and n e g a t i v e .
I n the ordinary statement o f the theory o f undulations
t h e s e c o n d i t i o n s are d e s c r i b e d as m o t i o n o f t h e m e d i u m i n
opposite directions. T h e essential character o f the theory
w o u l d r e m a i n the same i f w e w e r e to substitute for ordinary
motion to and fro any other succession of oppositely
directed conditions. Professor R a n k i n e has s u g g e s t e d o p
posite rotations o f m o l e c u l e s about their axes, a n d I have
suggested oppositely directed magnetizations and electro
m o t i v e forces ; but the a d o p t i o n o f either o f these hypotheses
w o u l d i n n o w a y a l t e r t h e e s s e n t i a l c h a r a c t e r o f the u n d u l a -
tory theory.
N o w i t is f o u n d t h a t i f a v e r y n a r r o w t h e r m o - e l e c t r i c p i l e
b e p l a c e d in t h e p o s i t i o n o f t h e screen, a n d m o v e d so that
s o m e t i m e s a b r i g h t b a n d a n d s o m e t i m e s a d a r k o n e falls on
the pile, the g a l v a n o m e t e r indicates that the pile receives
m o r e heat w h e n in the bright than w h e n in the dark band,
a n d t h a t w h e n o n e p o r t i o n o f t h e b e a m is c u t o f f t h e h e a t in
the d a r k b a n d is i n c r e a s e d . H e n c e in the interference o f
radiations the heating effect obeys the same l a w s as the
luminous effect.
Indeed, it has been found that e v e n w h e n the source
of radiation is a hot b o d y which emits n o l u m i n o u s rays,

Polarisation.
237
the phenomena of interference can be traced, showing
that t w o rays o f d a r k h e a t c a n i n t e r f e r e n o l e s s t h a n two
rays o f light. H e n c e all that w e h a v e said a b o u t the waves
of light is a p p l i c a b l e t o t h e h e a t - r a d i a t i o n , w h i c h is t h e r e f o r e
a series o f w a v e s .
It is also k n o w n i n t h e c a s e o f l i g h t t h a t after passing
through a p l a t e c u t from a crystal o f tourmaline parallel to
its axis t h e t r a n s m i t t e d b e a m c a n n o t pass through a s e c o n d
similarly cut p l a t e o f t o u r m a l i n e w h o s e a x i s is p e r p e n d i c u l a r
to that o f t h e first, t h o u g h i t c a n pass t h r o u g h it w h e n t h e a x i s
is in a n y o t h e r p o s i t i o n . Such a b e a m o f light, w h i c h has
different p r o p e r t i e s a c c o r d i n g as t h e s e c o n d p l a t e is t u r n e d
into different p o s i t i o n s r o u n d t h e b e a m as an a x i s , is c a l l e d
a polarized b e a m . T h e r e are m a n y other ways o f polarizing
a b e a m o f l i g h t , b u t t h e result is a l w a y s o f t h e s a m e k i n d .
N o w this p r o p e r t y o f p o l a r i z e d l i g h t s h o w s t h a t t h e motion
which c o n s t i t u t e s l i g h t c a n n o t b e i n the direction o f the
ray, for t h e n t h e r e c o u l d b e n o d i f f e r e n c e b e t w e e n d i f f e r e n t
sides o f t h e ray. T h e m o t i o n must b e transverse to the
d i r e c t i o n o f t h e r a y , s o that w e m a y n o w d e s c r i b e a r a y o f
p o l a r i z e d l i g h t as a c o n d i t i o n o f d i s t u r b a n c e i n a direction
at right a n g l e s t o t h e r a y p r o p a g a t e d t h r o u g h a m e d i u m , so
that the d i s t u r b a n c e i s i n o p p o s i t e d i r e c t i o n s at e v e r y h a l f
wave-length measured a l o n g t h e ray. Since Principal J . D .
Forbes s h o w e d that a ray o f dark heat can b e p o l a r i z e d , w e
can m a k e t h e s a m e a s s e r t i o n a b o u t t h e h e a t r a d i a t i o n .
L e t us n o w c o n s i d e r t h e consequences o f admitting that

what w e c a l l r a d i a t i o n , w h e t h e r o f heat, light, or i n v i s i b l e
rays w h i c h a c t o n c h e m i c a l p r e p a r a t i o n s , is o f t h e n a t u r e o f
a transverse u n d u l a t i o n i n a m e d i u m .
A transverse undulation is c o m p l e t e l y d e f i n e d w h e n we
know—
1. I t s w a v e - l e n g t h , o r t h e d i s t a n c e b e t w e e n t w o p l a c e s i n
w h i c h t h e d i s t u r b a n c e is i n t h e s a m e p h a s e .
2. I t s a m p l i t u d e , o r the greatest extent o f the disturb
ance.

23S Radiation.
3. T h e p l a n e in w h i c h t h e d i r e c t i o n o f t h e disturbance
lies.
4. T h e p h a s e o f t h e w a v e at a p a r t i c u l a r p o i n t .
5. T h e v e l o c i t y o f p r o p a g a t i o n t h r o u g h t h e m e d i u m .
W h e n w e k n o w these particulars about an undulation, it
is c o m p l e t e l y defined, and cannot b e a l t e r e d in any way
without changing s o m e o f these specifications.
N o w b y passing a b e a m consisting o f any assemblage o f
undulations t h r o u g h a prism, w e c a n separate it i n t o p o r t i o n s
a c c o r d i n g to their wave-lengths, a n d w e can select rays o f a
particular w a v e - l e n g t h for e x a m i n a t i o n . O f these w e may, b y
means of a plate o f tourmaline, select those whose plane of
p o l a r i z a t i o n is t h e p r i n c i p a l p l a n e o f t h e t o u r m a l i n e , b u t this
is u n n e c e s s a r y f o r o a r p u r p o s e . W e h a v e n o w g o t rays o f a
definite wave-length. Their velocity o f propagation depends
o n l y o n the nature o f the ray a n d o f the m e d i u m , so that w e
c a n n o t alter it at pleasure, a n d the phase c h a n g e s so r a p i d l y
( b i l l i o n s o f t i m e s in a s e c o n d ) t h a t it c a n n o t b e d i r e c t l y
observed. H e n c e the o n l y v a r i a b l e q u a n t i t y r e m a i n i n g is
the amplitude o f the disturbance, or, in other words, the
intensity o f the ray.
N o w the ray m a y b e o b s e r v e d in various ways. W e may,
i f it e x c i t e s t h e s e n s a t i o n o f s i g h t , r e c e i v e it i n t o our e y e . If
it affects c h e m i c a l c o m p o u n d s , w e m a y o b s e r v e its effect o n
them, or w e m a y r e c e i v e the ray o n a thermo-electric pile
a n d d e t e r m i n e its h e a t i n g effect.
B u t all these effects, b e i n g effects o f one and the same
t h i n g , m u s t rise a n d fall t o g e t h e r . A ray o f specified w a v e
length and specified plane o f polarization cannot be a
c o m b i n a t i o n o f s e v e r a l d i f f e r e n t t h i n g s , s u c h as a l i g h t - r a y , a
heat-ray, a n d an a c t i n i c ray. I t must b e one and the same
t h i n g , w h i c h has l u m i n o u s , t h e r m a l , a n d a c t i n i c effects, and
e v e r y t h i n g "which i n c r e a s e s o n e o f t h e s e effects m a s t i n c r e a s e
the others also.
T h e chief reason w h y so m u c h t h a t has b e e n w r i t t e n on
t h i s s u b j e c t is t a i n t e d w i t h t h e n o t i o n t h a t h e a t is o n e t h i n g

Light and Heat. 239
and l i g h t is a n o t h e r seems to be that the arrangements
for o p e r a t i n g on radiations o f a selected wave-length are
troublesome, and w h e n m i x e d radiations are e m p l o y e d , in
which the l u m i n o u s a n d t h e t h e r m a l effects are in different
proportions, anything which alters the proportion o f the
different r a d i a t i o n s i n t h e m i x t u r e a l t e r s a l s o t h e p r o p o r t i o n
of the r e s u l t i n g thermal and luminous effect, a s , i n d e e d it
g e n e r a l l y alters t h e c o l o u r o f t h e m i x e d l i g h t .
W e h a v e seen that the existence o f these radiations may
be detected in various w a y s — b y photographic preparations,
by the e y e , a n d b y the thermometer. T h e r e can b e no
doubt, h o w e v e r , as t o w h i c h o f t h e s e m e t h o d s g i v e s t h e true
measure o f the e n e r g y transmitted b y the radiation. This
is e x a c t l y m e a s u r e d b y the heating effect o f the ray w h e n
completely absorbed b y a n y substance.
W h e n t h e w a v e - l e n g t h is g r e a t e r t h a n 812 m i l l i o n t h s o f a
m i l l i m e t r e n o l u m i n o u s effect is p r o d u c e d o n t h e e y e , t h o u g h
the effect o n t h e t h e r m o m e t e r may be very great When
the w a v e - l e n g t h is 650 m i l l i o n t h s o f a m i l l i m e t r e t h e r a y is
visible as a r e d l i g h t , a n d a considerable heating effect is
observed. B u t w h e n t h e w a v e - l e n g t h is 500 m i l l i o n t h s o f a
m i l l i m e t r e , t h e r a y , w h i c h is s e e n as a b r i l l i a n t green, has
much less h e a t i n g effect t h a n t h e d a r k o r t h e r e d rays, a n d
it is difficult t o o b t a i n s t r o n g thermal effects w i t h r a y s o f
smaller w a v e - l e n g t h s , e v e n w h e n concentrated.
But, o n t h e o t h e r hand, the photographic effect o f the
radiation o n salts o f s i l v e r , w h i c h is v e r y f e e b l e i n t h e red
rays, a n d e v e n in the g r e e n rays, b e c o m e s m o r e p o w e r f u l
the s m a l l e r t h e w a v e - l e n g t h , t i l l f o r r a y s w h o s e w a v e - l e n g t h
is 400, w h i c h h a v e a f e e b l e violet luminosity and a still
feebler thermal effect, the photographic effect is very
powerful; a n d e v e n far b e y o n d t h e v i s i b l e s p e c t r u m , for w a v e
lengths o f less t h a n 200 m i l l i o n t h s o f a m i l l i m e t r e , w h i c h
are q u i t e i n v i s i b l e t o o u r e y e s a n d q u i t e u n d i s c o v e r a b l e b y
our t h e r m o m e t e r s , t h e p h o t o g r a p h i c effect is still o b s e r v e d .
This s h o w s t h a t n e i t h e r the l u m i n o u s n o r the photographic

Radiation.
•ZAP
e f f e c t is in a n y w a y p r o p o r t i o n a l t o t h e e n e r g y o f t h e radia
tion w h e n different kinds o f radiation are c o n c e r n e d . It
is p r o b a b l e that w h e n the radiation produces the photo
graphic effect i t is n o t b y its energy doing work on the
chemical c o m p o u n d , but rather b y a w e l l - t i m e d vibration of
the m o l e c u l e s d i s l o d g i n g t h e m f r o m the p o s i t i o n o f almost
indifferent equilibrium into which they h a d b e e n thrown by
p r e v i o u s c h e m i c a l m a n i p u l a t i o n s , a n d e n a b l i n g t h e m t o rush
together a c c o r d i n g t o their m o r e p e r m a n e n t affinities, so as
to f o r m stabler c o m p o u n d s . I n c a s e s o f t h i s k i n d t h e effect
is n o m o r e a d y n a m i c a l m e a s u r e o f t h e c a u s e t h a n t h e effect
of t h e fall o f a t r e e is a m e a s u r e o f t h e e n e r g y o f t h e w i n d
w h i c h u p r o o t e d it.
It is t r u e t h a t i n m a n y c a s e s t h e a m o u n t o f t h e radiation
m a y b e very accurately estimated b y m e a n s o f its c h e m i c a l
effects, e v e n w h e n t h e s e c h e m i c a l e f f e c t s t e n d to diminish
the intrinsic energy o f the system. But b y estimating the
h e a t i n g e f f e c t o f a r a d i a t i o n w h i c h is e n t i r e l y a b s o r b e d by
t h e h e a t e d b o d y w e o b t a i n a true m e a s u r e o f the e n e r g y of
the radiation. It is f o u n d that a surface thickly coated
with lampblack absorbs nearly the w h o l e o f e v e r y k i n d o f
r a d i a t i o n w h i c h falls o n it. H e n c e surfaces o f this k i n d a r e
of great value in the thermal study o f radiation.
We h a v e n o w to consider the conditions w h i c h determine
the a m o u n t and quality o f the radiation from a heated b o d y .
We must bear in m i n d that temperature is a p r o p e r t y o f
h o t b o d i e s a n d n o t o f r a d i a t i o n s , a n d t h a t q u a l i t i e s such as
wave-lengths, & c , b e l o n g to radiations, but n o t to the heat
w h i c h p r o d u c e s t h e m o r is p r o d u c e d b y t h e m .
o x PREVOST'S T H E O R Y O F E X C H A N G E S .
W h e n a s y s t e m o f b o d i e s at d i f f e r e n t t e m p e r a t u r e s is left
t o itself, t h e transfer o f h e a t w h i c h t a k e s p l a c e a l w a y s has
the effect o f rendering the temperatures o f the different
b o d i e s m o r e n e a r l y e q u a l , a n d this c h a r a c t e r o f the transfer

Theory of Exchanges. 241
o f heat, t h a t it passes f r o m h o t t e r t o c o l d e r b o d i e s , is the

same w h e t h e r i t is b y r a d i a t i o n o r b y c o n d u c t i o n t h a t t h e
transfer takes p l a c e .
Let us consider a number of bodies, a l l at t h e same
temperature, p l a c e d in a chamber t h e w a l l s o f w h i c h are
m a i n t a i n e d at that t e m p e r a t u r e , a n d t h r o u g h w h i c h n o heat
can pass by radiation (suppose the walls o f metal, for
instance). N o change o f temperature will occur in any o f
these b o d i e s . They will b e in thermal equilibrium with
each o t h e r a n d w i t h t h e w a l l s o f t h e c h a m b e r . T h i s is a
c o n s e q u e n c e o f t h e d e f i n i t i o n o f e q u a l t e m p e r a t u r e a t p . 32.
N o w if any o n e o f these bodies had been taken out o f
the c h a m b e r a n d p l a c e d a m o n g c o l d e r b o d i e s t h e r e would
be a transfer o f h e a t b y r a d i a t i o n f r o m t h e h o t b o d y t o the
colder o n e s ; o r i f a c o l d e r b o d y h a d b e e n i n t r o d u c e d i n t o
the c h a m b e r i t w o u l d i m m e d i a t e l y b e g i n t o r e c e i v e h e a t by
radiation f r o m the hotter b o d i e s r o u n d it. But the cold
b o d y has n o p o w e r o f a c t i n g d i r e c t l y o n t h e h o t b o d i e s at a
distance, so as t o c a u s e them to b e g i n to emit radiations,
nor has t h e h o t c h a m b e r a n y p o w e r , t o s t o p t h e r a d i a t i o n o f
any o n e o f t h e h o t b o d i e s p l a c e d w i t h i n it. W e therefore
c o n c l u d e w i t h P r e v o s t t h a t a h o t b o d y is a l w a y s e m i t t i n g
radiations, e v e n w h e n no c o l d e r b o d y is t h e r e to receive
them, a n d t h a t t h e reason w h y there is n o c h a n g e o f t e m
perature w h e n a b o d y is p l a c e d i n a c h a m b e r o f t h e same
temperature is t h a t i t r e c e i v e s f r o m t h e r a d i a t i o n o f t h e w a l l s
of the c h a m b e r e x a c t l y a s m u c h h e a t as it l o s e s b y r a d i a t i o n
towards t h e s e w a l l s .
I f this is t h e t r u e e x p l a n a t i o n o f t h e t h e r m a l equilibrium
of radiation, i t f o l l o w s t h a t i f t w o b o d i e s h a v e the same
temperature t h e r a d i a t i o n e m i t t e d b y t h e first a n d a b s o r b e d
by the s e c o n d is e q u a l i n a m o u n t to the radiation emitted
by the s e c o n d a n d absorbed b y t h e first d u r i n g t h e same
time.
The higher the temperature o f a b o d y , the g r e a t e r its
radiation is f o u n d t o b e , so t h a t w h e n t h e t e m p e r a t u r e s o f t h e
R

242 Radiation
bodies are unequal the hotter b o d i e s w i l l e m i t m o r e radia

tion than they r e c e i v e from the c o l d e r b o d i e s , a n d therefore,
o n the w h o l e , heat will b e lost b y the hotter a n d g a i n e d b y
the c o l d e r b o d i e s till t h e r m a l e q u i l i b r i u m is a t t a i n e d . We
shall r e t u r n t o t h e c o m p a r i s o n o f t h e r a d i a t i o n at different
t e m p e r a t u r e s after .we h a v e e x a m i n e d t h e r e l a t i o n s b e t w e e n
t h e r a d i a t i o n o f d i f f e r e n t b o d i e s at t h e s a m e temperature.
T h e a p p l i c a t i o n o f t h e t h e o r y o f e x c h a n g e s h a s at v a r i o u s
times been extended to the phenomena o f h e a t as they
w e r e successively investigated F o u r i e r has c o n s i d e r e d the
l a w o f radiation as d e p e n d i n g o n the a n g l e which the ray
makes with the surface, and Leslie has investigated its
relation to the state o f p o l i s h o f the surface ; b u t i t is in
recent times, and chiefly b y the researches o f B . Stewart,
Kirchhoff, and De la P r o v o s t a y c , that the theory o f ex
changes has been shown to b e applicable, not only to the
total amount o f the radiation, but to every distinction in
quality o f w h i c h t h e r a d i a t i o n is c a p a b l e .
For, b ) ' placing b e t w e e n t w o bodies o f the same tempera
t u r e a c o n t r i v a n c e s u c h as t h a t a l r e a d y n o t i c e d at p . 218, so
that o n l y radiations of a determinate w a v e - l e n g t h a n d in a
d e t e r m i n a t e p l a n e can pass f r o m the o n e b o d y t o the other,
w e reduce the general proposition about thermal equilibrium
to a p r o p o s i t i o n about this particular k i n d o f radiation. We
m a y therefore transform it i n t o the following m o r e definite
proposition.
I f t w o b o d i e s are at the same temperature, the radiation
e m i t t e d b y t h e first a n d a b s o r b e d b y the second agrees with
the radiation emitted b y the s e c o n d and absorbed b y the
first, n o t o n l y i n its t o t a l h e a t i n g e f f e c t , b u t i n t h e i n t e n s i t y ,
wave-length, and plane o f polarization o f every component
part o f either radiation. A n d the l a w that the amount o f
radiation increases w i t h t h e t e m p e r a t u r e m u s t b e true, n o t
o n l y f o r t h e w h o l e r a d i a t i o n , b u t f o r a l l t h e c o m p o n e n t parts
o f it w h e n a n a l y s e d a c c o r d i n g t o their wave-lengths and
planes o f polarization.

and A bsorption. 243
T h e c o n s e q u e n c e s o f t h e s e t w o p r o p o s i t i o n s , a p p l y i n g as
they d o t o e v e r y k i n d o f r a d i a t i o n , w h e t h e r d e t e c t e d b y its
thermal or b y its l u m i n o u s effects, a r e s o n u m e r o u s and
varied that w e c a n n o t a t t e m p t a n y full e n u m e r a t i o n o f t h e m
in this treatise. W e must confine ourselves to a few ex
amples.
W h e n a r a d i a t i o n falls o n a b o d y , p a r t o f i t is r e f l e c t e d ,
and part enters t h e b o d y . T h e latter part again m a y either
he w h o l l y a b s o r b e d b y the b o d y or partly absorbed and
partly t r a n s m i t t e d .
N o w l a m p b l a c k reflects h a r d l y a n y o f the radiation w h i c h
falls on it, a n d it transmits none. Nearly the whole is
absorbed.
Polished silver reflects nearly the w h o l e o f the radiation
which falls u p o n it, a b s o r b i n g o n l y a b o u t a f o r t i e t h p a r t , a n d
transmitting n o n e .
R o c k salt r e f l e c t s l e s s t h a n a t w e l f t h p a r t o f t h e radiation
which falls o n i t ; it a b s o r b s h a r d l y a n y , a n d t r a n s m i t s n i n e t y -
two p e r c e n t .
T h e s e t h r e e s u b s t a n c e s , t h e r e f o r e , m a y b e t a k e n as t y p e s o f
absorption, r e f l e x i o n , a n d t r a n s m i s s i o n r e s p e c t i v e l y .
L e t us s u p p o s e that t h e s e p r o p e r t i e s h a v e b e e n o b s e r v e d
in these s u b s t a n c e s at t h e t e m p e r a t u r e , say, o f 212° F . , a n d
let t h e m b e p l a c e d a t this t e m p e r a t u r e within a chamber
whose w a l l s a r e at t h e s a m e t e m p e r a t u r e . T h e n the amount
of the r a d i a t i o n f r o m t h e l a m p b l a c k w h i c h is a b s o r b e d b y
the o t h e r t w o s u b s t a n c e s is, as w e h a v e seen, v e r y s m a l l .
N o w the l a m p b l a c k a b s o r b s t h e w h o l e o f the r a d i a t i o n f r o m
the silver o r t h e salt. H e n c e the radiation from these
substances m u s t a l s o b e s m a l l , o r , m o r e p r e c i s e l y —
The radiation of a substance at a given temperature is to
the radiation of lampblack at that temperature as the amount
of radiation absorbed by the substance at that temperature is to
the whole radiation which falls upon it.
H e n c e a b o d y w h o s e surface is m a d e o f p o l i s h e d s i l v e r
will e m i t a m u c h smaller amount o f radiation than one
R 2
244 Radiation
w h o s e surface is o f l a m p b l a c k . T h e b r i g h t e r t h e surface o f
a s i l v e r t e a p o t , t h e l o n g e r w i l l it r e t a i n t h e h e a t o f t h e t e a ;
a n d if o n t h e surface o f a m e t a l p l a t e s o m e p a r t s a r e p o l i s h e d ,
o t h e r s r o u g h , a n d o t h e r s b l a c k e n e d , w h e n t h e p l a t e is m a d e
r e d h o t t h e b l a c k e n e d parts w i l l a p p e a r b r i g h t e s t , t h e r o u g h
parts n o t s o b r i g h t , a n d t h e p o l i s h e d p a r t s d a r k e s t . T h i s is
w e l l s e e n w h e n m e l t e d l e a d is m a d e red hot. W h e n part
o f t h e d r o s s is r e m o v e d , t h e p o l i s h e d surface o f t h e m e l t e d
m e t a l , t h o u g h r e a l l y h o t t e r t h a n t h e d r o s s , a p p e a r s o f a less
brilliant red.
A p i e c e o f g l a s s w h e n t a k e n r e d h o t o u t o f t h e fire a p p e a r s
o f a v e r y faint r e d c o m p a r e d w i t h a p i e c e o f i r o n t a k e n f r o m
t h e s a m e p a r t o f t h e fire, t h o u g h t h e glass is r e a l l y h o t t e r
than t h e i r o n , b e c a u s e i t d o e s n o t t h r o w o f f its h e a t s o fast.
A i r o r a n y other transparent gas, e v e n w h e n raised to a
heat at w h i c h o p a q u e b o d i e s appear w h i t e hot, emits so little
light that its luminosity can hardly b e o b s e r v e d in the
d a r k , at l e a s t w h e n t h e t h i c k n e s s o f t h e h e a t e d air is n o t
very great.
Again, w h e n a s u b s t a n c e at a g i v e n t e m p e r a t u r e absorbs
c e r t a i n k i n d s o f r a d i a t i o n a n d t r a n s m i t s o t h e r s , i t e m i t s at
that temperature o n l y those kinds o f radiation w h i c h it
absorbs. A v e r y r e m a r k a b l e i n s t a n c e o f this is o b s e r v e d in
the vapour o f sodium. T h i s substance w h e n h e a t e d emits
r a y s o f t w o d e f i n i t e k i n d s , w h o s e w a v e - l e n g t h s a r e O'ooo5go53
and o'ooo58g89 millimetre respectively. T h e s e rays are
visible, a n d m a y b e seen in the f o r m o f t w o bright lines b y
directing a spectroscope u p o n a flame in w h i c h any com
p o u n d o f s o d i u m is p r e s e n t .
N o w i f t h e l i g h t e m i t t e d f r o m an intensely heated solid
b o d y , s u c h as a p i e c e o f l i m e i n t h e o x y h y d r o g e n l i g h t , b e
transmitted through sodium-vapour at a temperature lower
than that o f the lime, and then analysed b y the spectro
scope, t w o dark lines are seen, corresponding to the two
bright ones formerly o b s e r v e d , s h o w i n g that sodium-vapour
absorbs the s a m e definite kinds o f light w h i c h it radiates.

as dependi?ig on Temperature. 245
I f the t e m p e r a t u r e o f t h e s o d i u m - v a p o u r is r a i s e d , say by-
using a B u n s e n ' s b u r n e r i n s t e a d o f a spirit-lamp to p r o d u c e
it, or if the temperature o f t h e l i m e is l o w e r e d till i t is
the s a m e as t h a t o f t h e v a p o u r , the dark lines disappear,
because the s o d i u m - v a p o u r n o w radiates e x a c t l y as much
light as it a b s o r b s from the l i g h t o f t h e l i m e - b a l l at the
same t e m p e r a t u r e . I f the s o d i u m - f l a m e is h o t t e r than the
lime-ball the lines a p p e a r bright.
T h i s is a n illustration o f Kirchhoff's principle, that the
radiation o f e v e r y k i n d i n c r e a s e s as t h e t e m p e r a t u r e rises.
I n p e r f o r m i n g this e x p e r i m e n t w e suppose the light from
the l i m e - b a l l t o pass through the s o d i u m - f l a m e b e f o r e it
reaches t h e slit o f t h e s p e c t r o s c o p e . If, h o w e v e r , t h e flame
is i n t e r p o s e d b e t w e e n t h e slit a n d t h e e y e , o r t h e s c r e e n o n
which the s p e c t r u m is p r o j e c t e d , t h e d a r k l i n e s m a y b e s e e n
distinctly, e v e n w h e n t h e t e m p e r a t u r e o f t h e s o d i u m - f l a m e is
higher than that o f t h e l i m e - b a l l . F o r in t h e parts o f the
spectrum n e a r t h e l i l i e s t h e l i g h t is n o w c o m p o u n d e d o f t h e
analysed light o f the lime-ball and the direct light o f the
sodium-flame, w h i l e a t t h e l i n e s t h e m s e l v e s t h e l i g h t o f t h e
spectrum o f t h e l i m e - b a l l is c u t off, a n d o n l y t h e d i r e c t l i g h t
of the s o d i u m - f l a m e r e m a i n s , s o that t h e l i n e s a p p e a r darker
than the rest o f t h e f i e l d .
I t d o e s n o t b e l o n g t o t h e s c o p e o f this t r e a t i s e t o a t t e m p t
to g o o v e r t h e i m m e n s e field o f research w h i c h has been
opened up b y the application o f the spectroscope t o dis
tinguish d i f f e r e n t i n c a n d e s c e n t v a p o u r s , a n d w h i c h has l e d
to a great increase of our knowledge of the heavenly
bodies.
If the thickness of a m e d i u m , s u c h as sodium-vapour,
which r a d i a t e ; and absorbs definite kinds o f light, b e v e r y
great, the whole b e i n g at a high temperature, the light
emitted will b e o f e x a c t l y the same c o m p o s i t i o n as that
emitted from lampblack at the same temperature. For,
ttioug'ti some kinds o f radiation are much more feebly
emitted by the substance than others, these are also so

246 Radiation.
f e e b l y a b s o r b e d that t h e y can r e a c h the surface f r o m im
mense depths, whereas the rays which are so copiously
radiated are a l s o s o r a p i d l y a b s o r b e d t h a t i t is o n l y from
p l a c e s v e r y near the surface that they can escape out o f the
medium. H e n c e both the depth and the d e n s i t y o f an
incandescent g a s c a u s e its r a d i a t i o n t o a s s u m e more and
m o r e o f the character o f a continuous spectrum.
W h e n t h e t e m p e r a t u r e o f a s u b s t a n c e is g r a d u a l l y r a i s e d ,
n o t o n l y does the intensity o f e v e r y particular k i n d o f radia
tion increase, but n e w kinds of radiation are produced.
Bodies o f l o w temperature e m i t o n l y rays o f great wave
length. As the temperature rises these rays are more
copiously emitted, but at t h e same time other rays of
smaller wave-length m a k e their appearance. W h e n the tem
p e r a t u r e has r i s e n t o a c e r t a i n p o i n t , p a r t o f t h e r a d i a t i o n is
l u m i n o u s a n d o f a r e d colour, the l u m i n o u s rays o f greatest
wave-length being red. A s t h e t e m p e r a t u r e rises, t h e o t h e r
l u m i n o u s rays a p p e a r i n the o r d e r o f the spectrum, but e v e r y
rise o f temperature increases the intensity o f all the rays
w h i c h h a v e already m a d e their appearance. A white-hot
b o d y emits m o r e r e d rays than a r e d - h o t b o d y , a n d more
non-luminous rays than a n y n o n - l u m i n o u s b o d y .
The t o t a l t h e r m a l v a l u e o f t h e r a d i a t i o n at a n y t e m p e r a
t u r e , d e p e n d i n g as it d o e s u p o n t h e a m o u n t o f a l l t h e d i f f e r e n t
k i n d s o f r a y s o f w h i c h i t is c o m p o s e d , is n o t l i k e l y t o b e a
simple function o f the temperature. Nevertheless, Dulong
a n d P e t i t succeeded in obtaining a formula w h i c h expresses
t h e facts o b s e r v e d b y t h e m w i t h t o l e r a b l e e x a c t n e s s . I t is
of the form
R = m a, 9
w h e r e R is t h e t o t a l l o s s o f h e a t in unit o f t i m e b y radia
t i o n f r o m u n i t o f a r e a o f t h e surface o f t h e s u b s t a n c e at the
t e m p e r a t u r e 8, m is a c o n s t a n t quantity depending only on
the substance a n d the nature o f its surface, and a is a
numerical quantity which, w h e n R expresses the temperature
,
o n t h e C e n t i g r a d e s c a l e , is i o o 7 7 .

Total Quantity of Radiation. ' 247
I f the b o d y is p l a c e d i n a c h a m b e r d e v o i d of air, w h o s e
walls a r e at t h e t e m p e r a t u r e t, t h e n t h e heat radiated from
the w a l l s to t h e b o d y a n d a b s o r b e d b y i t w i l l b e
r — ma',
so that t h e a c t u a l l o s s o f h e a t w i l l b e
R—r = m a 6
— m a'.
T h e c o n s t a n c y of t h e a m o u n t o f r a d i a t i o n b e t w e e n t h e s a m e
surfaces at t h e s a m e t e m p e r a t u r e s affords a v e r y c o n v e n i e n t
method o f c o m p a r i n g quantities of heat This method was
r e f e r r e d t o i n o u r c h a p t e r o n C a l o r i m e t r y ( p . 74), under the
name of the M e t h o d o f C o o l i n g .
The s u b s t a n c e t o b e e x a m i n e d is h e a t e d a n d p u t i n t o a
thin c o p p e r v e s s e l , t h e o u t e r s u r f a c e o f w h i c h is b l a c k e n e d ,
or at l e a s t is p r e s e r v e d i n t h e s a m e s t a t e of r o u g h n e s s o r o f
polish t h r o u g h o u t the experiments. T h i s v e s s e l is p l a c e d
in a l a r g e r c o p p e r v e s s e l so as n o t t o t o u c h it, a n d t h e o u t e r
vessel is p l a c e d i n a b a t h o f w a t e r k e p t at a c o n s t a n t t e m
perature. T h e temperature o f the substance in the smaller
vessel is o b s e r v e d f r o m t i m e t o t i m e , or, still b e t t e r , t h e t i m e s
are o b s e r v e d at w h i c h the reading of a thermometer im
m e r s e d i n t h e s u b s t a n c e is a n e x a c t n u m b e r o f d e g r e e s . In
this w a y t h e t i m e o f c o o l i n g , say f r o m 100° t o 9 0 ° , f r o m 9 0 °
t o 80°, is r e g i s t e r e d , t h e t e m p e r a t u r e o f t h e o u t e r v e s s e l b e i n g
kept always the same.
Suppose t h a t this o b s e r v a t i o n o f t h e t i m e o f c o o l i n g is
m a d e first w h e n t h e v e s s e l is filled with water, and then
w h e n s o m e o t h e r s u b s t a n c e is p u t i n t o it. T h e rate at w h i c h
heat e s c a p e s b y r a d i a t i o n is t h e s a m e f o r t h e s a m e tempera
ture in both experiments. The quantity o f heat which
escapes d u r i n g t h e c o o l i n g , say f r o m 100° t o 90", in the t w o
e x p e r i m e n t s , is p r o p o r t i o n a l t o t h e t i m e o f c o o l i n g . Hence
the c a p a c i t y o f t h e v e s s e l a n d its c o n t e n t s i n the first e x p e r i
m e n t is t o its c a p a c i t y i n t h e s e c o n d e x p e r i m e n t as the time
0
of c o o l i n g f r o m 100° t o 9 0 i n t h e first e x p e r i m e n t is t o t h e
c
time o f c o o l i n g f r o m 100° t o g o in t h e s e c o n d experiment.

248 Radiation
T h e m e t h o d o f c o o l i n g is v e r y c o n v e n i e n t i n c e r t a i n cases,
b u t i t is n e c e s s a r y t o k e e p t h e t e m p e r a t u r e o f t h e w h o l e o f
t h e s u b s t a n c e i n t h e i n n e r v e s s e l a s n e a r l y u n i f o r m as p o s s i b l e ,
so that the m e t h o d must b e restricted to liquids w h i c h w e
can stir, and to solids w h o s e c o n d u c t i v i t y is g r e a t , and
w h i c h m a y b e cut i n p i e c e s a n d i m m e r s e d i n a l i q u i d .
The m e t h o d o f c o o l i n g has b e e n f o u n d v e r y a p p l i c a b l e to
the measurement of the quantity o f heat c o n d u c t e d through
a substance. ( S e e the chapter on C o n d u c t i o n . )
EFFECT OF RADIATION ON THERMOMETERS.
O n a c c o u n t o f the radiation passing in all d i r e c t i o n s t h r o u g h

t h e a t m o s p h e r e , i t i s a v e r y difficult t h i n g t o d e t e r m i n e the
true temperature o f the air i n a n y p l a c e o u t o f d o o r s by
means o f a thermometer.
I f the sun s h i n e s o n the thermometer, t h e r e a d i n g is o f
c o u r s e t o o h i g h ; b u t i f w e p u t it i n t h e s h a d e , i t m a y b e t o o
low, because the thermometer m a y b e emitting m o r e radia
t i o n t h a n i t r e c e i v e s f r o m t h e c l e a r sky. T h e ground, walls
o f houses, clouds, a n d the various d e v i c e s for shielding the
thermometer from radiation, may all b e c o m e sources of
error, b y causing an u n k n o w n amount o f radiation on the
bulb. F o r rough purposes the effects o f radiation may be
greatly r e m o v e d b y giving the bulb a surface o f p o l i s h e d
s i l v e r , o f w h i c h , as w e h a v e s e e n , t h e a b s o r p t i o n is o n l y a
fortieth o f that o f l a m p b l a c k .
A m e t h o d described b y D r . Joule in a communication to
t h e P h i l o s o p h i c a l S o c i e t y o f M a n c h e s t e r , N o v e m b e r 26, 1867,
s e e m s t h e o n l y o n e free f r o m all o b j e c t i o n s . T h e thermo
m e t e r is p l a c e d i n a l o n g v e r t i c a l c o p p e r t u b e o p e n at b o t h
ends, but with a cap to close the lower end, which may be
r e m o v e d or p u t o n w i t h o u t w a r m i n g it b y the h a n d . What
e v e r r a d i a t i o n a f f e c t s t h e t h e r m o m e t e r m u s t b e b e t w e e n it
and the inside o f the tube, and i f these are o f the same

as affecting Thermometers. 249
temperature, t h e r a d i a t i o n w i l l h a v e n o e f f e c t o n t h e o b s e r v e d
reading o f the t h e r m o m e t e r . H e n c e , i f w e c a n b e sure t h a t
the c o p p e r t u b e a n d t h e air w i t h i n i t a r e at t h e temperature
o f the a t m o s p h e r e , a n d t h a t t h e t h e r m o m e t e r is i n thermal
equilibrium, the t h e r m o m e t e r reading w i l l b e the true t e m
perature.
N o w , i f the a i r w i t h i n t h e t u b e is o f t h e s a m e temperature
as t h e air o u t s i d e , i t w i l l b e o f t h e s a m e d e n s i t y , a n d i t w i l l
therefore b e i n s t a t i c a l e q u i l i b r i u m w i t h it. I f i t is w a r m e r
it will b e l i g h t e r , a n d a n u p w a r d c u r r e n t will b e formed in
the tube w h e n t h e c a p is r e m o v e d . I f i t is c o l d e r , a d o w n
w a r d current w i l l b e f o r m e d .
T o d e t e c t t h e s e c u r r e n t s a s p i r a l w i r e is s u s p e n d e d i n t h e
tube b y a fine fibre, s o t h a t a n u p w a r d o r d o w n w a r d c u r r e n t
causes t h e spiral t o t w i s t t h e f i b r e , a n d a n y m o t i o n o f the
spiral is m a d e a p p a r e n t b y m e a n s o f a s m a l l m i r r o r a t t a c h e d
to it.
T o v a r y t h e t e m p e r a t u r e o f t h e c o p p e r t u b e , it is e n c l o s e d
in a w i d e r t u b e , so that w a t e r m a y b e p l a c e d in the space
b e t w e e n t h e t u b e s , a n d b y p o u r i n g in w a r m e r o r c o o l e r w a t e r
the t e m p e r a t u r e m a y b e a d j u s t e d till t h e r e is n o current.
We then k n o w t h a t t h e a i r is o f t h e s a m e temperature
within t h e t u b e a s i t is w i t h o u t B u t w e k n o w that the
tube is a l s o o f t h e s a m e t e m p e r a t u r e as t h e air, f o r i f it
w e r e n o t it w o u l d h e a t o r cool the a i r a n d p r o d u c e a cur
rent. Finally, w e k n o w that the thermometer, if stationary,
is at the t e m p e r a t u r e o f t h e a t m o s p h e r e ; for t h e a i r in c o n t a c t
with it, a n d t h e s i d e s o f t h e t u b e , which alone can exchange
radiations w i t h it, h a v e t h e s a m e t e m p e r a t u r e as t h e atmo
sphere.

250 Convection.
C H A P T E R XVII.
ON CONVECTION CURRENTS.
W H E N t h e a p p l i c a t i o n o f h e a t t o a fluid c a u s e s i t t o e x p a n d
o r t o c o n t r a c t , it is t h e r e b y r e n d e r e d r a r e r o r d e n s e r t h a n the
neighbouring parts o f the fluid ; a n d i f t h e f l u i d is at the
s a m e t i m e a c t e d o n b y g r a v i t y , it t e n d s t o f o r m a n u p w a r d
o r d o w n w a r d c u r r e n t o f t h e h e a t e d fluid, w h i c h is o f c o u r s e
a c c o m p a n i e d with a current o f the m o r e r e m o t e parts o f the
fluid in the opposite direction. T h e fluid is t h u s m a d e t o
c i r c u l a t e , fresh p o r t i o n s o f fluid a r e b r o u g h t i n t o t h e n e i g h
bourhood o f the source o f heat, and these when heated
travel, carrying their heat with them into other regions.
S u c h c u r r e n t s , c a u s e d b y t h e a p p l i c a t i o n o f h e a t , a n d carry
i n g this h e a t with them, are called convection currents.
T h e y play a most important part in natural p h e n o m e n a , b y
causing a much m o r e rapid diffusion o f h e a t than w o u l d
t a k e p l a c e b y c o n d u c t i o n a l o n e in t h e s a m e m e d i u m i f re
strained from moving. T h e actual diffusion o f heat from
o n e part o f the fluid t o another takes p l a c e , o f course, by
c o n d u c t i o n ; but, o n a c c o u n t o f t h e m o t i o n o f t h e fluid, the
i s o t h e r m a l surfaces a r e s o e x t e n d e d , a n d i n s o m e c a s e s c o n
torted, that their areas are g r e a t l y i n c r e a s e d w h i l e t h e dis
tances b e t w e e n t h e m are d i m i n i s h e d , so that true conduction
goes on much more rapidly than if the m e d i u m w e r e at
rest.
C o n v e c t i o n currents d e p e n d o n changes o f density in a

fluid acted on b y gravity. I f the action o f heat does not
produce a change o f d e n s i t y , as in t h e c a s e o f w a t e r at a
temperature of about 39° F . , n o c o n v e c t i o n current will be
produced. I f t h e fluid is n o t a c t e d o n b y g r a v i t y , as w o u l d

Production of Currents. 251
b e the c a s e i f t h e fluid w e r e r e m o v e d t o a sufficient d i s t a n c e
from t h e e a r t h a n d o t h e r g r e a t b o d i e s , n o c o n v e c t i o n cur
rents would be formed. A s this c o n d i t i o n is n o t easily-
realised, w e m a y t a k e t h e case o f a vessel c o n t a i n i n g fluid,
and d e s c e n d i n g a c c o r d i n g t o t h e l a w o f m o r i o n o f a b o d y
falling freely. T h e pressure in this fluid will b e the same
in every part, a n d a c h a n g e o f density in a n y p a r t o f the
fluid w i l l n o t o c c a s i o n c o n v e c t i o n c u r r e n t s .
When w e wish to avoid the formation of convection
currents w e m u s t arrange matters so t h a t d u r i n g t h e whole
course o f the experiment the density o f each horizontal
stratum is t h e s a m e t h r o u g h o u t , a n d t h a t t h e d e n s i t y i n c r e a s e s
with t h e d e p t h . If, for instance, w e are studying the c o n
duction o f heat i n a fluid which expands w h e n heated, w e
must m a k e t h e h e a t flow d o w n w a r d s t h r o u g h t h e fluid. If
w e w i s h t o d e t e r m i n e t h e l a w o f diffusion o f fluids w e m u s t
p l a c e t h e d e n s e r fluid u n d e r n e a t h t h e rarer o n e .
C o n v e c t i o n currents are p r o d u c e d b y changes o f density
arising f r o m o t h e r c a u s e s . T h u s if a crystal of a soluble
salt b e s u s p e n d e d in a v e s s e l o f w a t e r , t h e w a t e r i n c o n t a c t
w i t h t h e c r y s t a l w i l l d i s s o l v e a p o r t i o n o f it, a n d , b e c o m i n g
denser, w i l l b e g i n t o sink, a n d its p l a c e w i l l b e s u p p l i e d b y
fresh w a t e r . T h u s a c o n v e c t i o n current will be formed, a
solution o f t h e salt w i l l d e s c e n d f r o m t h e c r y s t a l , a n d this
will cause a n u p w a r d c u r r e n t o f purer water, and a circula
tion w i l l b e k e p t u p till e i t h e r t h e c r y s t a l is e n t i r e l y d i s s o l v e d ,
or the l i q u i d h a s b e c o m e s a t u r a t e d w i t h t h e salt u p t o t h e
level o f the t o p o f the crystal. I n this c a s e i t is t h e salt
w h i c h is c a r r i e d t h r o u g h t h e l i q u i d b y c o n v e c t i o n .
A c o n v e c t i o n current m a y b e p r o d u c e d in w h i c h electricity
is the t h i n g c a r r i e d . I f a c o n d u c t o r terminating in a fine
p o i n t is s t r o n g l y e l e c t r i f i e d , t h e p a r t i c l e s o f air n e a r t h e p o i n t
will b e c h a r g e d w i t h e l e c t r i c i t y , a n d then urged from the
p o i n t t o w a r d s a n y surface o p p o s i t e l y e l e c t r i f i e d . A current
of e l e c t r i f i e d air is thus f o r m e d , w h i c h diffuses i t s e l f about
the r o o m , a n d g e n e r a l l y r e a c h e s t h e w a l l s , w h e r e t h e e l e c t r i f i e d

252 Convection.
air c l i n g s t o t h e o p p o s i t e l y e l e c t r i f i e d w a l l , a n d is s o m e t i m e s
n o t discharged for a l o n g time.
The method o f determining b y c o n v e c t i o n currents the
t e m p e r a t u r e at w h i c h w a t e r has its m a x i m u m d e n s i t y s e e m s
to have been first e m p l o y e d b y Hope. He cooled the
m i d d l e p a r t o f a t a l l v e s s e l o f w a t e r b y s u r r o u n d i n g this p a r t
o f the vessel with a freezing mixture. A s l o n g as t h e t e m p e
r a t u r e is a b o v e 4 0 ° F . t h e c o o l e d w a t e r d e s c e n d s , a n d c a u s e s
a fall o f t e m p e r a t u r e i n a t h e r m o m e t e r p l a c e d i n t h e l o w e r
part o f the vessel. A n o t h e r thermometer, placed in the
upper part o f the vessel, remains stationary. But when the
0
t e m p e r a t u r e is b e l o w 39 F . the water c o o l e d b y the freezing
mixture b e c o m e s lighter and ascends, causing the upper
thermometer to fall, while the lower one remains star
tionary.
T h e investigation o f the m a x i m u m density o f water has
been greatly improved b y Joule, w h o also
made use o f c o n v e c t i o n currents. H e em
ployed a vessel consisting of two vertical
cylinders, each 4^ feet high and 6 inches
diameter, connected below by a wide tube
with a cock, and a b o v e by an open trough
or c h a n n e l . T h e w h o l e was filled with water
u p t o such a l e v e l that t h e water could flow
freely through the channel. A glass specific
g r a v i t y b e a d w h i c h w o u l d just float i n water
was p l a c e d in the channel, and served to
indicate any motion o f the water in the
channel. The very smallest difference of
d e n s i t y b e t w e e n t h e p o r t i o n s o f w a t e r in t h e
two columns was sufficient to produce a
current, and to move the bead in the
channel.
The c o c k in the connecting tube being

closed, the t e m p e r a t u r e o f t h e w a t e r in t h e t w o t u b e s w a s
adjusted, the water well m i x e d in each tube by stirring,

Maximum Density of Water. 253
and when it had come to rest the temperature of each
column was observed, and the cock was opened. I f a cur
rent was then observed in the channel, it indicated that
the water in the tube towards which the current flowed was
the denser. By finding a pair of different temperatures
at which the density is exactly the same, we may be sure
that one of them is below and the other above the tempe
rature of maximum density: and by obtaining a series of
such pairs of temperatures of which the difference is smaller
and smaller, Dr. Joule determined the temperature of maxi
mum density to be 39°'i F. within a very small fraction of a
degree.
CHAPTER XVIII.
ON T H E DIFFUSION OF HEAT BY CONDUCTION.
W H E N E V E R different parts of a b o d y are at different tem

peratures, heat flows from the hotter parts to the neigh
bouring colder parts. T o obtain an
exact notion of conduction, let us
consider a large boiler with a flat
bottom, whose thickness is c. T h e
fire maintains the lower surface
c
at the temperature T, and h e a t
flows upwards through the boiler
plate to the upper surface, which is
in contact with the water at the lower temperature, s.
Let us now restrict ourselves to the consideration of a
rectangular portion of the boiler plate, whose length is a,
its breadth b, and its thickness c.
The things to be considered are the dimensions of this
portion of the body, and the nature o f the material of which
it is made, the temperatures of its upper and lower surfaces,
and the flow of heat through it as determined by these

254 Diffusion of Heat by Conduction.
conditions. I n t h e first p l a c e i t is f o u n d that w h e n the

difference o f the temperatures S and T is n o t so g r e a t as t o
make a sensible difference b e t w e e n the p r o p e r t i e s o f the
substance at these t w o temperatures, the flow of heat is
exactly p r o p o r t i o n a l t o the difference o f temperatures, other
things being the same.
L e t us s u p p o s e t h a t w h e n a, b, a n d c a r e each e q u a l to
t h e unit o f l e n g t h , a n d w h e n T is o n e d e g r e e a b o v e s, t h e
steady flow o f heat is s u c h t h a t t h e q u a n t i t y w h i c h e n t e r s
t h e l o w e r surface o r l e a v e s t h e u p p e r surface in t h e unit o f
time is k, then k is d e f i n e d as t h e specific thermal con
ductivity o f the substance. T o find H , t h e q u a n t i t y o f h e a t
w h i c h f l o w s in a t i m e t t h r o u g h t h e p o r t i o n o f b o i l e r p l a t e
w h o s e a r e a is a b, a n d w h o s e t h i c k n e s s is c, w h e n t h e l o w e r
surface is k e p t at a temperature T, and the upper at a
temperature s, till t h e f l o w has b e c o m e steady, d i v i d e the
plate into c horizontal layers, the thickness o f each layer
b e i n g unity, a n d d i v i d e each layer i n t o a b cubes, the sides
o f e a c h Cube b e i n g u n i t y .
Since the flow o f heat is s t e a d y , t h e difference o f tem

perature o f the upper and l o w e r faces o f each cube will
be — (T — s ) . T h e flow o f heat through each cube will
be — (T — s ) i n u n i t o f time. N o w , in e a c h layer there
a r e a b s u c h c u b e s , a n d t h e flow g o e s o n for t u n i t s o f t i m e ,
s o t h a t w e o b t a i n f o r t h e w h o l e h e a t c o n d u c t e d in t i m e /
a bi k , ,
H = —- (T-S),
w h e r e a b is t h e a r e a a n d c t h e t h i c k n e s s o f the plate, / the

t i m e , T — s t h e d i f f e r e n c e o f t e m p e r a t u r e w h i c h causes t h e
flow, and k the specific thermal c o n d u c t i v i t y o f the sub
stance o f the plate.
I t appears, therefore, that the heat c o n d u c t e d is d i r e c t l y
p r o p o r t i o n a l t o t h e a r e a o f t h e p l a t e , t o t h e t i m e , t o t h e differ-

Measures of Conductivity.
ence o f temperature, and to the conductivity, and inversely

proportional t o the thickness o f the plate.
O N T H E D I M E N S I O N S O F k, T H E SPECIFIC T H E R M A L
C O N D U C T I V I T Y .
F r o m the equation w e find
H
k = ' ,_ .
a bt (T—s)
H e n c e if [ L ] b e the unit o f length, [ T ] the unit o f time,
[ 1 1 ] t h e u n i t o f heat, a n d [ ® ] t h e u n i t o f t e m p e r a t u r e , t h e
[ H ]
dimensions o f k will b e - r —
[LT6]
T h e further d i s c u s s i o n o f t h e d i m e n s i o n s o f k w i l l d e p e n d
on the m o d e o f m e a s u r i n g h e a t a n d t e m p e r a t u r e .
(r) I f heat is measured as e n e r g y , its dimensions are
r
L i J
I, and those o f k become
|_T
-^-^-1.
3
© J
This may be
c a l l e d the dynamical m e a s u r e o f the conductivity.

(2) I f h e a t is m e a s u r e d i n t h e r m a l units, such t h a t e a c h
thermal unit is c a p a b l e o f r a i s i n g u n i t o f m a s s o f a s t a n d a r d
substance through o n e degree o f temperature, the d i m e n
sions o f H are [ M © ] , and those o f k will b e J ^ " ~ ~ " J · T h i s
may b e c a l l e d t h e calorimetric m e a s u r e o f t h e c o n d u c t i v i t y .
(3) I f w e t a k e as the unit o f h e a t t h a t w h i c h w i l l raise unit
o f volume o f t h e s u b s t a n c e i t s e l f o n e d e g r e e , t h e d i m e n s i o n s
8
of H are [ L ® ] , a n d t h o s e o f k a r e £ J . This may be
called t h e tkermomdric m e a s u r e o f the conductivity.
In order to obtain a distinct c o n c e p t i o n o f the flow of
heat t h r o u g h a s o l i d b o d y , l e t us s u p p o s e t h a t at a g i v e n
instant w e k n o w t h e t e m p e r a t u r e o f e v e r y p o i n t o f t h e b o d y .
I f w e n o w s u p p o s e a surface o r i n t e r f a c e t o b e d e s c r i b e d
within t h e b o d y s u c h t h a t at e v e r y p o i n t o f this i n t e r f a c e t h e
temperature has a g i v e n v a l u e T ° , w e m a y call this i n t e r f a c e

the isothermal interface of T ° . ( O f course, w h e n w e suppose
this i n t e r f a c e t o e x i s t in t h e b o d y , w e d o n o t c o n c e i v e the
b o d y t o b e a l t e r e d i n a n y w a y b y t h i s s u p p o s i t i o n , as i f t h e
b o d y w e r e r e a l l y cut i n t w o b y i t . ) T h i s isothermal interface
separates those parts o f the b o d y which are hotter than
the temperature T ° from those w h i c h are c o l d e r t h a n this
temperature.
L e t us n o w s u p p o s e the isothermal interfaces drawn for
e v e r y exact d e g r e e o f temperature, from that o f the hottest
part o f the b o d y t o that o f the c o l d e s t part. T h e s e interfaces
m a y b e c u r v e d in a n y w a y , but n o t w o different interfaces
can m e e t each other, because n o part o f the b o d y can at
the s a m e t i m e h a v e t w o different temperatures. T h e body
w i l l t h e r e f o r e b e d i v i d e d i n t o l a y e r s o r shells b y t h e s e i n t e r
f a c e s , a n d t h e s p a c e b e t w e e n t w o i s o t h e r m a l surfaces d i f f e r i n g
b y o n e d e g r e e o f temperature w i l l b e in the f o r m o f a thin
shell, w h o s e thickness m a y v a r y f r o m o n e part t o another.
At e v e r y p o i n t o f this s h e l l t h e r e is a flow o f h e a t from
t h e h o t t e r surface t o t h e c o l d e r surface t h r o u g h t h e s u b s t a n c e
o f t h e shell.
T h e d i r e c t i o n o f this flow is p e r p e n d i c u l a r t o t h e surface
o f t h e s h e l l , a n d t h e r a t e o f flow i s g r e a t e r t h e t h i n n e r the
s h e l l is at t h e p l a c e , a n d t h e g r e a t e r its c o n d u c t i v i t y .
I f w e d r a w a l i n e p e r p e n d i c u l a r t o t h e surface o f t h e shell,
a n d o f l e n g t h u n i t y , t h e n i f c is t h e t h i c k n e s s o f t h e shell,
a n d i f the n e i g h b o u r i n g shells are o f n e a r l y the s a m e thick
ness, this l i n e w i l l c u t a n u m b e r o f shells e q u a l t o - . This,
t h e n , is t h e d i f f e r e n c e o f t e m p e r a t u r e b e t w e e n t w o p o i n t s in
the b o d y at unit o f distance, m e a s u r e d i n the direction o f
t h e flow o f heat, a n d therefore the flow o f heat a l o n g this
line is m e a s u r e d by — , w h e r e k is t h e c o n d u c t i v i t y .
W e can n o w i m a g i n e , with the h e l p o f the isothermal inter

faces, the s t a t e o f t h e b o d y at a g i v e n i n s t a n t . Wherever
there is inequality of temperature between neighbouring

Conduction in a Solid. 257
parts o f t h e b o d y a flow o f h e a t is g o i n g o n . T h i s flow is
everywhere perpendicular to the isothermal interfaces, and
the flow t h r o u g h unit o f a r e a o f o n e o f t h e s e i n t e r f a c e s in u n i t
o f t i m e is e q u a l t o t h e c o n d u c t i v i t y d i v i d e d b y t h e distance
between t w o c o n s e c u t i v e isothermal interfaces.
T h e k n o w l e d g e o f the actual thermal state o f t h e body,
and o f the l a w o f c o n d u c t i o n o f h e a t , thus e n a b l e s us to
d e t e r m i n e the flow o f h e a t at e v e r y p a r t o f t h e b o d y . I f the
f l o w o f h e a t is s u c h t h a t t h e a m o u n t o f h e a t w h i c h f l o w s i n t o
any p o r t i o n o f t h e b o d y is e x a c t l y e q u a l t o t h a t w h i c h flows
out o f it, t h e n t h e t h e r m a l s t a t e o f t h i s p o r t i o n o f t h e b o d y
will r e m a i n t h e s a m e a s l o n g as t h e flow o f h e a t fulfils this
condition.
I f this c o n d i t i o n is fulfilled f o r e v e r y p a r t o f t h e b o d y , t h e
temperature at a n y p o i n t w i l l n o t a l t e r w i t h t h e t i m e , the
system o f i s o t h e r m a l i n t e r f a c e s w i l l c o n t i n u e the same, a n d
the flow o f h e a t w i l l g o o n w i t h o u t a l t e r a t i o n , b e i n g a l w a y s
the s a m e at t h e s a m e p a r t o f t h e b o d y .
T h i s state o f t h i n g s is r e f e r r e d to as t h e state of steady flow
of heat. I t cannot exist unless heat is s t e a d i l y s u p p l i e d t o
the h o t t e r p a r t s o f t h e s u r f a c e o f t h e b o d y , f r o m s o m e s o u r c e
external t o t h e b o d y , a n d an e q u a l q u a n t i t y r e m o v e d from
the c o l d e r p a r t s o f t h e s u r f a c e .by s o m e c o o l i n g m e d i u m , o r
by r a d i a t i o n .
T h e s t a t e o f s t e a d y flow o f h e a t r e q u i r e s t h e f u l f i l m e n t at
every part o f the b o d y o f a certain c o n d i t i o n , similar to that
which is fulfilled i n t h e flow o f an i n c o m p r e s s i b l e fluid.
W h e n this c o n d i t i o n is n o t fulfilled, the quantity o f heat
w h i c h e n t e r s a n y p o r t i o n o f t h e b o d y m a y b e g r e a t e r o r less
than that w h i c h e s c a p e s f r o m it. I n the o n e case heat will
accumulate, a n d t h e p o r t i o n o f t h e b o d y w i l l rise i n t e m p e
rature. In the other case the heat o f the p o r t i o n will
diminish, a n d it w i l l fall in temperature. T h e amount of
this rise o r fall o f t e m p e r a t u r e w i l l b e m e a s u r e d n u m e r i c a l l y
by the g a i n o r l o s s o f h e a t , d i v i d e d b y t h e c a p a c i t y f o r h e a t
of the p o r t i o n c o n s i d e r e d .
s
If t h e p o r t i o n c o n s i d e r e d is u n i t o f v o l u m e , a n d if w e
m e a s u r e h e a t as i n t h e t h i r d m e t h o d g i v e n at p . 255 b y t h e
quantity required t o raise unit o f v o l u m e o f the substance,
i n its a c t u a l s t a t e , o n e d e g r e e , t h e n t h e rise o f t e m p e r a t u r e
o f this p o r t i o n w i l l b e n u m e r i c a l l y e q u a l t o t h e t o t a l f l o w
o f h e a t i n t o it.
W e are n o w able, b y m e a n s o f a thorough knowledge of
t h e t h e r m a l s t a t e o f t h e b o d y at a g i v e n i n s t a n t , t o d e t e r m i n e
the r a t e at w h i c h t h e t e m p e r a t u r e o f every part must be
changing, and therefore w e a r e a b l e t o p r e d i c t its state in
the succeeding instant. Knowing this, w c c a n p r e d i c t its
state in the n e x t instant following, a n d so on.
T h e o n l y p a r t s o f t h e b o d y t o w h i c h this m e t h o d d o c s n o t
a p p l y a r e t h o s e p a r t s o f its surface t o w h i c h h e a t is s u p p l i e d ,
o r f r o m w h i c h h e a t is a b s t r a c t e d , b y a g e n c i e s e x t e r n a l t o t h e
body. I f w e k n o w e i t h e r t h e r a t e at w h i c h h e a t is s u p p l i e d
o r a b s t r a c t e d at e v e r y p a r t o f t h e s u r f a c e , o r t h e a c t u a l t e m
p e r a t u r e o f e v e r y p a r t o f t h e surface d u r i n g t h e w h o l e t i m e ,
either o f these conditions, together w i t h the original thermal
state o f the b o d y , will afford sufficient data for calculating
the temperature o f e v e r y p o i n t d u r i n g all t i m e t o c o m e .
T h e d i s c u s s i o n o f this p r o b l e m i s t h e s u b j e c t o f t h e g r e a t
work o f Joseph Fourier, Theorit de la Chaleur. I t is n o t
p o s s i b l e in a treatise o f the size a n d s c o p e o f this b o o k to
reproduce, or e v e n t o explain, the powerful analytical methods
e m p l o y e d b y F o u r i e r t o e x p r e s s t h e v a r i e d c o n d i t i o n s , as to
t h e f o r m o f its s u r f a c e a n d its o r i g i n a l t h e r m a l state, t o w h i c h
the b o d y m a y b e subjected. T h e s e m e t h o d s b e l o n g , rather,
t o the general theory o f the application of mathematics to
p h y s i c s ; for in e v e r y b r a n c h o f physics, w h e n the investiga
t i o n turns u p o n t h e e x p r e s s i o n o f arbitrary conditions, we
h a v e t o f o l l o w t h e m e t h o d w h i c h F o u r i e r first p o i n t e d out
in his ' T h e o r y o f H e a t . '
I shall o n l y m e n t i o n o n e o r t w o o f t h e results g i v e n by
Fourier, in w h i c h the intricacies arising f r o m the arbitrary
conditions o f the p r o b l e m are a v o i d e d .

Sketch of Fourier s TJieory. 259
T h e first o f t h e s e is t h e c a s e i n w h i c h t h e s o l i d is s u p p o s e d
of infinite extent, a n d o f t h e s a m e c o n d u c t i v i t y in e v e r y part.
T h e temperature o f e v e r y p o i n t o f this b o d y at a giv^n
t i m e is s u p p o s e d t o b e k n o w n , a n d i t is r e q u i r e d to deter
m i n e the t e m p e r a t u r e o f a n y g i v e n p o i n t P after a t i m e t has
elapsed.
F o u r i e r has g i v e n a c o m p l e t e s o l u t i o n o f t h i s p r o b l e m , o f
which w e m a y obtain s o m e idea b y means o f the following
considerations. L e t k b e the conductivity, measured by the
third method, in w h i c h the unit o f heat adopted is that
which w i l l r a i s e u n i t o f v o l u m e o f t h e s u b s t a n c e o n e d e g r e e ;
then i f w e m a k e
k t = A 2
,
a will be a line the length o f which will b e proportional

to the s q u a r e r o o t o f t h e t i m e .
L e t Q b e a n y p o i n t i n t h e b o d y , a n d l e t its d i s t a n c e from
p b e r. L e t t h e o r i g i n a l t e m p e r a t u r e o f Q b e 6. N o w take
r*_
a quantity of matter proportional to e *** a n d of the
t e m p e r a t u r e fl, a n d m i x i t with portions o f matter taken
from e v e r y o t h e r p a r t o f t h e b o d y , t h e t e m p e r a t u r e o f e a c h
portion b e i n g the o r i g i n a l temperature o f that p o i n t , and
u
the quantity o f each portion being proportional to e ^
The mean temperature o f a l l such p o r t i o n s will be the
t e m p e r a t u r e o f t h e p o i n t P after a t i m e / .
I n other words, the temperature o f P after a t i m e t may
be r e g a r d e d as i n s o m e s e n s e the mean o f the original
temperatures o f all p a r t s o f t h e b o d y . I n t a k i n g this mean,
however, different parts are a l l o w e d different weights, de
pending o n t h e i r d i s t a n c e f r o m P , t h e parts n e a r p having
more i n f l u e n c e o n t h e r e s u l t than those at a g r e a t e r d i s
tance.
T h e mathematical formula w h i c h indicates the w e i g h t t o
be g i v e n to the temperature . o f each part in taking the
mean is a very important one. It occurs in several
s 2

26o Diffusion of Heat by Conductio7z
branches o f physics, particularly in the theory of errors
and in that o f the m o t i o n s o f systems o f m o l e c u l e s .
It follows from this result that, i n calculating the tem
perature o f the point p," w e m u s t take into account the
temperature of every other point Q, however distant, a n d
h o w e v e r short the t i m e m a y b e during w h i c h the propaga
tion o f heat has b e e n going on. H e n c e , i n a strict sense,
the influence o f a h e a t e d part o f the b o d y e x t e n d s t o the
m o s t distant parts o f the b o d y in an i n c a l c u l a b l y short time,
s o t h a t it is i m p o s s i b l e t o a s s i g n t o t h e p r o p a g a t i o n o f h e a t
a definite velocity. T h e velocity o f propagation o f thermal
effects depends entirely on the magnitude of the effect
which w e are able to r e c o g n i s e ; and if there w e r e n o limit
to the sensibility o f our instruments, there would be no
limit to the rapidity with w h i c h w e could detect the in
fluence of heat a p p l i e d t o distant parts o f the b o d y . But
w h i l e this influence on distant points can be expressed
mathematically from the first i n s t a n t , its n u m e r i c a l v a l u e is
e x c e s s i v e l y s m a l l until, b y the lapse o f time, the line a has
g r o w n s o as t o b e c o m p a r a b l e w i t h r, t h e d i s t a n c e o f p f r o m
Q. I f w e t a k e this i n t o c o n s i d e r a t i o n , a n d r e m e m b e r t h a t it
is o n l y w h e n t h e c h a n g e s o f t e m p e r a t u r e a r e c o m p a r a b l e w i t h
the original differences o f temperature that w e can detect
them w i t h o u r i n s t r u m e n t s , w e shall s e e t h a t t h e sensible
p r o p a g a t i o n o f h e a t , s o far f r o m b e i n g i n s t a n t a n e o u s , is an
excessively slow process, and that the time required to
produce a similar change of temperature in two similar
systems of different dimensions is proportional to the
square o f the linear dimensions. F o r instance, if a red-hot
b a l l o f four i n c h e s d i a m e t e r f i r e d i n t o a s a n d b a n k has in an
h o u r raised the t e m p e r a t u r e o f t h e s a n d s i x i n c h e s f r o m its
c e n t r e 10° F . , t h e n a r e d - h o t b a l l o f e i g h t i n c h e s diameter
w o u l d t a k e f o u r h o u r s t o r a i s e the temperature o f the sand
t w e l v e i n c h e s f r o m its c e n t r e b y t h e s a m e n u m b e r o f d e g r e e s .
T h i s result, w h i c h is v e r y i m p o r t a n t i n p r a c t i c a l q u e s t i o n s
a b o u t t h e t i m e o f c o o l i n g o r h e a t i n g o f b o d i e s o f a n y form.

in an Infinite Solid. 261
may be deduced directly from the consideration of the
d i m e n s i o n s o f t h e q u a n t i t y k—namely, the square o f a length
divided by a time. I t follows f r o m this t h a t i f i n t w o un
equally heated systems o f similar form but different dimen
sions t h e c o n d u c t i v i t y a n d t h e t e m p e r a t u r e are t h e s a m e at
c o r r e s p o n d i n g p o i n t s at first, t h e n t h e p r o c e s s o f d i f f u s i o n o f
heat w i l l g o o n at d i f f e r e n t r a t e s in t h e t w o s y s t e m s , so t h a t
if for e a c h system the time be taken proportional to the
square o f t h e l i n e a r d i m e n s i o n s , t h e t e m p e r a t u r e s o f c o r r e
s p o n d i n g p o i n t s w i l l still b e t h e s a m e i n b o t h s y s t e m s .
T h e m e t h o d j u s t d e s c r i b e d affords a c o m p l e t e d e t e r m i n a
tion o f the t e m p e r a t u r e o f -any p o i n t of a homogeneous
infinite s o l i d at a n y future t i m e , the temperature of every
p o i n t o f t h e s o l i d b e i n g g i v e n at t h e i n s t a n t f r o m w h i c h w e
begin t o count the t i m e . But w h e n w e attempt to d e d u c e
from a k n o w l e d g e o f t h e p r e s e n t thermal state o f the b o d y
what must h a v e b e e n its s t a t e at s o m e p a s t t i m e , w e f i n d
that t h e m e t h o d c e a s e s t o b e a p p l i c a b l e .
To make this attempt, we have only to m a k e t, the
symbol o f the time, a n e g a t i v e quantity in t h e expressions
given b y Fourier. I f w e adopt the m e t h o d o f taking the
mean o f the temperatures o f all the particles o f the solid, each
p a r t i c l e h a v i n g a c e r t a i n w e i g h t a s s i g n e d t o it i n t a k i n g the
m e a n , w e find t h a t this w e i g h t , a c c o r d i n g t o t h e f o r m u l a , is
greater f o r t h e d i s t a n t p a r t i c l e s than f o r t h e n e i g h b o u r i n g o n e s ,
-a result s u f f i c i e n t l y s t a r t l i n g i n itself. But when we find
that, in o r d e r t o o b t a i n t h e m e a n , after t a k i n g t h e s u m of
the t e m p e r a t u r e s m u l t i p l i e d b y t h e i r p r o p e r f a c t o r s , w e h a v e
to divide by a quantity involving the square r o o t o f /,
the t i m e , w e a r e a s s u r e d t h a t w h e n t is t a k e n n e g a t i v e t h e
o p e r a t i o n is s i m p l y i m p o s s i b l e , a n d devoid o f any physical
meaning, for the square r o o t o f a n e g a t i v e quantity, though
it m a y b e i n t e r p r e t e d w i t h r e f e r e n c e to s o m e g e o m e t r i c a l
o p e r a t i o n s , is a b s o l u t e l y w i t h o u t m e a n i n g w i t h r e f e r e n c e to
time.
It appears, therefore, that Fourier's solution of this

p r o b l e m , t h o u g h c o m p l e t e c o n s i d e r e d w i t h r e f e r e n c e t o future
time, fails w h e n w e attempt to discover the state of the
b o d y in past time.
I n t h e d i a g r a m fig. 33 t h e c u r v e s s h o w the distribution of
Fig. 33.
[6 Ji
C-—•—fx
/ih
' neh
1 ilo is
Sc/!L£ OF TEMPERATURE
temperature in an infinite mass at d i f f e r e n t t i m e s , after the

sudden introduction of a hot horizontal stratum in the
m i d s t o f the infinite solid. T h e temperature is i n d i c a t e d b y
the horizontal distance t o the right o f the vertical line, and

Harmonic Distribution of Temperature. 263
t h e h o t s t r a t u m is s u p p o s e d t o h a v e b e e n i n t r o d u c e d at t h e
m i d d l e o f the figure.
T h e c u r v e s i n d i c a t e t h e t e m p e r a t u r e s o f t h e v a r i o u s strata
o n e hour, four hours, and sixteen h o u r s after the intro
duction o f the hot stratum. T h e gradual diffusion of the
heat is e v i d e n t , a n d a l s o t h e d i m i n i s h i n g r a t e o f d i f f u s i o n as
its e x t e n t i n c r e a s e s .
T h e p r o b l e m o f the diffusion o f heat i n an infinite solid
does not present t h o s e d i f f i c u l t i e s w h i c h o c c u r in problems
relating to a solid o f definite shape. These difficulties
arise f r o m t h e c o n d i t i o n s t o w h i c h t h e s u r f a c e o f the solid
m a y b e subjected, as, for instance, the temperature m a y b e
g i v e n o v e r p a r t o f t h e surface, t h e q u a n t i t y o f h e a t s u p p l i e d
to another part m a y b e g i v e n , or w e m a y o n l y k n o w that
the surface is e x p o s e d t o air o f a c e r t a i n temperature.
T h e method b y which Fourier was enabled to solve many
questions o f this k i n d depends o n t h e d i s c o v e r y o f har
m o n i c distributions o f heat.
Suppose the temperatures o f the different parts o f the b o d y
t o b e s o a d j u s t e d t h a t w h e n t h e b o d y is left t o i t s e l f u n d e r
, the g i v e n c o n d i t i o n s r e l a t i n g to the surface, the tempera
tures o f all t h e parts converge to the final temperature,
their d i f f e r e n c e s f r o m t h e final t e m p e r a t u r e always preserv
ing the same proportion during the process ; then this
distribution of temperature is called an harmonic dis
tribution. I f w e s u p p o s e t h e final t e m p e r a t u r e t o b e t a k e n
as z e r o , t h e n t h e t e m p e r a t u r e s i n t h e h a r m o n i c distribution
d i m i n i s h i n a g e o m e t r i c a l p r o g r e s s i o n as t h e t i m e s increase
in a r i t h m e t i c a l p r o g r e s s i o n , t h e r a t i o o f c o o l i n g b e i n g the
s a m e for all p a r t s o f t h e b o d y .
In each o f the cases i n v e s t i g a t e d b y F o u r i e r there m a y

be an infinite series of harmonic distributions. One of
these, w h i c h h a s the slowest rate o f diminution, may be
called the fundamental harmonic; the rates o f d i m i n u t i o n
of t h e o t h e r s a r e p r o p o r t i o n a l t o t h e s q u a r e s o f t h e n a t u r a l
numbers.

I f t h e b o d y is o r i g i n a l l y h e a t e d i n a n y a r b i t r a r y manner,
F o u r i e r s h o w s h o w t o e x p r e s s t h e o r i g i n a l t e m p e r a t u r e as t h e
s u m o f a series o f h a r m o n i c d i s t r i b u t i o n s . W h e n the b o d y
is l e f t t o i t s e l f t h e p a r t d e p e n d i n g o n t h e h i g h e r h a r m o n i c s
r a p i d l y d i e s a w a y , s o t h a t a f t e r a c e r t a i n t i m e t h e distribu
tion o f heat continually a p p r o x i m a t e s to that d u e to the
fundamental harmonic,' which therefore represents the law
o f c o o l i n g o f a b o d y after t h e p r o c e s s o f d i f f u s i o n o f h e a t
has g o n e o n f o r a l o n g t i m e .
Sir W i l l i a m T h o m s o n has s h o w n , i n a p a p e r p u b l i s h e d i n
t h e ' C a m b r i d g e a n d D u b l i n M a t h e m a t i c a l J o u r n a l ' i n 1844,
h o w to d e d u c e , in certain cases, the t h e r m a l state o f a b o d y
in p a s t t i m e f r o m its o b s e r v e d c o n d i t i o n at p r e s e n t .
F o r this p u r p o s e , t h e p r e s e n t distribution o f temperature
must b e expressed ( a s i t a l w a y s m a y b e ) as t h e sum o f a
series o f h a r m o n i c d i s t r i b u t i o n s . E a c h o f these harmonic
d i s t r i b u t i o n s is such t h a t t h e d i f f e r e n c e o f t h e t e m p e r a t u r e o f
any point from the final t e m p e r a t u r e diminishes in a geo
metrical progression as the t i m e i n c r e a s e s in arithmetical
progression, the ratio o f the geometrical progression being
the greater the higher the degree o f the harmonic.
I f w e n o w make t negative, and trace the history o f the
distribution o f temperature up the stream o f t i m e , w e shall
find e a c h h a r m o n i c i n c r e a s i n g as w e g o b a c k w a r d s , a n d the
h i g h e r h a r m o n i c s i n c r e a s i n g faster t h a n t h e l o w e r o n e s .
I f the present distribution o f temperature is s u c h that it
m a y b e e x p r e s s e d i n a f i n i t e s e r i e s o f h a r m o n i c s , t h e distri
b u t i o n o f t e m p e r a t u r e at a n y p r e v i o u s t i m e m a y b e c a l c u l a t e d ;
but i f ( a s is g e n e r a l l y t h e c a s e ) t h e s e r i e s o f h a r m o n i c s is
infinite, then the t e m p e r a t u r e can be calculated only when
this s e r i e s is c o n v e r g e n t . F o r p r e s e n t a n d future t i m e it is
a l w a y s c o n v e r g e n t , b u t f o r p a s t t i m e it b e c o m e s u l t i m a t e l y
divergent w h e n the t i m e is t a k e n at a sufficiently r e m o t e
epoch. T h e n e g a t i v e v a l u e o f t, f o r w h i c h t h e series b e c o m e s
ultimately divergent, indicates a certain date in past time
such that t h e present state o f things c a n n o t b e d e d u c e d from

Steady and Periodic Flow of Heat. 265
any distribution o f temperature occurring p r e v i o u s l y t o that
date, a n d b e c o m i n g d i f f u s e d b y o r d i n a r y c o n d u c t i o n . Some
other e v e n t b e s i d e s o r d i n a r y c o n d u c t i o n must h a v e o c c u r r e d
since t h a t d a t e i n o r d e r t o p r o d u c e t h e p r e s e n t s t a t e o f t h i n g s .
T h i s is o n l y o n e o f t h e c a s e s i n w h i c h a c o n s i d e r a t i o n o f
the dissipation o f e n e r g y leads t o the determination o f a
superior limit to the antiquity o f the observed order of
things.
A v e r y i m p o r t a n t c l a s s o f p r o b l e m s is t h a t i n w h i c h t h e r e
is a s t e a d y f l o w of heat into the body at o n e p o i n t of
its surface, and o u t o f i t at another part. There is a
certain distribution o f t e m p e r a t u r e i n all such cases, w h i c h
if once established will not afterwards change: this is
called the permanent distribution. I f the o r i g i n a l distri
b u t i o n differs f r o m this, t h e effect o f t h e d i f f u s i o n o f h e a t w i l l
b e t o cause t h e distribution o f temperature to approximate
without limit to this permanent distribution. Questions
relating t o the permanent distribution o f temperature and
the steady flow of heat are in general less difficult than
t h o s e in w h i c h this s t a t e is n o t e s t a b l i s h e d .
A n o t h e r i m p o r t a n t class o f p r o b l e m s is t h a t in w h i c h h e a t
is s u p p l i e d t o a p o r t i o n o f t h e s u r f a c e i n a p e r i o d i c m a n n e r ,
as in the c a s e o f t h e s u r f a c e o f t h e earth, w h i c h r e c e i v e s a n d
emits heat a c c o r d i n g to the periods of day and night, and
the l o n g e r p e r i o d s o f s u m m e r a n d w i n t e r .
T h e e f f e c t o f s u c h p e r i o d i c c h a n g e s o f t e m p e r a t u r e at t h e
surface is t o p r o d u c e w a v e s o f h e a t , w h i c h d e s c e n d i n t o t h e
earth a n d g r a d u a l l y d i e a w a y . T h e l e n g t h o f t h e s e w a v e s is
proportional to the square r o o t o f the p e r i o d i c time. If we
e x a m i n e t h e w a v e at a depth such that t h e greatest heat
o c c u r s w h e n it is c o l d e s t at t h e surface, t h e n t h e extent of
the v a r i a t i o n o f t e m p e r a t u r e at this d e p t h is o n l y - £ o f its s
v a l u e at t h e surface. I n t h e r o c k s o f this c o u n t r y this d e p t h

is a b o u t 25 f e e t f o r the a n n u a l v a r i a t i o n s .
I n the d i a g r a m fig. 34 t h e d i s t r i b u t i o n o f temperature in
t h e d i f f e r e n t s t r a t a is r e p r e s e n t e d at t w o d i f f e r e n t t i m e s . If

we suppose the figure to represent the diurnal v a r i a t i o n of
temperature, then the curves indicate the temperatures at
Frc. 34.
SURFACE
\
w
\\
01373
I
\\ I
I
TEMPERATURES
• , V . . • .
2 A.M. and 8 A.M. I f w e s u p p o s e it t o r e p r e s e n t the annual

variation, then the curves c o r r e s p o n d to January and April.

Underground Temperature. 267
S i n c e t h e d e p t h o f t h e w a v e v a r i e s as t h e s q u a r e r o o t o f t h e
periodic time, the wave-length o f the annual variation of
temperature will b e about nineteen times the depth o f those
of the diurnal variation. A t a depth o f about 50 f e e t t h e
v a r i a t i o n o f a n n u a l t e m p e r a t u r e is a b o u t a y e a r i n a r r e a r .
T h e actual variation o f temperature at t h e surface d o e s
n o t f o l l o w t h e l a w w h i c h g i v e s a s i m p l e h a r m o n i c w a v e , but,
however complicated the actual variation m a y b e , F o u r i e r
shows how to d e c o m p o s e it i n t o a n u m b e r of harmonic
w a v e s o f w h i c h it is t h e s u m . A s w e d e s c e n d into the earth
these w a v e s die a w a y , the shortest m o s t rapidly, so that w e
lose the irregularities o f the diurnal variation in a few inches,
and the diurnal variation itself in a f e w feet. T h e annual
variation can b e traced to a much greater depth ; but at
d e p t h s o f 50 f e e t a n d u p w a r d s the temperature is s e n s i b l y
constant throughout the year, the v a r i a t i o n b e i n g less than
t h e f i v e - h u n d r e d t h p a r t o f t h a t at t h e s u r f a c e .
But if w e c o m p a r e the mean temperatures at different

depths, w e find t h a t as w e d e s c e n d t h e m e a n temperature
rises, a n d t h a t a f t e r w e h a v e p a s s e d t h r o u g h t h e u p p e r strata,
in w h i c h t h e p e r i o d i c v a r i a t i o n s o f t e m p e r a t u r e a r e o b s e r v e d ,
this i n c r e a s e o f t e m p e r a t u r e g o e s o n as w e d e s c e n d t o the
greatest depths k n o w n t o m a n . I n this c o u n t r y t h e r a t e o f
increase o f temperature appears to b e about i ° F . for 5 0
feet o f d e s c e n t .
T h e f a c t t h a t the strata o f t h e e a r t h a r e h o t t e r b e l o w t h a n
a b o v e shows that heat must b e flowing through t h e m from
below upwards. The amount o f h e a t w h i c h thus flows
upwards in a year through a square f o o t o f t h e surface c a n
easily b e f o u n d i f w e k n o w t h e c o n d u c t i v i t y o f the substance
through w h i c h it passes. For several kinds o f rock the
conductivity has b e e n ascertained b y means o f experiments
m a d e u p o n d e t a c h e d p o r t i o n s o f t h e r o c k in t h e l a b o r a t o r y .
B u t a still m o r e s a t i s f a c t o r y m e t h o d , w h e r e i t c a n b e e m p l o y e d ,
is t o m a k e a r e g i s t e r o f t h e t e m p e r a t u r e at different depths
t h r o u g h o u t t h e y e a r , a n d f r o m this t o d e t e r m i n e t h e length

of the annual w a v e o f temperature, o r its rate o f decay.

F r o m either o f these data the conductivity o f the substance
of the earth m a y b e found without r e m o v i n g the rocks from
their b e d .
B y o b s e r v a t i o n s o f this k i n d m a d e at d i f f e r e n t p o i n t s o f
the earth's surface w e m i g h t d e t e r m i n e the quantity o f heat
which flows out o f the e a r t h in a y e a r . T h i s can be done
o n l y r o u g h l y at p r e s e n t , o n a c c o u n t o f t h e s m a l l n u m b e r o f
p l a c e s at w h i c h s u c h o b s e r v a t i o n s h a v e b e e n m a d e , b u t w e
know enough to b e certain that a great quantity of heat
escapes from the earth e v e r y year. I t is n o t p r o b a b l e t h a t
a n y g r e a t p r o p o r t i o n o f this h e a t is g e n e r a t e d by chemical
action within the earth. W e must therefore c o n c l u d e that
t h e r e is l e s s h e a t i n t h e earth n o w t h a n i n f o r m e r p e r i o d s o f
its e x i s t e n c e , a n d t h a t its i n t e r n a l parts w e r e f o r m e r l y v e r y
much hotter than t h e y are n o w .
In this w a y Sir W . T h o m s o n has c a l c u l a t e d that, if n o
c h a n g e has o c c u r r e d in the o r d e r o f t h i n g s , it c a n n o t h a v e
b e e n m o r e than 2 0 0 , 0 0 0 , 0 0 0 years since the earth was in
the condition o f a mass o f m o l t e n matter, o n w h i c h a solid
crust w a s j u s t b e g i n n i n g t o f o r m .
ON THE DETERMINATION OF T H E T H E R M A L CONDUCTIVITY

OF BODIES.
The most obvious method of determining the conduc

t i v i t y o f a s u b s t a n c e is t o f o r m it i n t o a p l a t e o f uniform
t h i c k n e s s , t o b r i n g o n e o f its surfaces t o a k n o w n tempera
ture a n d the other to a k n o w n l o w e r temperature, and to
determine the quantity o f heat w h i c h passes through the
p l a t e in a g i v e n t i m e .
F o r i n s t a n c e , i f w e c o u l d b r i n g o n e surface to the tem
perature o f b o i l i n g water b y a current o f steam, a n d keep
the other at t h e f r e e z i n g t e m p e r a t u r e b y means o f ice, w e
might measure the heat transmitted either b y the quantity
of steam c o n d e n s e d , or b y the quantity of i c e m e l t e d .

Measurement of Conductivity. 269
T h e c h i e f d i f f i c u l t y i n this m e t h o d is that t h e surface o f
the p l a t e d o e s n o t acquire the temperature o f the steam or
t h e i c e w i t h w h i c h i t is i n c o n t a c t , a n d t h a t i t is difficult t o
ascertain its r e a l t e m p e r a t u r e w i t h t h e accuracy necessary
for a d e t e r m i n a t i o n o f this k i n d .
M o s t o f the actual determinations o f conductivity h a v e
b e e n m a d e in a m o r e i n d i r e c t w a y — b y o b s e r v i n g t h e per
manent distribution o f temperature in a bar, o n e e n d o f
w h i c h is m a i n t a i n e d at a h i g h t e m p e r a t u r e , w h i l e t h e rest
o f its surface is e x p o s e d t o t h e c o o l i n g effects o f t h e a t m o
sphere.
The temperatures of a series o f p o i n t s i n t h e b a r are
ascertained b y m e a n s o f thermometers inserted into holes
d r i l l e d i n it, a n d b r o u g h t i n t o t h e r m a l c o n n e x i o n w i t h its
s u b s t a n c e b y m e a n s o f fluid m e t a l s u r r o u n d i n g t h e b u l b s .
I n this w a y t h e r a t e o f d i m i n u t i o n o f t e m p e r a t u r e with
the d i s t a n c e c a n b e a s c e r t a i n e d at v a r i o u s p o i n t s o n t h e b a r .
To determine die conductivity, w e must c o m p a r e the
rate o f v a r i a t i o n o f t e m p e r a t u r e w i t h t h e flow o f h e a t w h i c h
is d u e t o it. I t is i n t h e d e t e r m i n a t i o n o f this flow o f h e a t
that the indirectness o f the m e t h o d consists. The most
t r u s t w o r t h y m e t h o d o f d e t e r m i n i n g t h e flow o f h e a t is t h a t
e m p l o y e d b y P r i n c i p a l F o r b e s in his e x p e r i m e n t s o n the
1
conduction o f heat in an iron bar. H e t o o k a bar o f exactly
t h e s a m e s e c t i o n a n d m a t e r i a l as t h e e x p e r i m e n t a l bar, a n d ,
after h e a t i n g i t u n i f o r m l y , a l l o w e d i t t o c o o l i n air o f t h e
s a m e t e m p e r a t u r e as t h a t s u r r o u n d i n g t h e e x p e r i m e n t a l b a r .
B y o b s e r v i n g t h e t e m p e r a t u r e o f t h e c o o l i n g b a r at f r e q u e n t
intervals o f t i m e , h e ascertained the quantity o f heat which
e s c a p e d f r o m t h e s i d e s o f t h e bar, this h e a t b e i n g m e a s u r e d
in t e r m s o f t h e quantity o f h e a t r e q u i r e d t o raise unit of
v o l u m e of the bar o n e d e g r e e . T h i s loss o f h e a t d e p e n d e d
o f course o n the temperature o f the bar at the time, a n d a
table was f o r m e d s h o w i n g the loss from a linear foot o f the
bar i n a m i n u t e at a n y t e m p e r a t u r e .
1
Traits. Roy. Soc. Edinb. 1861-2.

N o w , in the e x p e r i m e n t a l bar the temperature of every

part was k n o w n , a n d therefore the loss o f heat from any
g i v e n portion o f the bar c o u l d b e found b y m a k i n g use of
the table. T o d e t e r m i n e the flow o f h e a t across any par
ticular section, it w a s n eces s ar y to s u m up the loss o f h e a t
f r o m a l l p a r t s o f t h e b a r b e y o n d this s e c t i o n , a n d w h e n t h i s
was done, b y c o m p a r i n g the flow o f heat across the section
with the rate o f diminution o f temperature per linear foot
in the curve o f temperature, the conductivity o f the bar
for the temperature o f the section was ascertained. Prin
cipal Forbes found that the thermal conductivity o f iron
d e c r e a s e s as t h e t e m p e r a t u r e increases.
The c o n d u c t i v i t y thus d e t e r m i n e d is e x p r e s s e d i n t e r m s
o f t h e q u a n t i t y o f h e a t r e q u i r e d t o r a i s e u n i t o f v o l u m e of
tfie substance one degree. I f w e w i s h t o express it in the
ordinary w a y in terms o f the thermal u n i t as d e f i n e d w i t h
reference to water at its maximum density, we must
m u l t i p l y our result b y the specific heat o f the substance,
and b y its d e n s i t y ; f o r t h e quantity o f heat required to
r a i s e u n i t o f m a s s o f t h e s u b s t a n c e o n e d e g r e e is its s p e c i f i c
h e a t , a n d t h e n u m b e r o f u n i t s o f m a s s i n u n i t o f v o l u m e is
the density o f the substance.
A s l o n g as w e a r e o c c u p i e d w i t h q u e s t i o n s relating to the
diffusion o f heat and the w a v e s o f t e m p e r a t u r e in a single
substance, the quantity o n w h i c h the phenomena depend
is the t h e r m o m e t r i c c o n d u c t i v i t y e x p r e s s e d i n terms o f the
substance itself; but whenever we have to d o with the
effects o f t h e flow o f h e a t u p o n o t h e r b o d i e s , as i n t h e c a s e
of boiler plates, steam-condensers, & c , we must use a
definite thermal unit, and express the calorimetric con
ductivity in terms o f it. I t has b e e n shown by Professor
T y n d a l l that the w a v e o f temperature t r a v e l s faster i n b i s
m u t h than in iron, though the conductivity o f bismuth is
much less than that o f iron. The reason is that the
t h e r m a l c a p a c i t y o f t h e i r o n is m u c h g r e a t e r t h a n t h a t o f an
equal v o l u m e o f bismuth.

Conductivity of various Substances. 271
Forbes was the first to remark that the order in which

the metals follow one another in respect o f thermal con
ductivity is nearly the same as their order as regards electric
conductivity. T h i s remark is an important one as regards
certain metals, but it must not be pushed too far; for
there are substances which are almost perfect insulators of
electricity, whereas it is impossible to find a substance
which will not transmit heat.
T h e electric conductivity of metals diminishes as the
temperature rises. T h e thermal conductivity o f iron also
diminishes, but in a smaller ratio, as the temperature rises.
Professor T a i t has given reasons for believing that the
thermal conductivity o f metals may be inversely proportional
to their absolute temperature.
T h e electric conductivity of most non-metallic substances,
and of all electrolytes and dielectrics, increases as the tem
perature rises. W e have not sufficient data to determine
whether this is the case as regards their thermal conduc
tivity. According to the molecular theory o f Chapter X X I I .
the thermal conductivity o f gases increases as the tempera
ture rises.
ON T H E CONDUCTIVITY OF FLUIDS.
I t is very difficult to determine the thermal conductivity

of fluids, because the variation of temperature which is part
of the phenomenon produces a variation of density, and
unless the surfaces o f equal temperature are horizontal, and
the upper strata are the warmest, currents will be produced
in the fluid which will entirely mask the phenomena of true
conduction.
Another difficulty arises from the fact that most fluids
have a very small conductivity compared with solid bodies.
H e n c e the sides of the vessel containing the fluid are oftea
the principal channel for the conduction of heat
In the case of gaseous fluids the difficulty is increased by
the greater mobility of their parts, and by the great variation

o f density with change o f temperature. Their conductivity

is e x t r e m e l y s m a l l , a n d t h e m a s s o f t h e g a s is g e n e r a l l y s m a l l
c o m p a r e d w i t h t h a t o f t h e v e s s e l i n w h i c h i t is c o n t a i n e d .
Besides this, t h e effect of direct radiation from the source
of heat through the gas on the t h e r m o m e t e r produces a
heating effect w h i c h m a y , in s o m e cases, c o m p l e t e l y m a s k
t h e effect o f true c o n d u c t i o n . F o r all these reasons, the
determination o f the thermal c o n d u c t i v i t y o f a g a s is an
i n v e s t i g a t i o n o f e x t r e m e difficulty. (See Appendix.)
APPLICATIONS OF T H E THEORY.
The great thermal conductivity o f the metals, especially

o f c o p p e r , furnishes the means o f producing m a n y thermal
effects in a convenient manner. F o r instance, in order
to maintain a b o d y at a high temperature by means of a
s o u r c e o f h e a t at s o m e d i s t a n c e f r o m it, a t h i c k r o d o f c o p p e r
may be used to conduct the heat from the source 'to the
b o d y w c wish to h e a t ; a n d w h e n i t is d e s i r e d t o w a r m t h e
air o f a r o o m b y m e a n s o f a h o t p i p e o f small d i m e n s i o n s ,
the effect may be greatly increased b y attaching copper
plates to the pipe, which b e c o m e hot b y conduction, and
e x p o s e a g r e a t h e a t i n g surface t o t h e air.
To ensure an exact equality o f temperature in a l l the
p a r t s o f a b o d y , it m a y b e p l a c e d i n a c l o s e d c h a m b e r f o r m e d
of thick sheet copper. I f the temperature is n o t quite
u n i f o r m o u t s i d e this c h a m b e r , a n y d i f f e r e n c e of temperature
between one part o f the outer surface and another will
p r o d u c e such a flow ol heat in the substance o f the c o p p e r
t h a t t h e t e m p e r a t u r e o f t h e i n n e r surface w i l l b e v e r y n e a r l y
uniform. T o m a i n t a i n t h e c h a m b e r at a u n i f o r m h i g h t e m
perature b y means o f a flame, as is s o m e t i m e s n e c e s s a r y , it
m a y b e p l a c e d i n a l a r g e r c o p p e r c h a m b e r , a n d so s u s p e n d e d
by strings or supported on legs that v e r y little heat can
pass b y direct conduction from the outer to the inner w a l l
T h u s w e h a v e first a n o u t e r h i g h l y c o n d u c t i n g s h e l l o f c o p p e r ;

Chamber of Uniform Temperature. 273
n e x t a s l o w l y c o n d u c t i n g s h e l l o f air, w h i c h , h o w e v e r , t e n d s
to equalize the temperature b y convection ; then another
highly conducting shell of copper ; and lastly the inner
chamber. The whole arrangement facilitates the flow of
heat parallel t o the walls o f the chambers, and checks its
flow perpendicular to the walls. N o w differences o f t e m p e
rature w i t h i n the chamber must arise from the passage of
heat from w i t h o u t t o within, or i n the reverse d i r e c t i o n , a n d
the flow o f h e a t a l o n g t h e s u c c e s s i v e e n v e l o p e s t e n d s only
to equalize the temperature. H e n c e , b y the arrangement o f
successive shells, alternately o f h i g h l y c o n d u c t i n g a n d s l o w l y
conducting matter, and still m o r e i f t h e s l o w l y c o n d u c t i n g
m a t t e r is fluid, a n a l m o s t c o m p l e t e u n i f o r m i t y o f t e m p e r a t u r e
m a y b e m a i n t a i n e d w i t h i n the inner c h a m b e r , e v e n w h e n t h e
o u t e r c h a m b e r has a l l t h e h e a t a p p l i e d t o i t at o n e p o i n t .
This arrangement was employed by M . F i z e a u in his

researches o n the dilatation o f b o d i e s b y heat.
C H A P T E R X I X .
ON THE DIFFUSION OF FLUIDS.
THERE are m a n y liquids w h i c h , w h e n they are intermingled

b y b e i n g stirred together, r e m a i n m i x e d , and, though their
densities are different, they d o n o t separate from each other
as o i l a n d w a t e r do. W h e n liquids w h i c h are capable of
b e i n g p e r m a n e n t l y m i x e d a r e p l a c e d in c o n t a c t w i t h each
other, t h e p r o c e s s o f m i x t u r e g o e s o n i n a s l o w a n d gradual
m a n n e r , a n d c o n t i n u e s t i l l t h e c o m p o s i t i o n o f t h e m i x t u r e is
the s a m e i n e v e r y p a r t .
T h u s i f w e p u t a s t r o n g s o l u t i o n o f a n y salt i n t h e l o w e r
part o f a t a l l g l a s s j a r , w e m a y , b y p o u r i n g w a t e r in a g e n t l e
stream o n a small w o o d e n float, fill up the jar w i t h w a t e r
without disturbing the solution. T h e p r o c e s s o f diffusion
will t h e n g o o n b e t w e e n t h e w a t e r a n d the s o l u t i o n , a n d w i l l

274 Diffusion of Matter.
continue for weeks or months, according to the nature of

the salt and the height of the jar.
I f the solution of the salt is strongly coloured, as in the
case o f sulphate o f copper, bichromate of potash, & c , w e
may trace the process o f diffusion by the gradual rise of the
colour into the upper part o f the jar, and the weakening of
the colour in the lower part. A more exact method is that
employed by Sir William Thomson, o f placing a number of
glass bubbles or beads in the jar, whose specific gravities
are intermediate between that o f the strong solution and
that o f water. A t first the beads all float in the surface of
separation between the two liquids, but as diffusion goes on
they separate from each other, and indicate by their positions
the specific gravity of the mixture at various depths. I t is
necessary to expel the air very thoroughly from both liquids
by boiling before commencing this experiment. I f this is
not done, air separates from the liquids, and attaches itself
in the form of small bubbles to the specific gravity beads, so
that they no longer indicate the true specific gravity of the
fluid in which they float. I n order to determine the strength
of the solution at any point, as indicated b y one of the
beads, we have only to measure the amount of the salt
which must be added to a known quantity of pure water, in
order to make the bead swim in the mixture.
Voit has investigated the process of diffusion of a solution
of sugar by passing a ray of plane polarized light horizontally
through the liquid at various depths. T h e solution of sugar
causes the plane of polarization to rotate through a certain
angle, and from this angle the percentage of sugar in any
given stratum of the fluid can be determined without disturb
ing the vessel.
There are many pairs of liquids which do not diffuse into
each other, and there are others in which the diffusion, after
going on for some time, stops as soon as a certain small
proportion of the heavier liquid has become mixed with the
lighter, and a small proportion of the lighter has become
mixed with the heavier.

Law of Diffusion.
In t h e c a s e o f g a s e s , h o w e v e r , t h e r e is n o s u c h l i m i t a t i o n .
Every g a s diffuses into every other g a s , s o that, h o w e v e r
different the specific gravities o f t w o gases m a y b e , it is
impossible to k e e p them from mixing if they are p l a c e d in
t h e s a m e v e s s e l , e v e n w h e n t h e d e n s e r g a s is p l a c e d b e l o w
the rarer.
T h e fact o f the diffusion o f g a s e s w a s first r e m a r k e d by
Priestley. T h e laws c f the p h e n o m e n a w e r e first i n v e s t i g a t e d
by Graham. T h e r a t e at w h i c h t h e d i f f u s i o n o f a n y s u b s t a n c e
g o e s o n is in e v e r y c a s e p r o p o r t i o n a l t o t h e r a t e o f v a r i a t i o n
of the strength o f that substance in the f l u i d as w e p a s s
along the line in w h i c h the diffusion takes place. Each
substance in the m i x t u r e flows f r o m p l a c e s w h e r e it exists in
g r e a t e r q u a n t i t y t o p l a c e s w h e r e i t is less a b u n d a n t .
The l a w o f diffusion o f m a t t e r is t h e r e f o r e o f e x a c t l y t h e
same form as t h a t o f t h e diffusion o f heat b y conduction,
and w e c a n at o n c e a p p l y all that w e k n o w a b o u t t h e con
d u c t i o n o f h e a t t o assist us in u n d e r s t a n d i n g t h e phenomena
o f the diffusion o f matter.
T o fix our i d e a s , l e t us s u p p o s e t h e f l u i d t o be contained
in a v e s s e l w i t h v e r t i c a l s i d e s , a n d l e t us c o n s i d e r a h o r i z o n t a l
s t r a t u m o f t h e f l u i d o f t h i c k n e s s c. L e t the composition of
the fluid at t h e u p p e r surface o f t h i s s t r a t u m b e denoted by
A, and that o f the fluid at t h e l o w e r surface o f the stratum
b y B.
T h e effect o f t h e d i f f u s i o n which g o e s on in the stratum
w i l l b e the s a m e as i f a c e r t a i n v o l u m e o f fluid o f c o m p o s i t i o n
A h a d p a s s e d d o w n w a r d s t h r o u g h t h e s t r a t u m w h i l e an equal
v o l u m e o f fluid o f c o m p o s i t i o n B had p a s s e d upwards through
the s t r a t u m at t h e s a m e t i m e .
L e t d b e the thickness o f the stratum w h i c h either o f these
equal v o l u m e s o f fluid w o u l d f o r m i n t h e vessel, then d is
evidently proportional : —
i st. T o t h e t i m e o f diffusion.
2nd. Inversely to the thickness o f the stratum through
w h i c h t h e diffusion t a k e s p l a c e .
3rd. To a coefficient d e p e n d i n g on the nature of the
r 2
interdiffusing substances. Hence if t is the time o f dif

fusion a n d k the coefficient o f diffusion,
d or
We thus find that the dimensions o f k, the coefficient o f
diffusion, are equal to the square o f a l e n g t h divided by a
time.
Hence, in the experiment with the jar, the vertical
d i s t a n c e b e t w e e n strata o f c o r r e s p o n d i n g d e n s i t i e s , as i n d i
c a t e d b y t h e b e a d s w h i c h float i n t h e m , v a r i e s as t h e s q u a r e
r o o t o f the t i m e f r o m the b e g i n n i n g o f the diffusion.
W h e n t h e m i x t u r e o f t w o l i q u i d s o r g a s e s is e f f e c t e d in a
more rapid manner b y agitation or stirring, t h e o n l y effect
o f the m e c h a n i c a l d i s t u r b a n c e is t o i n c r e a s e t h e area o f the
surfaces through which diffusion takes place. Instead of
the surface o f separation b e i n g a s i n g l e h o r i z o n t a l p l a n e , it
becomes a surface of many convolutions, and of great
extent, and in o r d e r t o effect a c o m p l e t e m i x t u r e the dif
fusion has to extend o n l y o v e r the distance between the
successive c o n v o l u t i o n s o f t h i s surface instead o f o v e r half
the d e p t h o f the vessel.
S i n c e t h e t i m e r e q u i r e d f o r d i f f u s i o n v a r i e s as t h e s q u a r e
of the distance t h r o u g h w h i c h the diffusion t a k e s p l a c e , it
is easy t o s e e that b y stirring the solution in a jar along
w i t h t h e w a t e r a b o v e it, a c o m p l e t e m i x t u r e m a y b e e f f e c t e d
in a few seconds, which w o u l d h a v e required m o n t h s i f the
jar had been left u n d i s t u r b e d . That the mixture effected
by stirring is not instantaneous may be easily seen by
observing that during the operation the fluid a p p e a r s to
b e full o f s t r e a k s , w h i c h c a u s e i t t o l o s e its transparency.
T h i s arises from t h e d i f f e r e n t i n d i c e s o f r e f r a c t i o n o f different
portions o f the mixture, which have b e e n brought n e a r each
o t h e r b y stirring. T h e surfaces o f s e p a r a t i o n are so drawn
out and convoluted that the whole mass has a woolly
appearance, for no ray of light can pass without being
t u r n e d m a n y t i m e s o u t o f its p a t h .

Molecular Motion. 277
The same appearance may also be observed when we
mix hot water with c o l d , and even when v e r y h o t air is
mixed with cold air. This shows that what is c a l l e d t h e
equalization of temperature by convection currents really
takes p l a c e b y c o n d u c t i o n b e t w e e n p o r t i o n s o f t h e s u b s t a n c e
brought near each other by the currents.
If wc observe the process of diffusion with our most
powerful microscopes, w e cannot follow the m o t i o n o f any
individual portions o f t h e fluids. W e cannot point out one
p l a c e in w h i c h t h e l o w e r fluid is a s c e n d i n g , and another in
w h i c h t h e u p p e r fluid is d e s c e n d i n g . T h e r e are n o currents
v i s i b l e t o us, a n d t h e m o t i o n o f t h e m a t e r i a l s u b s t a n c e s g o e s
on as i m p e r c e p t i b l y as the c o n d u c t i o n of heat or o f elec
tricity. H e n c e the m o t i o n w h i c h constitutes diffusion must
b e d i s t i n g u i s h e d f r o m t h o s e m o t i o n s o f fluids w h i c h w e c a n
trace b y m e a n s o f floating motes. It may be described as
a motion o f the fluids, n o t in mass, but b y m o l e c u l e s .
We have not hitherto taken any notice of molecular

theories, because w e wish to draw a distinction between
that part o f our subject which depends only on the
universal axioms of dynamics, combined with observa
tions o f t h e properties o f bodies, and the part which en
d e a v o u r s t o a r r i v e at a n e x p l a n a t i o n o f these properties by
attributing certain motions to minute portions of matter
w h i c h a r e as y e t i n v i s i b l e t o us.
The description of diffusion as a molecular motion is
one which we shall justify when we come to treat of
molecular science. A t present, h o w e v e r , w e s h a l l use the
p h r a s e ' m o l e c u l a r m o t i o n ' as a c o n v e n i e n t m o d e o f d e s c r i b i n g
the t r a n s f e r e n c e o f a f l u i d w h e n t h e m o t i o n o f s e n s i b l e por
tions o f t h e fluid c a n n o t b e d i r e c t l y o b s e r v e d .
Graham o b s e r v e d that the diffusion b o t h o f liquids and
gases takes place through porous solid bodies, such as
p l a s t e r o f P a r i s a n d p r e s s e d p l u m b a g o , at a r a t e n o t v e r y m u c h
less t h a n w h e n n o s u c h b o d y is i n t e r p o s e d , and this even
when the s o l i d d i v i s i o n is a m p l y sufficient to check all

ordinary currents, a n d e v e n to support considerable differ

e n c e s o f p r e s s u r e o n its o p p o s i t e s i d e s .
B y taking a d v a n t a g e o f the different velocities with which
different liquids a n d gases pass through such substances, h e
w a s e n a b l e d t o effect m a n y important analyses a n d t o arrive
at n e w v i e w s o f the constitution-of various b o d i e s .
B u t t h e r e is a n o t h e r class o f c a s e s in w h i c h a liquid or
gas can pass throvigh a diaphragm w h i c h is n o t in the
o r d i n a r y sense porous. For instance, when carbonic acid
g a s is c o n f i n e d in a s o a p - b u b b l e it g r a d u a l l y e s c a p e s . The
liquid absorbs the g a s at its i n n e r surface, w h e r e it has t h e
greatest, d e n s i t y ; and o n the outside, w h e r e the density o f
t h e c a r b o n i c a c i d is less, t h e g a s diffuses o u t i n t o t h e a t m o
sphere. D u r i n g t h e p a s s a g e o f t h e g a s t h r o u g h t h e film it is
i n t h e state o f s o l u t i o n i n w a t e r . I t is a l s o f o u n d t h a t h y d r o g e n
and other gases can pass through a layer o f caoutchouc.
T h e r a t i o s in w h i c h d i f f e r e n t g a s e s p a s s t h r o u g h this s u b s t a n c e
are different from the ratios i n w h i c h t h e y p e r c o l a t e through
porous plugs. Graham s h o w s that the chemical relations
between the gases and the caoutchouc determine these
r a t i o s , a n d t h a t it i s n o t t h r o u g h p o r e s i n t h e o r d i n a r y s e n s e
that the m o t i o n takes p l a c e .
A c c o r d i n g t o G r a h a m ' s t h e o r y , t h e c a o u t c h o u c is a c o l l o i d
s u b s t a n c e — t h a t i s , o n e w h i c h is c a p a b l e o f b e i n g u n i t e d , i n a
temporary and v e r y loose manner, with various proportions
of other substances, j u s t as glue will form a jelly with
various proportions o f water. A n o t h e r class o f s u b s t a n c e s ,
w h i c h G r a h a m calls c r y s t a l l o i d , are distinguished from these
b y being always o f definite composition, and not admitting
o f these t e m p o r a r y associations. W h e n a c o l l o i d substance
has in different parts o f its mass different proportions of
water, alcohol, or solutions o f c r y s t a l l o i d b o d i e s , diffusion
takes place through the c o l l o i d substance, although n o part
o f it c a n b e s h o w n t o b e in t h e l i q u i d state.
On the other hand, a s o l u t i o n o f a c o l l o i d s u b s t a n c e is
almost incapable o f diffusion through a porous solid, or
through another colloid substance. T h u s , if a solution o f

Theory of Graham. 279
gum i n w a t e r c o n t a i n i n g salt b e p l a c e d i n contact with a
solid jelly o f gelatine containing a l c o h o l , salt and water
will b e diffused i n t o the g e l a t i n e , a n d a l c o h o l will b e diffused
into the g u m , but there will b e n o mixture o f the g u m -and
the gelatine.
T h e r e are certain metals w h o s e relation t o certain gases
Graham e x p l a i n e d b y this t h e o r y . F o r instance, hydrogen
c a n b e m a d e t o p a s s t h r o u g h i r o n a n d p a l l a d i u m at a high
temperature, and carbonic oxide can be made to pass
through iron. T h e gases form colloidal unions with the
m e t a l s , a n d a r e d i f f u s e d t h r o u g h t h e m j u s t as w a t e r is d i f f u s e d
through a jelly.
G r a h a m m a d e m a n y d e t e r m i n a t i o n s o f t h e r e l a t i v e diffu-
s i b i l i t y o f d i f f e r e n t salts. Accurate determinations o f the
coefficient o f diffusion o f l i q u i d s a n d gases are v e r y much
w a n t e d , as t h e y furnish important data for the molecular
theory o f these bodies. T h e most valuable determinations
o f this k i n d a r e t h o s e o f t h e c o e f f i c i e n t o f d i f f u s i o n b e t w e e n
pairs o f s i m p l e g a s e s m a d e by P r o f e s s o r J. Loschmidt of
1
Vienna.
H e has d e t e r m i n e d the coefficient o f diffusion in square
metres per hour for ten pairs o f the m o s t i m p o r t a n t gases.
W e shall c o n s i d e r t h e s e results w h e n w e c o m e t o t h e m o l e
cular t h e o r y o f g a s e s .
C H A P T E R XX.
CAPILLARITY.
WE have hitherto considered the energy of a body as

d e p e n d i n g o n l y o n its t e m p e r a t u r e and its volume. The
w h o l e o f the e n e r g y o f gases, a n d the most important part o f
t h e e n e r g y o f l i q u i d s , m a y b e e x p r e s s e d in t h i s w a y , b u t a
1
F.xperimental-Untersuchungen über die Diffusion von Gasen ohne
poröse Scheidewände Sitzb. d. k. Akad. d. Wissensch. 13d, bei.
(March and July 1870.) (See A p p e n d i x . )

28o Capillarity.
very important part o f the energy of a solid b o d y may

depend on the form w h i c h it is c o m p e l l e d t o a s s u m e as
w e l l as o n its v o l u m e . We shall return to this subject
w h e n t r e a t i n g o f E l a s t i c i t y a n d V i s c o s i t y , b u t w e shall c o n
s i d e r at present that part o f the energy o f a liquid which
d e p e n d s o n t h e n a t u r e a n d e x t e n t o f its surface.
I n m a n y cases t w o substances w h e n p l a c e d in contact d o
n o t diffuse i n t o e a c h other, and w h e n w e attempt to mix
t h e m t h e y s e p a r a t e f r o m e a c h o t h e r w h e n left t o t h e m s e l v e s .
T h u s , i f w e m i x w a t e r w i t h a l c o h o l t h e l i q u i d s diffuse into
each other. I f w e n o w attempt to m i x oil with the alcohol
a n d water, the t w o liquids separate f r o m each other o f t h e m
s e l v e s , a n d i n t h e a c t o f s e p a r a t i o n sufficient f o r c e is b r o u g h t
i n t o p l a y t o set i n m o t i o n c o n s i d e r a b l e m a s s e s o f the fluids,
e s p e c i a l l y w h e n , as i n P l a t e a u ' s experiments, the mixture
o f a l c o h o l a n d w a t e r is o f t h e s a m e d e n s i t y as t h e o i l .
T h e w o r k required to produce these motions must be
derived from t h e s y s t e m itself, as n o w o r k is d o n e o n i t by
external agency.
T h e s y s t e m o f t w o fluids m u s t t h e r e f o r e h a v e m o r e e n e r g y
w h e n the fluids are m i x e d than w h e n t h e y are separated.
N o w the o n l y difference b e t w e e n t h e s e t w o s t a t e s is o n e
of arrangement; a greater n u m b e r o f particles o f either fluid
b e i n g c l o s e t o t h e surface o f s e p a r a t i o n when the fluids are
m i x e d than w h e n they are separate.
We therefore c o n c l u d e that the energy o f a particle of
e i t h e r fluid is g r e a t e r w h e n i t is v e r y c l o s e t o t h e surface
o f t h a t fluid t h a n w h e n i t i s at a g r e a t e r d i s t a n c e f r o m the
surface. I t is p r o b a b l e t h a t i t is o n l y w i t h i n a distance of
a t h o u s a n d t h o f a m i l l i m e t r e o r l e s s f r o m t h e surface t h a t this
i n c r e a s e o f e n e r g y is s e n s i b l e .
O n e effect o f this w i l l b e t h a t t h e p a r t i c l e s near the sur
face will b e drawn inwards towards the mass o f their o w n
f l u i d ; b u t as this f o r c e a c t s e q u a l l y o n a l l t h e s u r f a c e par
ticles, it will o n l y increase the internal pressure b y a constant
quantity, a n d n o v i s i b l e effect will b e p r o d u c e d .
W e m a y calculate the w h o l e e n e r g y o f the system o f t w o

Capillarity. 28l
fluids i f w e k n o w their arrangement. Each fluid occupies
t h e s a m e t o t a l v o l u m e i n w h a t e v e r w a y i t is a r r a n g e d ; and
if the energy o f e v e r y particle w e r e the same, the total e n e r g y
would not d e p e n d o n the arrangement.
Since, h o w e v e r , the particles in a v e r y thin stratum c l o s e
t o t h e surface o f s e p a r a t i o n have greater energy than those
i n t h e i n t e r i o r o f t h e fluid m a s s , t h e e x c e s s o f e n e r g y d u e t o
this c a u s e w i l l b e p r o p o r t i o n a l t o t h e t o t a l a r e a o f t h e sur
face o f separation.
H e n c e the e n e r g y o f the system consists o f t w o parts : the
first d e p e n d s o n the v o l u m e , temperature, & c . o f the fluids,
a n d is u n a f f e c t e d b y t h e f o r m o f t h e i r s u r f a c e . The second
is p r o p o r t i o n a l t o the area o f the surface separating the
two fluids.
I t is o n this s e c o n d p a r t o f t h e e n e r g y t h a t t h e p h e n o m e n a
o f what is called capillary attraction depend.
I n the case o f a s o a p - b u b b l e t h e e n e r g y is g r e a t e r the
g r e a t e r t h e e x t e n t o f surface e x p o s e d t o air. T h e amount o f
this e n e r g y f o r a s o a p - b u b b l e at o r d i n a r y t e m p e r a t u r e s is,
according to Plateau, about 5 '6 g r a m m e - m e t r e s p e r square
metre in gravitation units. T h i s is t h e amount of work
required to b l o w a soap b u b b l e w h o s e superficial extent is
one square metre. A s t h e s o a p - b u b b l e has two surfaces
e x p o s e d t o air, t h e e n e r g y o f a s i n g l e s u r f a c e is o n l y 2 8
gramme-metres per square metre.
We shall call this the superficial energy o f the soap-
bubble. I t is m e a s u r e d b y the e n e r g y in u n i t o f surface,
a n d its d i m e n s i o n s w h e n expressed in d y n a m i c a l measure
are therefore :
2
energy L M 1
M
area T 2
L 2
T 2
or it is o f o n e d i m e n s i o n as r e g a r d s m a s s , a n d o f t w o d i m e n
sions i n v e r s e l y a s r e g a r d s t i m e , a n d i t is i n d e p e n d e n t o f t h e
unit o f l e n g t h . Superficial e n e r g y depends o n the nature
of both the media o f which the surface i s a boundary.
T h e m e d i a m u s t b e s u c h as d o n o t m i x w i t h e a c h other,
otherwise diffusion occurs, and the surface o f separation
becomes indefinite; but t h e r e is a c o e f f i c i e n t o f superficial
282 Capillarity.
e n e r g y for e v e r y surface w h i c h separates two liquids which

d o n o t m i x — a l i q u i d a n d a g a s , o r its o w n v a p o u r ; a n d for
t h e surface w h i c h s e p a r a t e s a l i q u i d a n d a s o l i d , w h e t h e r it
dissolves the solid or n o t T h e r e is also a coefficient of
superficial energy for the surface s e p a r a t i n g a gas and a
s o l i d , o r t w o s o l i d s ; b u t as a n y t w o g a s e s diffuse into each
other, t h e y can h a v e n o surface o f separation.
Superficial Tension.
W h e n t h e a r e a o f t h e s u r f a c e is i n c r e a s e d i n a n y w a y , w o r k
m u s t b e d o n e ; a n d w h e n t h e s u r f a c e is a l l o w e d t o c o n t r a c t ,
it d o e s w o r k o n o t h e r b o d i e s . H e n c e it a c t s l i k e a s t r e t c h e d
sheet o f india-rubber, a n d exerts a tension o f the s a m e kind.
The only difference is, t h a t the tension in the sheet of
india-rubber d e p e n d s on the a m o u n t o f stretching, a n d m a y
be greater in one direction than in a d i r e c t i o n at right
a n g l e s t o it, w h e r e a s t h e t e n s i o n i n t h e s o a p - b u b b l e r e m a i n s
t h e s a m e h o w e v e r m u c h t h e film is e x t e n d e d , a n d t h e t e n s i o n
a t a n y p o i n t is t h e s a m e i n all d i r e c t i o n s .
I f w e d r a w a s t r a i g h t l i n e , p Q, a c r o s s t h e s u r f a c e A B D c , '
and if the w h o l e tension exerted b y
F I G . 35.
1k 5 c the surface a c r o s s the line P Q is
a
F, t h e n the superficial tension is
measured b y t h e t e n s i o n across unit
B b — ' o f l e n g t h o f t h e l i n e p Q ; or, s i n c e F
a is t h e t e n s i o n a c r o s s t h e w h o l e l i n e ,
~ 1
i f T is t h e s u p e r f i c i a l t e n s i o n across
unit o f length,
F = T . P Q.
Now l e t us s u p p o s e t h a t t h e lines A B and c D were
originally in contact, and that t h e surface A B D C was
p r o d u c e d b y d r a w i n g c D away from A B b y the action o f
t h e f o r c e F.
I f w e s u p p o s e A B a n d B C t o b e r o d s w e t w i t h soapsuds,
placed b e t w e e n t w o parallel rods A c and B D and then
d r a w n asunder, the soap film A B D C will b e formed. If s

Superficial Tension. 283
is t h e s u p e r f i c i a l e n e r g y o f the film per u n i t o f area, t h e n

the w o r k d o n e in d r a w i n g it out will b e s . A B . A C. But i f
F is t h e f o r c e r e q u i r e d t o d r a w A B f r o m c D, t h e s a m e w o r k
m a y b e w r i t t e n F . A c, or, p u t t i n g f o r F its v a l u e i n t e r m s o f
T , a n d e q u a t i n g the t w o expressions for the w o r k ,
S . AB . AC = T . I'Q . A C
or = T . A B . AC-
Hence
S = T,
or the numerical value o f the superficial e n e r g y p e r unit

o f a r e a is e q u a l t o t h a t o f t h e superficial t e n s i o n p e r u n i t of
length. This q u a n t i t y is u s u a l l y c a l l e d t h e Coefficient of
C a p i l l a r i t y , b e c a u s e it w a s first c o n s i d e r e d w i t h r e f e r e n c e t o
the a s c e n t o f liquids in capillary tubes. T h e s e tubes de
rived their n a m e from the smallness o f their bore, which
w o u l d only admit a hair (capilla). I h a v e used the phrases
' superficial e n e r g y ' a n d ' s u p e r f i c i a l t e n s i o n ' b e c a u s e I t h i n k
they help us to direct our attention to the facts, a n d to
understand the various p h e n o m e n a o f l i q u i d surfaces better
than a name which is purely technical, and which has
already d o n e a great deal o f harm w h e n used without being
understood. I f b y t h e h e l p o f this treatise, o r o t h e r w i s e , a n y
o n e has o b t a i n e d a c l e a r c o n c e p t i o n o f t h e r e a l phenomena
called Capillary Attraction and Capillarity, he may use
these w o r d s quite freely. The t h e o r y as w e shall state i t
does not differ essentially from that originally given by
L a p l a c e , t h o u g h b y t h e f r e e use o f the i d e a o f superficial
tension we avoid some of the mathematical operations
which are required to deduce the phenomena from the
hypothesis o f molecular attractions.
We shall n o w suppose that the superficial tension is

known for the surfaces which bound every pair of the
media with which w e have to do. For instance, w e may
denote by the superficial tension o f the surface which
s e p a r a t e s t h e m e d i u m a f r o m t h e m e d i u m b.

284 Capillarity.
L e t t h e r e b e t h r e e fluid m e d i a , a, b, c, a n d l e t t h e surface o f
separation b e t w e e n a and b m e e t the surface of separation
b e t w e e n b and c along a line o f any form having continuous
curvature. L e t o b e a p o i n t in this line, a n d let the p l a n e
o f the paper represent a section perpendicular to the line.
The three tensions T n 4 , Tj,., and TCU must be in equili
b r i u m a l o n g this l i n e , a n d , since w e k n o w these tensions,
we can easily determine the angles w h i c h they m a k e with
each other. I n fact, i f w c c o n s t r u c t a t r i a n g l e A B C h a v i n g
l i n e s p r o p o r t i o n a l t o t h e s e t e n s i o n s f o r its s i d e s , t h e e x t e r i o r
a n g l e s o f this t r i a n g l e w i l l b e e q u a l t o t h e a n g l e s f o r m e d b y
t h e t h r e e surfaces o f s e p a r a t i o n w h i c h m e e t i n a l i n e .
B y trigonometry, i f A B C are the angles o f the edges
f o r m e d b y t h e m e d i a ab c, t h e n
sin A sin B sin c
I t appears f r o m this that w h e n e v e r three fluid m e d i a are
Fig. 36.
in contact and in equilibrium, the angles between their

surfaces o f separation depend only on the v a l u e s o f the
superficial tensions o f these three surfaces, and are there
fore a l w a y s the s a m e for the s a m e three fluids.
B u t i t is n o t always possible to construct a triangle with

Angles of Contact of Three Fluids. 285
t h r e e g i v e n l i n e s as its s i d e s . I f any one o f the l i n e s is

greater than the sum o f the other t w o , the triangle cannot b e
formed. F o r the s a m e reason, i f a n y o n e o f the three super
ficial t e n s i o n s is g r e a t e r t h a n t h e sum o f t h e o t h e r t w o , t h e
t h r e e fluids c a n n o t b e i n e q u i l i b r i u m i n c o n t a c t .
F o r instance, i f the tension o f t h e surface s e p a r a t i n g air
a n d w a t e r is g r e a t e r t h a n t h e sum o f the tensions o f the
surfaces separating air and oil, and oil and water, then a
d r o p o f o i l c a n n o t b e i n e q u i l i b r i u m o n t h e surface o f w a t e r .
T h e e d g e o f the drop, where the o i l m e e t s the air and the
water, b e c o m e s thinner and thinner ; but even when the
a n g l e is r e d u c e d t o t h e t h i n n e s t e d g e , t h e t e n s i o n o f t h e free
s u r f a c e o f t h e w a t e r e x c e e d s t h e t e n s i o n s o f t h e t w o surfaces
o f the o i l , s o t h a t t h e o i l is d r a w n o u t t h i n n e r a n d thinner,
till it c o v e r s a v a s t e x p a n s e o f w a t e r . I n fact, t h e process
m a y g o o n till the o i l b e c o m e s so thin, a n d contains so
small a number o f m o l e c u l e s i n its t h i c k n e s s , that it no
l o n g e r has t h e p r o p e r t i e s o f t h e l i q u i d i n m a s s .
W h e n a s o l i d b o d y is i n c o n t a c t w i t h t w o fluids, then i f
the tension o f the surface separating the solid from the first
fluid e x c e e d s t h e sum o f t h e t e n s i o n s o f t h e o t h e r t w o sur
faces, the first fluid will gather itself up into a drop, and
the second will spread over the surface. If one of the
fluids is air, and the other a liquid, then t h e l i q u i d , i f it
c o r r e s p o n d s t o t h e first f l u i d mentioned above, will stand
in d r o p s w i t h o u t w e t t i n g t h e s u r f a c e ; b u t i f it corresponds
to the second, it w i l l s p r e a d i t s e l f o v e r t h e w h o l e surface,
and wet the solid.
W h e n t h e t e n s i o n o f t h e surface s e p a r a t i n g t h e t w o fluids
is g r e a t e r t h a n t h e d i f f e r e n c e o f t h e t e n s i o n s o f t h e surfaces
s e p a r a t i n g t h e m f r o m t h e s o l i d , t h e n t h e surface o f s e p a r a t i o n
o f the t w o f l u i d s w i l l b e i n c l i n e d at a finite angle to the
surface o f t h e s o l i d . T h u s , i f a a n d b a r e t h e t w o fluids, a n d c
the s o l i d , t h e n t o find t h e angle o f contact P O Q w e must
make p o = T„,„ a n d o Q = T 6 C — T.
ac T h i s a n g l e is c a l l e d
the a n g l e o f c a p i l l a r i t y .

286 Capillarity
O N T H E RISE O F A LIQUID I N A T U B E .
Let a b e a l i q u i d i n a t u b e o f a s u b s t a n c e c, w h o s e r a d i u s
F i g . 37. is r. L e t the fluid b be air or any
other fluid. L e t a be the a n g l e o f ca
pillarity. The circumference of the
t u b e is 2 7T r. A l l r o u n d this circum
f e r e n c e t h e r e is a t e n s i o n T ab a c t i n g at
an a n g l e i n c l i n e d a to t h e v e r t i c a l , and
t h e r e f o r e t h e w h o l e v e r t i c a l f o r c e is
2 it r T^j c o s a.
1l
If this f o r c e raises the liquid to a
h e i g h t h, t h e n , n e g l e c t i n g t h e w e i g h t o f
the sides o f the h o l l o w p o r t i o n x Y Z,
t h e w e i g h t o f fluid s u p p o r t e d is
3
tv p g r A.
Equating this force to the weight
A w h i c h it s u p p o r t s , w e find
A = 2 £>»_£21? .
Pgr
Hence the height to which the fluid is drawn up is
i n v e r s e l y as t h e r a d i u s o f t h e t u b e .
A l i q u i d is d r a w n up in the s a m e w a y in the space be
t w e e n t w o p a r a l l e l p l a t e s s e p a r a t e d b y a d i s t a n c e d. I f we
now s u p p o s e fig. 38 t o r e p r e s e n t a s e c t i o n o f t h e film o f l i q u i d ,
t h e h o r i z o n t a l b r e a d t h o f w h i c h is / , t h e n t h e surface-tension
of the liquid on the line which bounds the wet and dry
p a r t s o f e a c h p l a t e is T /, a n d this f o r c e a c t s a t an angle a
with the vertical. T h e w h o l e force, therefore, arising from
t h e s u r f a c e - t e n s i o n , a n d t e n d i n g t o r a i s e t h e l i q u i d , is
2 T / COS a.
The w e i g h t o f t h e l i q u i d r a i s e d is
p g h I d.
Equating the force to the w e i g h t w h i c h it supports, w e
find

in Relation to Evaporation and Condensation. 287
* , T cos a
h = 2 .
?gd
This expression differs f r o m that for the height in a
cylindrical tube o n l y b y the s u b s t i t u t i o n o f d, t h e distance
between the parallel p l a t e s , f o r r, t h e radius o f the tube.
Hence the height to which a liquid will ascend between
t w o p l a t e s is e q u a l t o t h e h e i g h t t o w h i c h it rises i n a t u b e
w h o s e r a d i u s is e q u a l to the distance b e t w e e n the plates,
o r w h o s e d i a m e t e r is t w i c e t h a t d i s t a n c e .
A remarkable a p p l i c a t i o n o f the principles of thermo
dynamics to capillary phenomena has r e c e n t l y b e e n made
1
b y Sir W . T h o m s o n . L e t a fine t u b e b e
p l a c e d in a liquid, a n d let the w h o l e be
placed i n a v e s s e l f r o m w h i c h air is ex
hausted, so that t h e w h o l e space above
the l i q u i d b e c o m e s f i l l e d w i t h its v a p o u r
and nothing else.
L e t the permanent level o f the liquid
b e at A i n t h e s m a l l tube, a n d at B in the
vessel, a n d let us suppose the tempera
ture the s a m e t h r o u g h o u t t h e a p p a r a t u s .
T h e r e is a s t a t e o f e q u i l i b r i u m b e t w e e n
t h e l i q u i d a n d its v a p o u r , b o t h at yi a n d at
B ; otherwise evaporation or condensa
tion would occur, and the permanent
state w o u l d n o t e x i s t .
N o w t h e p r e s s u r e o f t h e v a p o u r at B e x c e e d s t h a t at A b y
the pressure due to a c o l u m n o f the vapour o f the height
A B.
It follows that the vapour is i n equilibrium with the
l i q u i d at a l o w e r p r e s s u r e w h e r e t h e surface o f t h e l i q u i d is
c o n c a v e , as a t A , t h a n w h e r e it is p l a n e , as at B.
N o w let the lower end o f the tube b e closed, and let
s o m e o f t h e l i q u i d b e t a k e n o u t o f it, so that t h e l i q u i d in t h e
t u b e d o e s n o t r e a c h u p t o t h e p o i n t A.
• Proceedings of the Royal Society of Edinburgh, F e b . 7, 1870.

288 Capillarity.
T h e n v a p o u r will c o n d e n s e i n s i d e the tube, o w i n g to the
c o n c a v i t y o f its s u r f a c e , a n d this w i l l g o o n till i t is filled
with liquid up t o t h e l e v e l A , t h e s a m e as i f it h a d been
o p e n at the b o t t o m .
H e n c e , i f at a n y p o i n t o f a c o n c a v e l i q u i d _surface r a n d
1
r a r e t h e p r i n c i p a l r a d i i o f c u r v a t u r e o f t h e surface, a n d i f
the pressure o f v a p o u r i n e q u i l i b r i u m w i t h a p l a n e surface
o f its l i q u i d at t h e g i v e n t e m p e r a t u r e is CT, a n d i f p is t h e
pressure o f equilibrium o f the vapour in contact with the
curved surface,
where a is t h e density o f the vapour, and p that of the

liquid.
I f h is t h e h e i g h t t o w h i c h t h e l i q u i d w o u l d r i s e i n v i r t u e
o f t h e c u r v a t u r e o f its s u r f a c e i n a c a p i l l a r y t u b e , a n d i f <§
is t h e h e i g h t o f a h o m o g e n e o u s a t m o s p h e r e o f t h e v a p o u r ,
Sir W. T h o m s o n has calculated that in a tube whose

r a d i u s is a b o u t a thousandth o f a millimetre, and in which
water would rise about thirteen metres a b o v e the plane
ler-el, t h e e q u i l i b r i u m p r e s s u r e o f a q u e o u s v a p o u r w o u l d b e
l e s s t h a n t h a t o n a p l a n e surface o f w a t e r b y a b o u t a thou
s a n d t h o f its o w n a m o u n t .
He thinks it p r o b a b l e that the moisture w h i c h v e g e t a b l e
substances, s u c h as c o t t o n , c l o t h , & c , a c q u i r e f r o m a i r at
temperatures far a b o v e t h e d e w p o i n t m a y b e e x p l a i n e d b y
the c o n d e n s a t i o n o f w a t e r in the n a r r o w tubes a n d cells o i
t h e v e g e t a b l e structure.
I n t h e c a s e o f a s p h e r i c a l b u b b l e o f s t e a m in w a t e r , the
increase or diminution o f the diameter depends on the
temperature and pressure o f the v a p o u r w i t h i n ; and the
condition that ebullition m a y t a k e p l a c e is t h a t t h e pres
sure o f saturated v a p o u r at the temperature o f the liquid

Conditions of Boiling. 289
must e x c e e d the actual pressure o f the l i q u i d b y a pressure

equal to that o f a column of the liquid o f the height to
w h i c h it w o u l d a s c e n d i n a t u b e w h o s e s e c t i o n is e q u a l to
that o f the bubbles.
I f the liquid contains any gas in solution, or any liquid
more volatile than itself, o r i f air or steam is made to
bubble up through the liquid, then bubbles will b e formed
of a visible diameter, and the ebullition will b e k e p t up b y
e v a p o r a t i o n at t h e s u r f a c e o f t h e s e b u b b l e s . B u t if, b y l o n g
b o i l i n g o r o t h e r w i s e , t h e l i q u i d is d e p r i v e d o f a n y s u b s t a n c e
m o r e v o l a t i l e t h a n itself, a n d i f t h e s i d e s o f t h e v e s s e l i n w h i c h
i t is c o n t a i n e d a r e s u c h that the liquid adheres closely to
t h e m , so t h a t b u b b l e s , i f f o r m e d a t t h e s u r f a c e o f t h e v e s s e l ,
will rather c o l l e c t i n t o a spherical form than spread along
the surface, then the temperature o f the liquid m a y be
raised far a b o v e the boiling point, a n d w h e n b o i l i n g at
last occurs, it g o e s on in an almost explosive manner,
and the liquid ' bumps' violently on the bottom o f the
vessel.
The highest temperature to which water may be raised

under the a t m o s p h e r i c pressure without ebullition c a n n o t b e
said to b e accurately k n o w n , for e v e r y i m p r o v e m e n t in the
a r r a n g e m e n t s for g e t t i n g rid o f c o n d e n s e d air, & c , h a s m a d e
it p o s s i b l e t o r a i s e l i q u i d w a t e r to a higher temperature,
I n an e x p e r i m e n t d u e t o Dufour, t h e water, instead o f b e i n g
a l l o w e d to touch the s i d e s o f t h e v e s s e l , is d r o p p e d i n t o a
mixture o f linseed oil and oil o f c l o v e s , w h i c h has nearly
the s a m e d e n s i t y as itself. B y this m e a n s , d r o p s o f liquid
w a t e r m a y s o m e t i m e s b e o b s e r v e d s w i m m i n g in t h e m i x t u r e
at a temperature of 356° F. The pressure of aqueous
vapour is at this t e m p e r a t u r e nearly ten atmospheres, or
a b o u t 147 p o u n d s w e i g h t o n t h e square inch. H e n c e the
cohesion o f the water must be able to support at l e a s t 132
pounds w e i g h t o n the square inch.
We may also a p p l y Sir W . T h o m s o n ' s principle to the
case o f e v a p o r a t i o n f r o m a small drop. In this case the
u

29« Capillarity.
surface o f t h e l i q u i d is c o n v e x , s o t h a t i f r is t h e r a d i u s o f
the drop,
p = W + T •
p— a r
H e r e <a is t h e p r e s s u r e o f s a t u r a t e d v a p o u r corresponding
t o the t e m p e r a t u r e w h e n t h e s u r f a c e o f t h e l i q u i d is p l a n e ,
' a n d p is the pressure of vapour required to prevent the
drop from evaporating. A small drop will therefore evapo
r a t e i n air c o n t a i n i n g so m u c h moisture that condensation
w o u l d t a k e p l a c e o n a flat surface.
Hence, if a vapour free from suspended particles, and
not in contact with any solid body e x c e p t such as are
w a r m e r t h a n itself, is c o o l e d b y e x p a n s i o n , it is probable
that the s u g g e s t i o n o f P r o f . J. T h o m s o n at p . 126 might
b e verified, and that the vapour might be cooled below its
o r d i n a r y p o i n t o f c o n d e n s a t i o n w i t h o u t l i q u e f a c t i o n , f o r the
first e f f e c t o f c o n d e n s a t i o n w o u l d b e t o p r o d u c e excessively
s m a l l d r o p s , a n d t h e s e , as w e h a v e s e e n , w o u l d n o t t e n d t o
increase unless the vapour surrounding them were more
than saturated.
The formation o f c l o u d in vapour often appears very

s u d d e n , as i f i t h a d b e e n at first r e t a r d e d b y s o m e c a u s e o f
t h i s k i n d , s o t h a t w h e n at l a s t t h e c l o u d is f o r m e d c o n d e n
s a t i o n o c c u r s w i t h g r e a t r a p i d i t y , r e m i n d i n g us o f the con
verse phenomenon o f the rapid b o i l i n g o f an overheated
liquid.
T h e d r o p s in a c l o u d , f o r t h e s a m e r e a s o n , c a n n o t remain
o f the s a m e size, e v e n i f t h e y are n o t j o s t l e d against each
o t h e r , f o r the smaller drops will e v a p o r a t e , w h i l e the larger
ones are increased b y condensation, so that v i s i b l e drops
will b e f o r m e d b y pure c o n d e n s a t i o n without a n y necessity
for the c o a l e s c e n c e o f smaller drops.
Up t o this p o i n t w e h a v e not considered the effect of
h e a t on the superficial tension o f liquids. I n all liquids on
which experiments have been made the superficial tension
diminishes as t h e t e m p e r a t u r e rises, b e i n g g r e a t e s t at the

Cooling of a Liquid Film by Extension. 291
freezing point o f the substance, a n d vanishing altogether at

t h e c r i t i c a l p o i n t w h e r e t h e l i q u i d a n d g a s e o u s states b e c o m e
continuous.
I t appears, therefore, that the p h e n o m e n o n is i n t i m a t e l y
related to the apparent discontinuity o f the liquid and
gaseous states, a n d that it must b e studied in connexion
with the conditions of evaporation and the phenomenon
called latent heat. M u c h light will probably b e thrown on
all these subjects b y i n v e s t i g a t i o n s w h i c h as y e t c a n h a r d l y
b e said t o b e b e g u n .
Sir W . T h o m s o n has a p p l i e d the principres of thermo
dynamics t o t h e c a s e o f a film o f w a t e r e x t e n d e d b y a f o r c e
a p p l i e d t o it, a n d has s h o w n that in order to maintain the
temperature o f the film constant an amount o f heat mus1
b e supplied t o it nearly equal in d y n a m i c a l measure to half
the w o r k d o n e in stretching the film.
I n fact, t h e third thermodynamical r e l a t i o n ( p . 168) m a y
b e a p p l i e d at once to the case by making the following
substitutions : for ' p r e s s u r e ' put ' superficial tension,' and.
for ' v o l u m e ' p u t 'area.'
W e thus find t h a t t h e l a t e n t heat of extension o f unit o f
a r e a is e q u a l to the product o f the absolute temperature
and the d e c r e m e n t o f superficial tension p e r d e g r e e o f t e m
perature. A t o r d i n a r y t e m p e r a t u r e s it appears f r o m e x p e r i
m e n t t h a t this p r o d u c t is a b o u t h a l f t h e s u p e r f i c i a l t e n s i o n .
H e n c e the latent heat o f extension in d y n a m i c a l measure
is a b o u t h a l f t h e w o r k s p e n t i n p r o d u c i n g t h e e x t e n s i o n .
The student m a y also a d a p t the investigation o f latent
h e a t as g i v e n at p . 173 to the case o f the extension of a
liquid film.
T h e following table, taken from the m e m o i r o f M . Quincke,
gives the superficial tension o f different liquids in contact
w i t h air, w a t e r , a n d mercury. T h e tension is m e a s u r e d in
grammes w e i g h t per linear metre, and the temperature is
20° C.
U2
2G2 Capillarity.
Table of Superficial Tension at 2O C. 0
TENSION OF SURFACE SEPARATING

LIQUID SP. GRAVITY THE LIQUID FROM
AIR WATER MERCURY
Water . . . . I O 8-253 0 42-58
42-58
MERCURY . . . . I3-543Z 55 ° 3
4-256
O
BISULPHIDE of Carbon . X -2687

,2
3 74 37-97
CHLOROFORM 1-4878 3-120 3-010 40-71
0-7906 2-599 40-71
ALCOHOL . . . . 0-9136 3-760
—
2-096
OLIVE OIL . 34-19
TURPENTINE 0-8867 3-030 I-I77 Z5'54
07977 3-233 2-834 28-94
PETROLEUM . . . . I-I 7-15
HYDROCHLORIC ACID —
SOLUTION of HYPOSULPHITE OF
1 -1248 7-903 45-n
SODA . . . .
It appears from this table that w a t e r has the greatest

superficial tension o f all ordinary liquids. F o r this r e a s o n it
is v e r y d i f f i c u l t t o p r e s e r v e a surface of pure water. It is
sufficient to touch any part o f the surface o f pure water
w i t h a g r e a s e d r o d t o r e d u c e its t e n s i o n considerably. The
smallest quantity o f any kind o f o i l i m m e d i a t e l y spreads
itself o v e r t h e surface, a n d c o m p l e t e l y alters the superficial
tension. H e n c e t h e i m p o r t a n c e i n all e x p e r i m e n t s o n super
ficial tension o f having the vessel thoroughly clean. This
h a s b e e n w e l l p o i n t e d o u t b y M r . T o m l i n s o n in his r e s e a r c h e s
o n the ' c o h e s i o n figures of liquids.'
W h e n o n e o f t h e l i q u i d s is s o l u b l e i n t h e o t h e r , t h e effects
o f superficial tension are very remarkable. F o r instance, if
a d r o p o f a l c o h o l b e p l a c e d o n the surface o f a thin l a y e r o f
water, the tension is i m m e d i a t e l y r e d u c e d t o 2-6, w h e r e the
a l c o h o l is p u r e , a n d v a i i e s f r o m this v a l u e t o 8-25, w h e r e the
w a t e r is p u r e . T h e r e s u l t is t h a t t h e e q u i l i b r i u m o f t h e sur
f a c e is d e s t r o y e d , a n d t h e s u p e r f i c i a l film o f t h e l i q u i d is set
in m o t i o n f r o m the a l c o h o l t o w a r d s the water, and i f the
w a i e r is shallow this m o t i o n o f the surface w i l l d r a g the
w h o l e o f the water with it, s o as to lay bare part o f the
bottom o f the vessel. A dimple may be formed on the

Tears of Strong Wine. 293
surface o f w a t e r b y b r i n g i n g a d r o p o f e t h e r c l o s e t o t h e sur
face. T h e vapour o f the ether condensed o n the surface
of the water is sufficient to cause the outward current
mentioned above.
W i n e c o n t a i n s a l c o h o l a n d w a t e r , a n d w h e n it is e x p o s e d t o
t h e air t h e a l c o h o l e v a p o r a t e s faster t h a n t h e w a t e r , s o that
the superficial l a y e r b e c o m e s w e a k e r . W h e n t h e w i n e is in a
d e e p v e s s e l , t h e s t r e n g t h is r a p i d l y e q u a l i z e d b y diffusion ;
but in the case o f the thin l a y e r o f w i n e w h i c h adheres to
the sides o f a wineglass, the liquid rapidly becomes more
watery. T h i s increases the superficial tension at the sides
o f t h e g l a s s , a n d c a u s e s t h e surface t o be dragged from the
strong wine to the weak. The w a t e r y p o r t i o n is always
u p p e r m o s t , a n d c r e e p s u p t h e s i d e s o f t h e glass, d r a g g i n g t h e
s t r o n g e r w i n e after i t till t h e q u a n t i t y o f t h e f l u i d b e c o m e s so
great that t h e different p o r t i o n s m i x , a n d t h e d r o p runs d o w n
the s i d e .
T h i s p h e n o m e n o n , k n o w n as t h e t e a r s o f s t r o n g w i n e , w a s
first e x p l a i n e d o n t h e s e p r i n c i p l e s b y P r o f e s s o r J a m e s T h o m
son. I t is p r o b a b l e t h a t i t is r e f e r r e d t o in Proverbs xxiii.
31, as a n i n d i c a t i o n o f t h e s t r e n g t h o f t h e w i n e . T h e m o t i o n
c e a s e s i n a s t o p p e r e d b o t t l e as s o o n as e n o u g h o f v a p o u r o f
a l c o h o l has b e e n f o r m e d in the bottle to b e in equilibrium
with the liquid a l c o h o l in the wine.
T h e fatty oils h a v e a greater superficial tension than tur
pentine, b e n z o l , or ether. H e n c e i f t h e r e is a g r e a s y s p o t o n
a p i e c e o f c l o t h , a n d i f o n e s i d e o f i t is w e t t e d w i t h o p e of
these substances, t h e tension is g r e a t e s t o n t h e s i d e of the
grease, a n d the p o r t i o n s consisting o f mixtures o f b e n z o l and
grease m o v e from the b e n z o l towards the grease.
I f i n o r d e r t o c l e a n s e the_ g r e a s e - s p o t w e b e g i n b y w e t t i n g
the m i d d l e o f t h e s p o t w i t h b e n z o l , w e d r i v e a w a y t h e g r e a s e
i n t o the c l e a n part o f the cloth. T h e benzol should there
f o r e b e a p p l i e d first i n a r i n g a l l r o u n d t h e s p o t , a n d gradu
ally brought nearer t o the centre o f the spot, and a fibrous
s u b s t a n c e , s u c h as b l o t t i n g - p a p e r , s h o u l d b e p l a c e d in c o n t a c t

with the c l o t h , go t h a t w h e n t h e grease is c h a s e d by the

b e n z o l t o t h e m i d d l e o f t h e s p o t it m a y m a k e its e s c a p e i n t o
the blotting-paper, instead o f remaining in globules o n the
surface, r e a d y to return into the cloth when the benzol
evaporates.
Another v e r y effectual method o f g e t t i n g rid o f g r e a s e -
s p o t s is f o u n d e d o n t h e f a c t t h a t t h e s u p e r f i c i a l t e n s i o n o f a
substance always diminishes as the temperature rises. If,
t h e r e f o r e , t h e t e m p e r a t u r e is d i f f e r e n t a t d i f f e r e n t p a r t s o f a
g r e a s y cloth, the g r e a s e tends t o m o v e from the h o t parts to
the cold. W e t h e r e f o r e a p p l y a h o t i r o n t o One s i d e o f the
cloth, and blotting-paper to the other, a n d the grease is
driven into the blotting-paper. I f t h e r e is b l o t t i n g - p a p e r o n
b o t h s i d e s it w i l l b e f o u n d t h a t t h e g r e a s e is driven mainly
into that o n the o p p o s i t e side f r o m the h o t iron.
C H A P T E R X X I .
ON ELASTICITY A N D VISCOSITY.
On Stresses and Strains.

WHEN the form of a connected s y s t e m is altered in any
way, the alteration o f f o r m is c a l l e d a S t r a i n . The force
or system o f f o r c e s b y w h i c h this strain is produced or
m a i n t a i n e d is c a l l e d t h e S t r e s s c o r r e s p o n d i n g t o t h e strain.
T h e r e are different k i n d s o f strains, a n d d i f f e r e n t k i n d s o f
stresses c o r r e s p o n d i n g t o t h e m .
The o n l y c a s e w h i c h w e h a v e h i t h e r t o c o n s i d e r e d is that
in w h i c h the three longitudinal stresses a r e equal. This
kind o f stress is called Hydrostatic Pressure, and is the
only kind w h i c h c a n e x i s t i n a fluid at rest. T h e pressure
is t h e s a m e in w h a t e v e r d i r e c t i o n it is e s t i m a t e d .

Shearing Stress. 295
A v e r y i m p o r t a n t k i n d o f stress is c a l l e d S h e a r i n g Stress :
it is c o m p o u n d e d o f t w o e q u a l l o n g i - Fir,. 3 9 .
t u d i n a l stresses, o n e b e i n g a t e n s i o n
and the other a pressure acting at
right angles to each other. When a
p a i r o f scissors
anything, the
shearing stress i n
is e m p l o y e d t o
two blades produce
the material
cut
be
a \
tween them, tending to m a k e
p o r t i o n slide o v e r the other.
W e have n o w to consider the
one
properties
/
b
of bodies when
a c t e d o n b y t h i s k i n d o f stress.
A b o d y which when subjected to a stress e x p e r i e n c e s n o
strain w o u l d , i f it existed, b e c a l l e d a P e r f e c t l y R i g i d Body.
T h e r e a r e n o s u c h b o d i e s , a n d this d e f i n i t i o n is g i v e n o n l y t o
i n d i c a t e w h a t is m e a n t b y p e r f e c t rigidity.
A b o d y w h i c h w h e n s u b j e c t e d t o a g i v e n stress a t a g i v e n
temperature e x p e r i e n c e s a strain o f d e f i n i t e a m o u n t , w h i c h
does not increase w h e n t h e stress is p r o l o n g e d , a n d w h i c h
d i s a p p e a r s c o m p l e t e l y w h e n t h e stress is r e m o v e d , is c a l l e d
a Perfectly Elastic B o d y .
Gases and liquids, and perhaps m o s t solids, are perfectly
e l a s t i c as r e g a r d s stress u n i f o r m i n a l l d i r e c t i o n s , b u t n o s u b
s t a n c e w h i c h has y e t b e e n t r i e d is p e r f e c t l y e l a s t i c as r e g a r d s
s h e a r i n g stress, e x c e p t p e r h a p s f o r e x c e e d i n g l y s m a l l values
o f t h e stress.
N o w s u p p o s e t h a t stresses o f t h e s a m e k i n d , b u t o f con
tinually increasing magnitude, are applied to a body in
succession. A s l o n g as t h e body returns t o its o r i g i n a l
form w h e n the stress is r e m o v e d it is s a i d t o b e p e r f e c t l y
elastic.
I f t h e f o r m o f t h e b o d y is f o u n d t o b e p e r m a n e n t l y a l t e r e d
when t h e stress e x c e e d s a c e r t a i n v a l u e , t h e b o d y is s a i d
to b e soft, o r p l a s t i c , a n d the state o f the body when the
a l t e r a t i o n is j u s t g o i n g t o t a k e p l a c e is c a l l e d t h e L i m i t o f
Perfect Elasticity.

295 Viscosity.
I f t h e stress b e i n c r e a s e d t i l l t h e b o d y b r e a k s o r g i v e s w a y
altogether, the value o f the stress is c a l l e d t h e S t r e n g t h of
t h e b o d y f o r that k i n d o f stress.
I f breaking takes place before there is any permanent
a l t e r a t i o n o f f o r m , t h e b o d y is s a i d t o b e B r i t t l e .
If the stress, when it is maintained constant, causes
a strain or displacement in the body which increases
continually with the time, the substance is said to be
Viscous.
W h e n t h i s c o n t i n u o u s a l t e r a t i o n o f f o r m is o n l y p r o d u c e d
b y stresses e x c e e d i n g a c e r t a i n v a l u e , t h e s u b s t a n c e is c a l l e d
a s o l i d , h o w e v e r soft i t m a y be. When the v e r y smallest
stress, i f continued long enough, will cause a constantly
increasing change o f form, the b o d y must be regarded as
a v i s c o u s fluid, h o w e v e r h a r d it m a y b e .
Thus, a tallow candle is much softer than a stick of
s e a l i n g - w a x ; but if the candle and the stick o f sealing-wax
are laid horizontally between two supports, the sealing-
wax will in a few weeks in s u m m e r bend w i t h its own
weight, while the candle remains straight. The candle is
therefore a soft solid, and the sealing-wax a v e r y viscous
fluid.
What is r e q u i r e d to alter the f o r m o f a soft s o l i d is a
sufficient f o r c e , a n d this, w h e n applied, produces its effect
at o n c e . In the case of a viscous fluid i t is time w h i c h is
required, and if enough time is g i v e n , t h e very smallest
force will p r o d u c e a sensible e f f e c t , such as w o u l d r e q u i r e a
very large force if suddenly applied.
Thus a block o f pitch m a y b e so hard that y o u cannot
make a d i n t in i t b y s t r i k i n g it with your knuckles ; and
yet it w i l l , i n the course o f t i m e , flatten i t s e l f o u t b y its
o w n weight, and g l i d e d o w n hill like a stream o f water.
1
A glass fibre was found by M . F. Kohlrausch to be
come more and m o r e twisted when constantly acted on by
« Fogg. 1863.

Viscous Solids.
the small twisting force arising from the action of the
earth o n a little m a g n e t suspended b y the fibre. I have
found slow changes in the torsion o f a steel wire g o i n g on
for m a n y d a y s after it h a d r e c e i v e d a s l i g h t p e r m a n e n t twist,
1
a n d Sir W . T h o m s o n has i n v e s t i g a t e d t h e v i s c o s i t y o f o t h e r
metals.
T h e r e are instances o f v i s c o s i t y a m o n g v e r y h a r d b o d i e s .
R e t u r n i n g t o o u r f o r m e r e x a m p l e , p i t c h : w e m a y m i x it i n
various proportions with tar so as to form a continuous
series of compounds passing from the apparently solid
c o n d i t i o n o f pitch t o the a p p a r e n t l y fluid c o n d i t i o n o f tar,
which may be taken as a type of a v i s c o u s fluid. By
mixing the tar with turpentine the viscosity m a y be still
further reduced, and so w e m a y f o r m a s e r i e s o f fluids ot
d i m i n i s h i n g v i s c o s i t y t i l l w e a r r i v e a t t h e m o s t m o b i l e fluids,
such as ether.
D E F I N I T I O N O F T H E C O E F F I C I E N T O F VISCOSITY.
C o n s i d e r a stratum o f the substance o f thickness c, c o n

tained between the horizontal fixed plane F j G 4 0
A B and the plane c D, w h i c h is m o v i n g c D
horizontally from c towards D, with the

v e l o c i t y v . L e t us s u p p o s e that t h e s u b s t a n c e
between the two planes is a l s o i n m o t i o n , the stratum in
contact with c D m o v i n g with velocity v , while the velocity
of any intermediate stratum is p r o p o r t i o n a l to its height
a b o v e A B.
The s u b s t a n c e b e t w e e n t h e p l a n e s is u n d e r g o i n g shearing
s t r a i n , a n d t h e r a t e at w h i c h this strain is i n c r e a s i n g is m e a s u r e d
by the v e l o c i t y v o f the upper plane, d i v i d e d b y the distance
c between the planes, or — .
The stress F is a s h e a r i n g stress, a n d is m e a s u r e d b y t h e

horizontal force exerted b y the substance o n unit o f area
1
Proc. Roy. Soc. May 18, 1865.

298 Viscosity.
o f either o f the planes, a n d a c t i n g from A t o B on the lower

plane, a n d from D to c o n the upper.
T h e r a t i o o f this f o r c e t o t h e r a t e o f i n c r e a s e o f t h e shear-
i n g stress is c a l l e d t h e c o e f f i c i e n t o f v i s c o s i t y , a n d i s d e n o t e d
b y the s y m b o l ¡1. W e m a y therefore write
v
I f R is t h e a m o u n t o f this f o r c e o n a r e c t a n g u l a r a r e a of
length a and breadth
R = a b F
a
= , _ b_ *,
v
and R C
h
~ VaT'
I f v, A, b, a n d C a r e e a c h u n i t y , t h e n FI = R.
Definition.—The v i s c o s i t y o f a s u b s t a n c e is m e a s u r e d by
the tangential force o n the unit o f area o f either o f t w o hori-
z o n t a l p l a n e s at t h e u n i t o f d i s t a n c e a p a r t , o n e o f w h i c h is
fixed, w h i l e t h e o t h e r m o v e s w i t h the unit o f velocity, the
space between being filled w i t h the viscous substance.
T h e d i m e n s i o n s o f jn m a y b e e a s i l y d e t e r m i n e d . I f R is
t h e m o v i n g f o r c e w h i c h w o u l d g e n e r a t e a c e r t a i n v e l o c i t y v in
the mass M in the t i m e /, then R = , and
M VC
^ ~ lv~a b
H e i e a, b, C a r e l i n e s , a n d v a n d v a r e v e l o c i t i e s , so that
- 1
t h e d i m e n s i o n s o f FT a r e [ M L _ 1
T ] , w h e r e M , L , a n d T are the
units o f mass, length, a n d t i m e .
W h e n w e wish to express the absolute forces called into
p l a y b y the viscosity o f a substance, w e must use the ordi-
n a r y unit o f m a s s ( a p o u n d , a g r a i n , o r a g r a m m e ) ; b u t i f w e
w i s h o n l y t o i n v e s t i g a t e t h e m o t i o n o f t h e v i s c o u s substance,
it is c o n v e n i e n t t o t a k e as o u r u n i t o f m a s s t h a t o f unit o f
v o l u m e o f the substance itself. I f p is t h e d e n s i t y o f t h e

Viscosity of Air. 299
substance, o r the mass o f unit o f v o l u m e , the viscosity v

m e a s u r e d i n t h i s k i n e m a t i c w a y is r e l a t e d t o / J , its v a l u e b y
the f o r m e r , or d y n a m i c a l m e t h o d , b y the e q u a t i o n
H- = " P-
T h e d i m e n s i o n s o f v, t h e k i n e m a t i c v i s c o s i t y , a r e [ L T~']. 2
I n v e s t i g a t i o n s o f the v a l u e o f v i s c o s i t y h a v e b e e n m a d e ,
for solids b y Sir W . T h o m s o n ; for liquids b y Poiseuille,
Graham, O . E. Meyer, and H e l m h o l t z ; and for gases by
G r a h a m , Stokes, O . E. M e y e r , and myself.
I find t h e v a l u e o f 11 f o r air at 0° C e n t i g r a d e t o b e
fi = - 0 0 0 1 8 7 8 (1 +-0036661),
t h e c e n t i m e t r e , g r a m m e , a n d s e c o n d b e i n g units.
In British measure, using the foot, the grain, and the
s e c o n d , a n d F a h r e n h e i t ' s t h e r m o m e t e r , this b e c o m e s
1 f
fx = - O O O I 7 9 (46 + ')-
T h e v i s c o s i t y /x i s p r o p o r t i o n a l t o t h e a b s o l u t e tempera
ture, a n d i n d e p e n d e n t o f t h e p r e s s u r e , b e i n g t h e s a m e f o r a
p r e s s u r e o f h a l f an i n c h as for a p r e s s u r e o f t h i r t y i n c h e s o f
mercury. T h e s i g n i f i c a n c e o f this r e m a r k a b l e result w i l l b e
seen w h e n w e c o m e to the molecular theory o f gases.
The k i n e m a t i c m e a s u r e , v, o f t h e v i s c o s i t y i s f o u n d by
d i v i d i n g fj. b y t h e density. I t is t h e r e f o r e d i r e c t l y p r o p o r
tional to the square o f the absolute temperature, a n d in
versely proportional to the pressure.
T h e v a l u e o f /x f o r h y d r o g e n is l e s s t h a n h a l f t h a t f o r
air. O x y g e n , o n t h e o t h e r h a n d , has a v i s c o s i t y g r e a t e r t h a n
t h a t o f air. T h a t o f c a r b o n i c a c i d is less t h a n that o f air.
It appears, from the calculations o f Professor Stokes,
c o m b i n e d w i t h t h e v a l u e o f t h e v i s c o s i t y o f air g i v e n a b o v e ,
t h a t a d r o p o f w a t e r f a l l i n g t h r o u g h air o n e t h o u s a n d t i m e s
rarer than itself (which w e m a y suppose to b e the case
S
at the ordinary height of a cloud) w o u l d fall a b o u t T D
o f a n i n c h i n a s e c o n d i f its d i a m e t e r w e r e t h e thousandth
part o f an inch. I f the d i a m e t e r o f the d r o p w e r e o n l y o n e

30O Viscosity.
t e n - t h o u s a n d t h o f a n i n c h t h e r a t e at w h i c h i t w o u l d m a k e
its w a y t h r o u g h t h e air w o u l d b e a h u n d r e d times smaller,
or half an i n c h in a minute. I f a c l o u d is f o r m e d o f l i t t l e
drops o f w a t e r o f this size, their m o t i o n through the air
w o u l d b e so s l o w that it w o u l d escape observation, and the
m o t i o n o f t h e c l o u d , so far as i t c a n b e o b s e r v e d , w o u l d b e
the same as that o f the air in that place. In fact, t h e
settling down through the air o f any v e r y small particles,
such as t h e fine spray o f w a v e s o r waterfalls, a n d all kinds
o f dust and s m o k e , is a v e r y s l o w p r o c e s s , a n d the time o f
settling d o w n through a given distance v a r i e s i n v e r s e l y as
the square o f the dimensions o f the particles, their density
and figure b e i n g the same. If, h o w e v e r , a cloud o f fine
dust c o n t a i n s so m a n y p a r t i c l e s t h a t t h e mass of a cubic
foot o f dusty a i r is sensibly greater than that o f a cubic
foot o f pure air, t h e dusty air w i l l d e s c e n d i n mass below
the l e v e l o f the p u r e air l i k e a fluid o f g r e a t e r d e n s i t y , so
that a room m a y h a v e its l o w e r half filled with d u s t y air
s e p a r a t e d b y a l e v e l surface f r o m t h e p u r e air a b o v e .
T h e r e are s o m e kinds o f fogs the m e a n density o f w h i c h

is g r e a t e r t h a n t h a t o f t h e p u r e r air i n t h e neighbourhood,
a n d these lie like lakes in hollows, and pour d o w n valleys
like streams. O n the other hand, the m e a n density o f a
c l o u d m a y b e less t h a n that o f the surrounding air, a n d it
will then ascend.
I n t h e c a s e o f s m o k e , b o t h t h e air a n d t h e s o o t y particles
are heated b y the fire before they escape into the atmo
s p h e r e , but, i n d e p e n d e n t l y o f this k i n d o f h e a t i n g , i f the sun
shines on a cloud o f dust or s m o k e , the particles absorb
heat, which they c o m m u n i c a t e to the air r o u n d them, and
thus, t h o u g h t h e p a r t i c l e s themselves remain much denser
t h a n t h e air i n t h e n e i g h b o u r h o o d , t h e y m a y c a u s e t h e c l o u d
which they form to appropriate so m u c h o f the sun's h e a t
that it b e c o m e s l i g h t e r as a w h o l e t h a n t h e surrounding pure
air, a n d s o rises.
In the case of a cloud o f watery particles, besides this

Molecular Theory. 301
k i n d o f a c t i o n , t h e r e is a n o t h e r , d e p e n d i n g on the evapora
tion from the surface o f the little drops. The vapour of
w a t e r is m u c h r a r e r t h a n air. a n d d a m p air is l i g h t e r t h a n
d r y air at the s a m e temperature and pressure. Hence the
little drops make the air o f the cloud damp, and i f the
m e a n d e n s i t y o f the c l o u d is b y this m e a n s m a d e less than
t h a t o f t h e s u r r o u n d i n g air, t h e c l o u d w i l l a s c e n d .
C H A P T E R XXII.
O N T H E M O L E C U L A R T H E O R Y O F T H E CONSTITUTION O F
BODIES.
W E h a v e a l r e a d y s h o w n t h a t h e a t is a f o r m o f energy—that
when a b o d y is h o t it p o s s e s s e s a s t o r e o f e n e r g y , p a r t at
least o f w h i c h can afterwards be exhibited in the f o r m of
visible work.
Now e n e r g y is k n o w n t o us in t w o f o r m s . O n e o f thc^e
is K i n e t i c E n e r g y , t h e e n e r g y o f m o t i o n . A b o d y in motion
has kinetic energy, which it m u s t communicate to some
other b o d y during the process of bringing it t o r e s t . This
is t h e f u n d a m e n t a l f o r m o f e n e r g y . W h e n w e have acquired
t h e n o t i o n o f m a t t e r i n m o t i o n , a n d k n o w w h a t is m e a n t b y
the e n e r g y o f that m o t i o n , w e are unable to c o n c e i v e that
any possible addition to our k n o w l e d g e could explain the
e n e r g y o f m o t i o n , o r g i v e us a m o r e p e r f e c t k n o w l e d g e o f it
than w e h a v e already.
T h e r e is a n o t h e r f o r m o f e n e r g y w h i c h a b o d y m a y h a v e ,
which depends, not on its o w n state, b u t on its position
with respect to other bodies. This is called Potential
Energy. T h e leaden weight o f a clock, when it is wound
up, has potential e n e r g y , w h i c h it l o s e s as it d e s c e n d s . It
is s p e n t i n d r i v i n g t h e c l o c k . T h i s energy depends, not on
t h e p i e c e o f l e a d c o n s i d e r e d in itself, but on the p o s i t i o n of

3 0 2 Molecular Theory.
the lead with respect to another b o d y — t h e earth—•which

a t t r a c t s it.
I n a watch, the mainspring, w h e n w o u n d u p , has poten
tial energy, which it spends in driving the wheels of the
watch. This energy arises from the coiling up of the
spring, w h i c h alters the relative position o f its parts. In
both cases, until the clock or watch is set a g o i n g , the
existence o f potential energy, whether in the clock-weight
o r i n t h e w a t c h - s p r i n g , is n o t accompanied with any visible
motion. W e m u s t therefore a d m i t that potential energy can
e x i s t i n a b o d y o r s y s t e m a l l w h o s e p a r t s a r e a t rest.
I t is t o b e o b s e r v e d , h o w e v e r , t h a t t h e p r o g r e s s o f s c i e n c e
is continually opening up new views of the forms and
relations o f different kinds of potential energy, and that
m e n o f science, so far from f e e l i n g that their k n o w l e d g e o f
p o t e n t i a l e n e r g y is p e r f e c t i n k i n d , a n d i n c a p a b l e o f e s s e n t i a l
change, are always endeavouring to explain the different
f o r m s o f p o t e n t i a l e n e r g y ; a n d i f t h e s e e x p l a n a t i o n s arc in
a n y c a s e c o n d e m n e d , i t is b e c a u s e t h e y fail t o g i v e a suffi
c i e n t r e a s o n f o r t h e fact, a n d not because the fact requires
no explanation.
We have now to determine to which o f these forms of

e n e r g y h e a t , as i t e x i s t s i n h o t b o d i e s , is t o b e r e f e r r e d . Is
a hot b o d y , like a coiled-up watch-spring, devoid of motion
at present, but capable of exciting motion under proper
conditions? or is it l i k e a fly-wheel, which derives all its
t r e m e n d o u s p o w e r f r o m t h e v i s i b l e m o t i o n w i t h w h i c h i t is
animated ?
I t is m a n i f e s t t h a t a b o d y m a y b e h o t w i t h o u t a n y m o t i o n
being visible, either o f the b o d y as a w h o l e , o r o f its parts
relatively to each other. If, therefore, the body is hot
i n v i r t u e o f m o t i o n , t h e m o t i o n m u s t b e c a r r i e d o n b y parts
o f the body too minute to be seen separately, and within
limits so narrow that w e c a n n o t detect the absence o f any
p a r t f r o m its o r i g i n a l p l a c e .
T h e e v i d e n c e for a state o f m o t i o n , the v e l o c i t y o f which

Heat is Motion. 303
m u s t far surpass t h a t o f a r a i l w a y train, e x i s t i n g i n bodies

w h i c h w e can place under the strongest m i c r o s c o p e , a n d in
which w e can detect nothing but the most perfect repose,
must b e o f a very c o g e n t nature before w e can admit that
h e a t is e s s e n t i a l l y m o t i o n .
L e t us t h e r e f o r e c o n s i d e r t h e a l t e r n a t i v e hypothesis—that
t h e e n e r g y o f a h o t b o d y is p o t e n t i a l e n e r g y , or, in other
w o r d s , t h a t t h e h o t b o d y is i n a s t a t e o f rest, b u t t h a t this
state o f rest d e p e n d s on the antagonism o f forces which
are in equilibrium as l o n g as a l l s u r r o u n d i n g bodies are
o f the same temperature, b u t w h i c h as s o o n as this e q u i
librium is destroyed are capable of setting bodies in
motion. With r e s p e c t t o a t h e o r y o f this k i n d , it is t o b e
observed that p o t e n t i a l energy depends essentially o n the
r e l a t i v e p o s i t i o n o f the parts o f the system in w h i c h it exists,
and that potential energy cannot be transformed in any
w a y without s o m e c h a n g e o f the relative position o f these
parts. I n e v e r y transformation o f potential energy, therefore,
m o t i o n o f s o m e k i n d is i n v o l v e d .
N o w w e k n o w that w h e n e v e r o n e b o d y o f a system is
hotter than another, heat is t r a n s f e r r e d from the hotter to
the c o l d e r b o d y , either b y c o n d u c t i o n or b y radiation. Let
us suppose that the transfer takes place by radiation.
W h a t e v e r theory w e adopt about the kind of motion which
c o n s t i t u t e s r a d i a t i o n , i t is m a n i f e s t t h a t r a d i a t i o n c o n s i s t s o f
m o t i o n o f s o m e k i n d , either the p r o j e c t i o n o f t h e particles
o f a substance c a l l e d c a l o r i c across the i n t e r v e n i n g space, or
a w a v e - l i k e m o t i o n p r o p a g a t e d t h r o u g h a m e d i u m filling that
space. I n either case, during the interval b e t w e e n the time
w h e n the heat leaves the hot b o d y and the time when it
reaches t h e c o l d b o d y , its e n e r g y exists in t h e i n t e r v e n i n g
space in t h e f o r m o f the m o t i o n o f matter.
Hence, whether wc consider the radiation o f heat as
effected b y the projection o f material caloric, or b y the
undulations o f an intervening m e d i u m , the o u t e r surface o f
a hot b o d y m u s t b e i n a state o f m o t i o n , p r o v i d e d any c o l a

3 °4 Molecular Theory.
b o d y is i n its n e i g h b o u r h o o d t o r e c e i v e t h e r a d i a t i o n s w h i c h
it e m i t s . But w e have n o reason to b e l i e v e that the pre
s e n c e o f a c o l d b o d y is e s s e n t i a l t o t h e radiation of heat by
a hot one. W h a t e v e r b e the m o d e in w h i c h the hot b o d y
s h o o t s f o r t h its h e a t , it m u s t d e p e n d o n t h e s t a t e o f t h e hot
b o d y alone, and not on the existence o f a c o l d b o d y at a
d i s t a n c e , so t h a t e v e n i f all t h e b o d i e s i n a c l o s e d region
were equally hot, every one of them would be radiating
heat; and the reason w h y each b o d y remains o f the same
t e m p e r a t u r e is, that it r e c e i v e s f r o m t h e o t h e r b o d i e s e x a c t l y
as m u c h h e a t as it e m i t s . T h i s , i n fact, is t h e f o u n d a t i o n of
Prevost's T h e o r y of Exchanges. W e must therefore admit
t h a t at e v e r y p a r t o f t h e surface o f a h o t b o d y t h e r e is a
radiation o f heat, and therefore a state o f m o t i o n of the
superficial parts o f the b o d y . N o w t h i s m o t i o n is c e r t a i n l y
invisible to us by any direct mode of observation, and
therefore the mere fact o f a b o d y a p p e a r i n g t o b e at rest
cannot be taken as a demonstration that its parts may
not b e in a state o f m o t i o n .
H e n c e part, at least, o f t h e e n e r g y o f a h o t b o d y m u s t b e
e n e r g y a r i s i n g f r o m t h e m o t i o n o f its p a r t s , o r k i n e t i c e n e r g y .
The conclusion at which w e shall arrive, that a very
c o n s i d e r a b l e p a r t o f t h e e n e r g y o f a h o t b o d y is i n t h e form
of motion, will b e c o m e m o r e evident w h e n w e consider the
thermal e n e r g y o f gases.
Every hot b o d y , t h e r e f o r e , is i n m o t i o n . W e have next
to enquire into the n a t u r e o f this m o t i o n . It is evidently
not a m o t i o n o f the w h o l e b o d y i n o n e direction, for how
ever small w e m a k e the b o d y by m e c h a n i c a l processes, each
visible particle remains apparently in the same place, how
e v e r h o t it is. T h e m o t i o n w h i c h w e call h e a t must there
fore b e a m o t i o n o f p a r t s t o o s m a l l t o b e o b s e r v e d s e p a r a t e l y ;
t h e m o t i o n s o f d i f f e r e n t p a r t s at the same instant must be
i n d i f f e r e n t d i r e c t i o n s ; a n d t h e m o t i o n o f a n y o n e p a r t must,
at least i n s o l i d b o d i e s , b e s u c h t h a t , h o w e v e r fast it moves,
it n e v e r r e a c h e s a s e n s i b l e distance from the point from
w h i c h it s t a r t e d .

Kinette Theory of Gases. 305
We h a v e n o w a r r i v e d at the conception o f a b o d y as
c o n s i s t i n g o f a g r e a t m a n y s m a l l p a r t s , e a c h o f w h i c h is i n
motion. W e shall c a l l a n y o n e o f t h e s e p a r t s a m o l e c u l e o f
the substance. A m o l e c u l e m a y t h e r e f o r e b e d e f i n e d as a
small mass o f matter the parts o f w h i c h d o n o t part com
p a n y during the excursions w h i c h the m o l e c u l e m a k e s w h e n
t h e b o d y t o w h i c h i t b e l o n g s is h o t .
T h e d o c t r i n e that visible b o d i e s consist o f a d e t e r m i n a t e
n u m b e r o f m o l e c u l e s is c a l l e d t h e m o l e c u l a r t h e o r y o f m a t t e r .
T h e o p p o s i t e d o c t r i n e is that, h o w e v e r s m a l l t h e p a r t s m a y
b e into which w e divide a b o d y , each part retains all the
properties o f the substance. T h i s is t h e theory of the
infinite divisibility o f b o d i e s . W e d o n o t assert t h a t there
is a n a b s o l u t e l i m i t t o t h e d i v i s i b i l i t y o f m a t t e r : w h a t we
a s s e r t is, t h a t after w e h a v e d i v i d e d a b o d y into a certain
finite number o f constituent parts called molecules, then
a n y further d i v i s i o n o f t h e s e m o l e c u l e s w i l l d e p r i v e Uhem
of the p r o p e r t i e s w h i c h g i v e rise t o the phenomena ob
served in the substance.
T h e o p i n i o n that the o b s e r v e d p r o p e r t i e s o f visible b o d i e s
apparently at rest are due to the action o f invisible mole
cules in r a p i d m o t i o n is t o b e found in L u c r e t i u s .
D a n i e l B e r n o u l l i w a s t h e first t o s u g g e s t t h a t t h e p r e s s u r e
o f air is d u e t o t h e i m p a c t o f its p a r t i c l e s o n the sides o f
the vessel containing i t ; but he m a d e v e r y little progress in
the theory w h i c h he suggested.
L e s a g e and P r e v o s t o f G e n e v a , and afterwards Herapath
in his ' M a t h e m a t i c a l P h y s i c s , ' m a d e s e v e r a l i m p o r t a n t appli
cations o f the theory.
D r . J o u l e i n 1848 e x p l a i n e d t h e p r e s s u r e o f g a s e s b y t h e
i m p a c t o f their molecules, and calculated the v e l o c i t y w h i c h
t h e y must h a v e to p r o d u c e the o b s e r v e d pressure.
K r o n i g also directed attention t o this explanation o f the
p h e n o m e n a o f gases.
I t is t o P r o f e s s o r C l a u s i u s , h o w e v e r , t h a t w e o w e t h e r e c e n t
•development o f the d y n a m i c a l theory o f gases. Since he
x
306 Molecular Theory.
t o o k up the subject a great advance has been made by

m a n y enquirers. I shall n o w e n d e a v o u r to g i v e a sketch of
the present state o f the t h e o r y .
A l l b o d i e s consist o f a finite n u m b e r o f small parts called
molecules. E v e r y m o l e c u l e consists o f a definite quantity
o f matter, w h i c h is e x a c t l y the same for all the m o l e c u l e s o f
the same substance. T h e m o d e i n w h i c h t h e m o l e c u l e is
bound t o g e t h e r is also the same for all m o l e c u l e s o f the
same substance. A m o l e c u l e m a y consist o f several distinct
portions o f matter held together by chemical bonds, and
m a y b e set in vibration, rotation, or a n y other kind of
relative m o t i o n , but so l o n g as the different portions do
not part c o m p a n y , but travel together in the excursions
m a d e b y the m o l e c u l e , our t h e o r y calls the w h o l e c o n n e c t e d
mass a single molecule.
T h e m o l e c u l e s o f all b o d i e s are i n a state o f continual
agitation. T h e hotter a b o d y is, t h e m o r e v i o l e n t l y a r e its
molecules agitated. In s o l i d b o d i e s , a m o l e c u l e , t h o u g h in
continual motion, n e v e r gets b e y o n d a certain v e r y small
distance from its o r i g i n a l p o s i t i o n i n t h e b o d y . The path
w h i c h it d e s c r i b e s is c o n f i n e d w i t h i n a v e r y s m a l l region
o f space.
I n fluids, o n t h e o t h e r h a n d , t h e r e is n o such restriction
to the excursions of a molecule. I t is t r u e t h a t t h e m o l e
cule generally can travel but a v e r y small distance before
its p a t h is d i s t u r b e d b y a n encounter with some other mole
c u l e ; b u t after this e n c o u n t e r t h e r e is n o t h i n g w h i c h d e t e r
m i n e s the m o l e c u l e rather to return towards the place from
w h e n c e it c a m e than to p u s h its w a y i n t o new regions.
Hence in fluids the p a t h o f a m o l e c u l e is n o t confined
w i t h i n a l i m i t e d r e g i o n , as i n t h e c a s e o f solids, but may
p e n e t r a t e t o a n y p a r t o f t h e s p a c e o c c u p i e d b y t h e fluid.
The actual p h e n o m e n a o f diffusion b o t h in liquids and
i n g a s e s furnish the strongest evidence that these bodies
consist o f m o l e c u l e s in a state o f continual agitation.
But when w e apply the methods o f dynamics to the

Encounters between Molecules. 307
investigation of the properties of a system consisting o f a

great number o f s m a l l b o d i e s in m o t i o n t h e resemblance
o f such a s y s t e m to a gaseous b o d y becomes still m o r e
apparent.
I shall e n d e a v o u r t o g i v e s o m e a c c o u n t o f w h a t i s k n o w n
of such a system, a v o i d i n g all unnecessary mathematical
calculations.
ON THE KINETIC THEORY OF GASES.
A g a s e o u s b o d y is s u p p o s e d t o c o n s i s t o f a g r e a t number
of molecules m o v i n g with great velocity. D u r i n g the greater
part o f their course these molecules are not a c t e d o n b y any
sensible force, and therefore move in straight lines with
uniform velocity. When two molecules come within a
certain distance o f each other, a mutual action takes place
between them, which m a y b e c o m p a r e d to the collision o f
t w o billiard balls. Each m o l e c u l e has its c o u r s e c h a n g e d ,
a n d starts on a n e w path. I have c o n c l u d e d from some
e x p e r i m e n t s o f m y own- t h a t t h e c o l l i s i o n b e t w e e n t w o h a r d
spherical balls is n o t an accurate representation o f what
takes place during the encounter of two molecules. A
b e t t e r r e p r e s e n t a t i o n o f such a n e n c o u n t e r will be obtained
b y supposing the m o l e c u l e s t o act o n o n e another in a m o r e
gradual manner, so that the action b e t w e e n t h e m g o e s o n for
a finite t i m e , d u r i n g w h i c h t h e c e n t r e s o f t h e m o l e c u l e s first
approach each other a n d then separate.
We shall refer to this mutual a c t i o n as an Encounter

between two molecules, and w e shall c a l l t h e c o u r s e o f a
m o l e c u l e b e t w e e n o n e encounter and another the F r e e P a t h
of the molecule. In o r d i n a r y gases the free motion of a
m o l e c u l e t a k e s up m u c h m o r e t i m e t h a n t h a t o c c u p i e d b y a n
encounter. A s t h e d e n s i t y o f t h e g a s i n c r e a s e s , t h e free p a t h
diminishes, and in liquids n o part o f the course of a m o l e c u l e
c a n b e s p o k e n o f as its free p a t h .
I n an encounter b e t w e e n t w o m o l e c u l e s w e k n o w that,
s i n c e t h e f o r c e o f t h e i m p a c t acts b e t w e e n t h e t w o b o d i e s ,
x 2

3o8 Molecular Theory.
the m o t i o n o f the centre of gravity o f the t w o molecules

r e m a i n s t h e s a m e after the encounter as it w a s b e f o r e . We
also k n o w b y the principle o f the c o n s e r v a t i o n o f e n e r g y that
the velocity o f each m o l e c u l e r e l a t i v e l y to the centre of
g r a v i t y r e m a i n s t h e s a m e i n m a g n i t u d e , a n d is o n l y c h a n g e d
in d i r e c t i o n .
L e t us n e x t s u p p o s e a number o f molecules in m o t i o n
contained in a vessel w h o s e sides are such that if any
e n e r g y is c o m m u n i c a t e d t o t h e v e s s e l b y t h e encounters o f
molecules against its sides, the vessel communicates as
much energy to other molecules during their encounters
w i t h it, s o a s t o p r e s e r v e t h e total energy o f the enclosed
system. T h e first t h i n g w e m u s t n o t i c e a b o u t this moving
s y s t e m is t h a t e v e n i f a l l t h e m o l e c u l e s h a v e t h e same velo
city originally, their encounters will produce an inequality
o f v e l o c i t y , a n d that this d i s t r i b u t i o n o f v e l o c i t y will g o o n
continually. Every molecule will then change both its
d i r e c t i o n a n d its v e l o c i t y at every encounter; a n d , as w e
are not supposed to k e e p a r e c o r d o f the exact particulars
o f every encounter, these changes o f m o t i o n must appear to
us v e r y i r r e g u l a r i f w e f o l l o w t h e c o u r s e o f a s i n g l e m o l e c u l e .
If, h o w e v e r , w e a d o p t a statistical v i e w o f the system, and
distribute the molecules' into groups, according to the
v e l o c i t y w i t h w h i c h at a given instant they happen to be
m o v i n g , w e shall o b s e r v e a r e g u l a r i t y o f a n e w k i n d i n t h e
p r o p o r t i o n s o f t h e w h o l e n u m b e r o f m o l e c u l e s w h i c h fall i n t o
each of these groups.
And here I wish to point out that, in adopting this

statistical method o f considering the average number of
groups o f m o l e c u l e s s e l e c t e d a c c o r d i n g t o their velocities, w e
have abandoned the strict kinetic m e t h o d o f tracing the
exact circumstances o f each i n d i v i d u a l m o l e c u l e i n a l l its
encounters. I t is t h e r e f o r e p o s s i b l e t h a t w e m a y a r r i v e at
results w h i c h , t h o u g h t h e y f a i r l y r e p r e s e n t t h e facts as l o n g
as w e a r e s u p p o s e d t o d e a l w i t h a g a s i n m a s s , w o u l d c e a s e
to b e a p p l i c a b l e i f o u r faculties a n d instruments w e r e so

Distribution of Energy. 309
sharpened that w e c o u l d d e t e c t a n d l a y h o l d o f each m o l e
c u l e a n d t r a c e it t h r o u g h a l l its c o u r s e .
For t h e s a m e r e a s o n , a t h e o r y o f t h e effects o f e d u c a t i o n
d e d u c e d f r o m a study o f the returns o f registrars, in w h i c h n o
names o f individuals are given, might b e found not to be
a p p l i c a b l e t o t h e e x p e r i e n c e o f a s c h o o l m a s t e r w h o is a b l e
to trace the progress o f each individual pupil.
T h e distribution o f the m o l e c u l e s a c c o r d i n g to their v e l o c i
ties is f o u n d t o b e o f e x a c t l y t h e s a m e m a t h e m a t i c a l f o r m as
the distribution o f observations a c c o r d i n g t o the m a g n i t u d e of
t h e i r e r r o r s , as d e s c r i b e d i n t h e t h e o r y o f e r r o r s o f o b s e r v a t i o n .
T h e distribution o f bullet-holes in a target a c c o r d i n g to their
d i s t a n c e s f r o m t h e p o i n t a i m e d at is f o u n d t o b e o f t h e s a m e
form, p r o v i d e d a great m a n y shots are fired b y persons of
the same d e g r e e o f skill.
W e h a v e already m e t with the same form in t h e c a s e o f
h e a t diffused f r o m a h o t s t r a t u m b y c o n d u c t i o n . Whenever
in physical p h e n o m e n a s o m e cause exists over which w e
have no control, and which produces a scattering of the
p a r t i c l e s o f m a t t e r , a d e v i a t i o n o f o b s e r v a t i o n s f r o m t h e truth,
o r a diffusion o f v e l o c i t y o r o f h e a t , m a t h e m a t i c a l e x p r e s s i o n s
o f this e x p o n e n t i a l f o r m a r e sure t o m a k e t h e i r a p p e a r a n c e .
It appears then that o f the molecules composing the
system s o m e are m o v i n g v e r y slowly, a v e r y f e w are m o v i n g
with e n o r m o u s v e l o c i t i e s , a n d the greater n u m b e r w i t h inter
mediate velocities. To compare one such system with
a n o t h e r , t h e b e s t m e t h o d is t o t a k e t h e m e a n o f t h e s q u a r e s
o f all the v e l o c i t i e s . T h i s q u a n t i t y is c a l l e d t h e M e a n S q u a r e
of the velocity. The s q u a r e r o o t o f t h i s q u a n t i t y is c a l l e d
the V e l o c i t y o f M e a n Square.
DISTRIBUTION OF KINETIC ENERGY BETWEEN TWO
DIFFF.RF.NT SETS OF MOLECULES.
I f t w o sets o f m o l e c u l e s w h o s e m a s s is d i f f e r e n t a r e in
motion in the s a m e vessel, t h e y will b y their encounters

3io Molecular Theory.
exchange energy with each o t h e r till t h e average kinetic

e n e r g y o f a s i n g l e m o l e c u l e o f e i t h e r s e t is t h e same. This
follows from the same investigation w h i c h d e t e r m i n e s the
law o f distribution o f v e l o c i t i e s i n a single set o f m o l e c u l e s .
H e n c e i f t h e m a s s o f a m o l e c u l e o f o n e k i n d is M L ; and
that o f a m o l e c u l e o f t h e o t h e r k i n d is M , a n d i f t h e i r a v e r a g e
2
velocities o f agitation are v , and Vg, then

2 2
Mj V j = M 2 V 2 ( l )
T h e quantity \ M V 2
is c a l l e d t h e average kinetic energy
of agitation o f a single m o l e c u l e . W e shall return t o this
result w h e n w e c o m e to G a y - L u s s a c ' s L a w o f the Volumes
o f Gases.
INTERNAL KINETIC ENERGY OF A MOLECULE.
If a molecule were a mathematical point endowed with

inertia and with attractive and repulsive forces, the only
kinetic energy it c o u l d p o s s e s s is t h a t o f t r a n s l a t i o n as a
whole. B u t i f it b e a b o d y h a v i n g parts and magnitude,
these parts may have motions of rotation or of vibration
relative to each other, i n d e p e n d e n t o f the motion of the
centre o f gravity o f the m o l e c u l e . W e must therefore admit
that part o f the kinetic e n e r g y o f a m o l e c u l e m a y d e p e n d on
t h e r e l a t i v e m o t i o n s o f its p a r t s . W e c a l l this t h e Internal
energy, to d i s t i n g u i s h it f r o m t h e energy due to the trans
l a t i o n o f t h e m o l e c u l e as a w h o l e . T h e ratio o f the internal
energy to the energy of agitation may be different in
d i f f e r e n t .gases.
DEFINITION OF T H E VELOCITY OF A GAS.
I t is e v i d e n t t h a t i f a g a s c o n s i s t s o f a g r e a t number of
m o l e c u l e s m o v i n g a b o u t in all directions w e cannot identify
the v e l o c i t y o f any o n e o f these m o l e c u l e s with what w e are
accustomed to consider as the velocity o f the gas itself.
L e t us c o n s i d e r the c a s e o f a g a s w h i c h has remained in a
fixed vessel for a sufficient time to arrive at the normal

Agitation of Molecules.
distribution o f velocities. T h i s gas, a c c o r d i n g to the ordi

n a r y n o t i o n s , is a t rest, t h o u g h t h e m o l e c u l e s o f w h i c h it is
c o m p o s e d m a y b e f l y i n g a b o u t in all d i r e c t i o n s .
Now consider any plane area o f an imaginary surface
d e s c r i b e d within the vessel. T h i s surface d o e s n o t i n t e r f e r e
with the motion o f the molecules. Some molecules pass
through the surface in one direction, and others in the
o p p o s i t e d i r e c t i o n • b u t it is e v i d e n t , s i n c e t h e g a s d o e s n o t
tend to accumulate on o n e side rather than on the other,
that e x a c t l y the s a m e n u m b e r o f m o l e c u l e s pass in t h e one
direction as in t h e o t h e r . If, t h e r e f o r e , a g a s is at rest, as
many molecules pass through a fixed surface in the one
d i r e c t i o n as i n t h e o t h e r i n t h e s a m e t i m e .
I t is e v i d e n t t h a t i f t h e v e s s e l , i n s t e a d o f b e i n g at r e s t , h a d
b e e n in a state o f uniform m o t i o n , an equal n u m b e r o f m o l e
cules w o u l d pass in b o t h directions through any surface
fixed with respect to the vessel. Hence w e find t h a t i f a
g a s is i n m o t i o n , a n d i f t h e v e l o c i t y o f ' a surface coincides in
direction and magnitude with that o f the gas, the same
n u m b e r o f m o l e c u l e s will pass through that surface in the
p o s i t i v e d i r e c t i o n as i n t h e n e g a t i v e .
T h i s leads to the following definition o f the v e l o c i t y o f a
gas :
I f w e d e t e r m i n e the m o t i o n o f the centre o f g r a v i t y o f all
the m o l e c u l e s within a v e r y small r e g i o n surrounding a p o i n t
in a gas, t h e n the v e l o c i t y o f the gas within that r e g i o n is
d e f i n e d as t h e v e l o c i t y o f t h e * c e n t r e o f g r a v i t y o f a l l t h e m o l e
cules within that r e g i o n .
T h i s is w h a t is m e a n t b y t h e m o t i o n o f a g a s i n common
language. B e s i d e s this m o t i o n , t h e r e a r e t w o o t h e r k i n d s o f
m o t i o n c o n s i d e r e d in the kinetic theory o f gases. T h e first is
the m o t i o n o f agitation o f the m o l e c u l e s . T h i s is t h e h i t h e r t o
invisible motion o f the molecule considered as a whole.
Its course consists of broken portions, c a l l e d free paths,
interrupted b y the encounters b e t w e e n different molecules.
The second is the internal motion o f each molecule,

312 Molecular Tlieory.
consisting partly o f rotation and partly o f vibrations among

the c o m p o n e n t parts o f the m o l e c u l e .
T h e v e l o c i t y o f t h e c e n t r e o f g r a v i t y o f a m o l e c u l e is the
resultant o f the v e l o c i t y o f the gas a n d the v e l o c i t y o f agita
t i o n o f t h e i n d i v i d u a l m o l e c u l e at t h e g i v e n instant. The
velocity o f a constituent p a r t o f a m o l e c u l e is t h e resultant
o f t h e v e l o c i t y o f its c e n t r e o f g r a v i t y a n d the velocity o f
the constituent part relatively t o the centre o f gravity o f the
molecule.
THEORY OF T H E PRESSURE OF A GAS.
L e t us c o n s i d e r t w o p o r t i o n s o f a g a s s e p a r a t e d b y a p l a n e
s u r f a c e w h i c h m o v e s w i t h t h e s a m e v e l o c i t y as
F I G . 41. g ^ a s-^y hayg e s t h a t in this c a s e t h e
e e n
number o f m o l e c u l e s w h i c h pass through the

p l a n e i n o p p o s i t e d i r e c t i o n s is t h e s a m e .
Each m o l e c u l e in crossing the plane from
t h e r e g i o n A t o the r e g i o n B enters the s e c o n d
r e g i o n in p r e c i s e l y the same, state as it l e a v e s the first. It
therefore carries o v e r i n t o t h e r e g i o n B, n o t o n l y its m a s s ,
but its m o m e n t u m a n d its k i n e t i c e n e r g y . Hence, if we
consider the quantity of momentum in a given direction
e x i s t i n g at a n y i n s t a n t in t h e p a r t i c l e s i n t h e r e g i o n B , this
quantity will b e altered w h e n e v e r a m o l e c u l e crosses the
b o u n d a r y , c a r r y i n g i t s m o m e n t u m a l o n g w i t h it.
Now l e t us consider all the molecules whose velocity
differs b y l e s s t h a n a c e r t a i n q u a n t i t y , c, f r o m a g i v e n v e l o c i t y
the components o f w h i c h are u in the direction perpen
dicular to the plane from A towards B , and v and w in t w o
other directions parallel to the plane. Let there be N
m o l e c u l e s w h o s e v e l o c i t y is w i t h i n t h e s e l i m i t s i n e v e r y u n i t
o f v o l u m e , and let the mass o f each o f these b e M .
T h e n t h e n u m b e r o f t h e s e m o l e c u l e s w h i c h w i l l c r o s s unit
o f a r e a o f t h e p l a n e f r o m A t o B i n u n i t o f t i m e is
N «.

Pressure of a Gas. 313
T h e momentum o f each o f these molecules r e s o l v e d in

the d i r e c t i o n A E is M U.
H e n c e t h e m o m e n t u m in this d i r e c t i o n c o m m u n i c a t e d to
t h e r e g i o n B i n u n i t o f t i m e is
3
M N u.
Since this bombardment o f the r e g i o n B d o e s not pro
duce motion of the gas, a pressure must b e exerted on
the gas b y the sides o f the vessel, and the a m o u n t o f this
p r e s s u r e f o r e v e r y u n i t o f a r e a m u s t b e M N U*.
T h e region A loses positive m o m e n t u m at t h e s a m e rate,
and in order t o preserve equilibrium there must b e a pressure
2
equal to M N U o n e v e r y unit o f area o f the surface o f the
r e g i o n A.
Hitherto w e have considered only one group o f molecules,
whose velocities lie between given limits. In e v e r y such
group that w h i c h determines the pressure in the direction A B
o n t h e surface s e p a r a t i n g A f r o m B is a q u a n t i t y o f t h e f o r m
2
M N u, w h e r e N is t h e n u m b e r o f m o l e c u l e s i n t h e g r o u p , a n d
u is t h e v e l o c i t y o f e a c h m o l e c u l e r e s o l v e d in the direction
A B. T h e other c o m p o n e n t s o f the v e l o c i t y d o not influence
t h e p r e s s u r e i n this d i r e c t i o n .
T o find t h e w h o l e pressure, w e must find the sum o f all
2
such expressions as M N U f o r a l l t h e groups o f molecules
1
in the system. W e m a y w r i t e this result p = M N U, where
N n o w signifies the total n u m b e r o f m o l e c u l e s in unit o f
2 2
volume, and u denotes the m e a n value o f u for all these
a
molecules. N o w if v is t h e s q u a r e o f t h e v e l o c i t y w i t h o u t
regard to direction,
2 2 2
v 2
= u + v •+- W ,
w h e r e uvw a r e t h e c o m p o n e n t s i n t h r e e d i r e c t i o n s at r i g h t
1 2 2
angles. H e n c e if u, zi , a n d 7i> d e n o t e the mean square o f
2
these c o m p o n e n t s , and v the m e a n square o f the resultant,
2 2
v a
= u + 7J 2
+ w.

R
3 4 Molecular Theory.
W h e n , as in e v e r y gas at rest, t h e p r e s s u r e is e q u a l in a l l
2 2 2 3 2
directions, u = v — w, and therefore v = 3 u.
H e n c e t h e p r e s s u r e o f a g a s is
p = £M N v 3
(2)
w h e r e M is t h e m a s s o f e a c h m o l e c u l e , N is t h e n u m b e r of
2
m o l e c u l e s in unit o f v o l u m e , a n d v is t h e m e a n square o f
the velocity.
I n this e x p r e s s i o n t h e r e a r e t w o quantities which h a v e
never been directly measured—the mass o f a single molecule,
a n d the n u m b e r o f m o l e c u l e s in unit o f volume. But w e
have here to d o with the product o f these quantities, which
is e v i d e n t l y t h e m a s s o f t h e s u b s t a n c e i n u n i t o f v o l u m e , o r , i n
o t h e r w o r d s , its d e n s i t y . H e n c e w e m a y write the expression
/ = a- P (3)
w h e r e p is t h e d e n s i t y o f t h e g a s .
I t is e a s y f r o m this e x p r e s s i o n t o d e t e r m i n e , a s w a s first
done by Joule, the mean square o f the velocity of the
molecules o f a gas, for
2
v = 3 - (4)
P
where p is t h e pressure, a n d p the density, which must of
course b e e x p r e s s e d in t e r m s o f the s a m e f u n d a m e n t a l units.
,
F o r instance, under the atmospheric pressure o f 2ii6 4
pounds weight o n t h e s q u a r e f o o t , a n d at t h e t e m p e r a t u r e o f
m e l t i n g i c e , t h e d e n s i t y o f h y d r o g e n is o ' o o s s o a p o u n d s i n
a cubic f o o t Hence
P= 378816 i n g r a v i t a t i o n units, a n d
if the intensity o f g r a v i t y w h e r e this r e l a t i o n was observed

w a s 32-2, w e h a v e
2 6 l 6
v = 3 5939 >
or, t a k i n g t h e s q u a r e r o o t o f this q u a n t i t y ,
v = 6097 f e e t p e r s e c o n d .

Laws of Boyle and Gay-Lussac.
T h i s is t h e v e l o c i t y o f m e a n square for the m o l e c u l e s o f

h y d r o g e n at 32° F . a n d at t h e a t m o s p h e r i c pressure.
LAW OF BOYLE.
Two bodies are said to be o f the same temperature

w h e n t h e r e is n o m o r e t e n d e n c y f o r h e a t t o pass from the
first t o the s e c o n d than in the reverse direction. In the
k i n e t i c t h e o r y o f h e a t , as w e h a v e s e e n , this t h e r m a l e q u i l i
b r i u m is e s t a b l i s h e d w h e n t h e r e is a c e r t a i n r e l a t i o n b e t w e e n
the v e l o c i t i e s o f agitation o f the m o l e c u l e s o f the t w o b o d i e s .
H e n c e the temperature of a gas must d e p e n d o n the velocity
o f a g i t a t i o n o f its m o l e c u l e s , a n d this v e l o c i t y m u s t b e the
s a m e at t h e s a m e t e m p e r a t u r e , w h a t e v e r b e t h e density'.
1 2
In the expression / = | p v , the quantity v depends
only on the temperature as l o n g as the gas remains the
same. Hence w h e n the density p varies, the pressure p
must v a r y in the same proportion. T h i s is B o y l e ' s law,
w h i c h is n o w r a i s e d f r o m t h e r a n k o f an e x p e r i m e n t a l fact
to t h a t o f a d e d u c t i o n f r o m t h e k i n e t i c t h e o r y o f g a s e s .
I f v d e n o t e s t h e v o l u m e o f unit o f m a s s , w e m a y w r i t e this
expression
t *=i v 2
(5)
N o w p v is p r o p o r t i o n a l t o t h e absolute temperature, as
measured by a thermometer, of the particular gas under
2
consideration. H e n c e v , the m e a n square o f the v e l o c i t y o f
a g i t a t i o n , is p r o p o r t i o n a l t o t h e a b s o l u t e temperature mea
s u r e d i n this w a y .
LAW OF GAY-LUSSAC.
L e t us n e x t c o n s i d e r t w o d i f f e r e n t g a s e s i n - t h e r m a l e q u i
librium. We h a v e already stated that if M j M 2 are the
masses of individual molecules o f these gases, and v , v 2
t h e i r r e s p e c t i v e v e l o c i t i e s o f a g i t a t i o n , it is n e c e s s a r y for
2
thermal equilibrium that M , V , 2
M 2 V 2 b y equation (1).
I f the pressures o f these gases are p l a n d Pi, and the

3i6 Molecular Theory.
number o f molecules in unit o f v o l u m e N j and N , then, by 2
equation (2),
P\ = i M,N T and/ 2 == £ M N V a 2 2
S
,
I f the pressures o f the t w o gases arc equal,
Mi N i v ,
2
= M 2 N 2 v 2
2
.
I f their temperatures are equal,

2 2
Mi V! = M 2 V . A
D i v i d i n g t h e t e r m s o f t h e first o f t h e s e e q u a t i o n s b y t h o s e
o f the second, w e find
Nj = N 2 (6)
or when two gases are at the same pressure and tempera

ture, the number of molecules in unit of volume is the same in
both gases.
I f w e put pi = M j N | and p 2 = M 2 N 2 for the densities o f
w e e t
the t w o g a s e s , then, since N , = x , 2 g
Pi : Pa : : M i : M 2 (7)
or the densities of two gases at the same temperature and
pressure are proportional to the masses of their individual
molecules.
T h e s e t w o equivalent p r o p o s i t i o n s are the e x p r e s s i o n o f a
v e r y important l a w established b y Gay-Lussac, that the den
sities o f g a s e s a r e p r o p o r t i o n a l t o t h e i r m o l e c u l a r w e i g h t s .
T h e proportion by weight in w h i c h different substances
c o m b i n e t o form chemical c o m p o u n d s depends, according to
D a l t o n ' s a t o m i c theory, o n the w e i g h t s o f their m o l e c u l e s ,
a n d it is o n e o f t h e m o s t i m p o r t a n t researches in chemistry
t o d e t e r m i n e the p r o p o r t i o n s o f the w e i g h t s o f the m o l e c u l e s
from the proportions in w h i c h they enter into combination.
G a y - L u s s a c d i s c o v e r e d that in the case o f gases the v o l u m e s
o f the c o m b i n i n g quantities o f different gases a l w a y s stand
in a s i m p l e ratio to e a c h other. This law o f volumes has
n o w b e e n raised from the r a n k o f a n e m p i r i c a l fact t o that o f
a deduction f r o m our t h e o r y , a n d w e m a y n o w assert, as a
d y n a m i c a l proposition, that the w e i g h t s o f the m o l e c u l e s o f

Law of Charles.
g a s e s ( t h a t is, t h o s e s m a l l p o r t i o n s w h i c h d o n o t p a r t c o m
p a n y d u r i n g t h e i r m o t i o n ) are p r o p o r t i o n a l t o t h e densities
o f t h e s e g a s e s at s t a n d a r d t e m p e r a t u r e a n d pressure.
LAW OF CHARLES.
W e m u s t n e x t c o n s i d e r t h e effect o f c h a n g e s o f t e m p e r a t u r e
o n different gases. S i n c e at a l l t e m p e r a t u r e s , w h e n t h e r e is
thermal equilibrium,
M, V j 2
= M v 2 2
2
;
and since the a b s o l u t e t e m p e r a t u r e , as measured by a gas
a
t h e r m o m e t e r , is p r o p o r t i o n a l t o v , w h e n t h e g a s is o f t h e
2
first k i n d , a n d t o v 2 w h e n t h e g a s is o f t h e s e c o n d k i n d ; it
2 2
follows, since V j is itself proportional to v 2 , that the
a b s o l u t e t e m p e r a t u r e s , as m e a s u r e d b y t h e t w o t h e r m o m e t e r s ,
are p r o p o r t i o n a l , a n d i f t h e y a g r e e at a n y o n e temperature
(as the freezing point), they agree throughout. This is
the law o f the equal dilatation o f gases discovered by
Charles.
. KINETIC ENERGY OF A MOLECULE.
T h e m e a n k i n e t i c e n e r g y o f a g i t a t i o n o f a m o l e c u l e is t h e
p r o d u c t o f its m a s s b y h a l f t h e m e a n s q u a r e o f its v e l o c i t y , o r
\ M v . 2
T h i s is t h e e n e r g y d u e t o t h e m o t i o n o f t h e m o l e c u l e as a
w h o l e , b u t its p a r t s m a y b e i n a s t a t e o f r e l a t i v e m o t i o n . If
we assume, w i t h Clausius, that the energy due to this
internal m o t i o n o f the parts o f the m o l e c u l e t e n d s t o w a r d s a
value h a v i n g a constant ratio to the energy o f agitation, the
w h o l e e n e r g y will b e proportional to the energy o f agitation,
and m a y be written
2 £ M v , 2
w h e r e /3 is a f a c t o r , a l w a y s g r e a t e r t h a n u n i t y , a n d p r o b a b l y
e q u a l t o i'634 f o r air a n d s e v e r a l o f t h e m o r e p e r f e c t g a s e s .
For steam it m a y b e as m u c h as 2TO, but this is v e r y
uncertain.

T o find t h e k i n e t i c e n e r g y o f t h e substance contained in
unit o f v o l u m e , w e h a v e o n l y to m u l t i p l y b y the n u m b e r o f
molecules, and w e obtain
T = 1 j3 M N v 2
(8)
C o m p a r i n g this w i t h t h e equation (2) which determines
the pressure, w e g e t
T V = -1/3/ (9)
o r t h e e n e r g y i n u n i t o f v o l u m e is n u m e r i c a l l y e q u a l t o the
p r e s s u r e o n u n i t o f a r e a m u l t i p l i e d b y | - [i.
The e n e r g y in unit o f m a s s is f o u n d b y , multiplying this
b y v, t h e v o l u m e o f u n i t o f m a s s :
T = I PPm v- (to)
SPECIFIC HEAT AT CONSTANT VOLUME.
S i n c e t h e p r o d u c t J> v is p r o p o r t i o n a l t o t h e a b s o l u t e t e m -
p e r a t u r e , t h e e n e r g y is p r o p o r t i o n a l t o t h e t e m p e r a t u r e .
T h e s p e c i f i c h e a t is m e a s u r e d d y n a m i c a l l y b y t h e increase
o f e n e r g y c o r r e s p o n d i n g t o a rise o f o n e d e g r e e o f t e m p e r a t u r e .
Hence
K T =f P ~p
(n)
T o e x p r e s s t h e s p e c i f i c h e a t i n o r d i n a r y t h e r m a l units, w e
m u s t d i v i d e this b y J, the specific heat o f water (Joule's
equivalent). I t f o l l o w s f r o m this expression that for any
o n e gas the specific heat o f unit o f mass at c o n s t a n t v o l u m e
is t h e s a m e f o r a l l p r e s s u r e s a n d t e m p e r a t u r e s , b e c a u s e
remains constant. F o r different gases the specific heat at

constant v o l u m e is i n v e r s e l y p r o p o r t i o n a l to the specific
g r a v i t y , a n d d i r e c t l y p r o p o r t i o n a l t o ¡3.
S i n c e ¡3 is n e a r l y t h e same for several gases, the specific
h e a t o f t h e s e g a s e s is i n v e r s e l y p r o p o r t i o n a l to their specific
gravity referred to air, o r , s i n c e t h e s p e c i f i c g r a v i t y is pro-
portional t o their m o l e c u l a r w e i g h t , the specific heat multi-
p l i e d b y t h e m o l e c u l a r w e i g h t is t h e s a m e for a l l t h e s e g a s e s .

Law of Dulong and Petit. 3 1 9
T h i s is the law o f Dulong and Petit. I t w o u l d b e accu

r a t e f o r a l l g a s e s i f t h e v a l u e o f j3 w e r e t h e s a m e i n every
case.
I t has b e e n s h o w n a t p . 183 t h a t t h e d i f f e r e n c e o f t h e t w o
s p e c i f i c h e a t s is H e n c e t h e i r r a t i o , 7, is
y = — + 1 and /3 = f —
1
3 P y -
I f u is t h e v e l o c i t y o f s o u n d i n a g a s , w e h a v e , as at p . 228,
U J
= yp V (12)
T h e m e a n s q u a r e o f t h e v e l o c i t y o f a g i t a t i o n is
2
v = / t / 3 (13)
Henceu=^/Z v, o r , i f 7 = 1-408, as i n a i r a n d several

3
other gases,
u = -6858 v or v = 1-458 u . . (14)
T h e s e are the relations b e t w e e n the v e l o c i t y o f sound and
the v e l o c i t y o f m e a n square o f agitation in a n y g a s for w h i c h
7 = 1-408.
T h e n a t u r e o f this b o o k a d m i t s only o f a brief account o f
s o m e o t h e r results o f t h e k i n e t i c t h e o r y o f g a s e s . T w o of
these are i n d e p e n d e n t o f the nature o f the action b e t w e e n
t h e m o l e c u l e s during their encounters.
T h e first o f t h e s e r e l a t e s t o t h e e q u i l i b r i u m o f a m i x t u r e o f
gases acted o n b y gravity. T h e r e s u l t o f o u r t h e o r y is that
the final distribution o f any number o f kinds o f gas in a
v e r t i c a l v e s s e l is such that the density o f each g a s at a
g i v e n h e i g h t is t h e same as i f all t h e o t h e r gases h a d b e e n
r e m o v e d , l e a v i n g it a l o n e in the vessel.
T h i s is e x a c t l y t h e m o d e o f distribution which Dalton
s u p p o s e d to exist in a m i x e d a t m o s p h e r e in equilibrium, the
law o f diminution o f density o f each constituent gas being
t h e s a m e as i f n o o t h e r g a s e s w e r e p r e s e n t .
I n our atmosphere the continual disturbances caused by
w i n d s carry portions o f the m i x e d gases f r o m o n e stratum

to another, so that the p r o p o r t i o n o f o x y g e n a n d n i t r o g e n at

different h e i g h t s is m u c h m o r e uniform than if these gases
had been allowed to take their p l a c e s b y diffusion during a
dead calm.
T h e s e c o n d result o f our t h e o r y relates t o the t h e r m a l equi
librium o f a vertical column. W e find that i f a vertical
column o f a gas w e r e left t o itself, t i l l b y t h e conduction
o f heat it h a d attained a condition o f thermal equilibrium,
t h e t e m p e r a t u r e w o u l d b e the s a m e t h r o u g h o u t , or, i n o t h e r
words, gravity produces n o effect i n m a k i n g the b o t t o m o f
the c o l u m n hotter or c o l d e r than the t o p .
T h i s r e s u l t is i m p o r t a n t i n t h e t h e o r y o f t h e r m o d y n a m i c s ,
for it p r o v e s that g r a v i t y has n o influence in altering the
conditions o f thermal equilibrium in any substance, whether
gaseous or not. F o r if two vertical columns o f different
substances stand o n the same perfectly conducting horizontal
plate, the temperature o f the b o t t o m o f each c o l u m n will b e
the same ; a n d if each c o l u m n is i n t h e r m a l e q u i l i b r i u m o f
itself, t h e t e m p e r a t u r e s at a l l e q u a l h e i g h t s m u s t b e t h e s a m e .
I n fact, i f t h e t e m p e r a t u r e s o f t h e t o p s o f t h e t w o c o l u m n s
w e r e d i f f e r e n t , w e m i g h t d r i v e a n e n g i n e w i t h this d i f f e r e n c e o f
t e m p e r a t u r e , a n d t h e r e f u s e h e a t w o u l d pass d o w n t h e c o l d e r
c o l u m n , through, t h e c o n d u c t i n g p l a t e , a n d up the warmer
c o l u m n ; a n d this w o u l d g o o n till all the heat was c o n v e r t e d
r
i n t o w ork, contrary t o the s e c o n d l a w o f t h e r m o d y n a m i c s .
But w e k n o w that i f o n e o f the columns is g a s e o u s , its
t e m p e r a t u r e is u n i f o r m . H e n c e that o f the other must be
u n i f o r m , w h a t e v e r its m a t e r i a l .
T h i s r e s u l t is b y n o m e a n s applicable to the case o f our
atmosphere. Setting aside the enormous d i r e c t effect of
the sun's r a d i a t i o n in disturbing thermal equilibrium, the
effect o f winds in carrying large masses o f air from one
height to another tends to produce a distribution o f tem
perature of a quite different kind, the t e m p e r a t u r e at any
h e i g h t b e i n g s u c h t h a t a m a s s o f air, b r o u g h t f r o m o n e h e i g h t
t o another w i t h o u t g a i n i n g or l o s i n g heat, w o u l d always find

Diffusion, Conduction, and Viscosity. 321
itself at the temperature o f the s u r r o u n d i n g air. In this

c o n d i t i o n o f w h a t S i r W i l l i a m T h o m s o n has c a l l e d t h e C o n -
v e c t i v e e q u i l i b r i u m o f h e a t , i t is n o t t h e temperature which
is c o n s t a n t , b u t t h e q u a n t i t y ij>, w h i c h d e t e r m i n e s the adia-
batic curves.
In the c o n v e c t i v e equilibrium o f temperature, the abso
lute temperature is p r o p o r t i o n a l t o the pressure raised to
the p o w e r -, or C233.
7
T h e extreme slowness o f the conduction o f h e a t i n air,

c o m p a r e d w i t h the r a p i d i t y w i t h w h i c h l a r g e m a s s e s o f air
are carried from o n e height to another b y the winds, causes
the temperature o f the different strata o f the a t m o s p h e r e to
d e p e n d far m o r e o n this c o n d i t i o n o f c o n v e c t i v e e q u i l i b r i u m
t h a n o n true t h e r m a l equilibrium.
W e now proceed to those phenomena o f gases which,
according to the kinetic theory, d e p e n d upon the particular
nature o f the action w h i c h takes place w h e n the molecules
encounter each other, and on the frequency of these
encounters.
There are three phenomena o f this k i n d o f w h i c h the
kinetic theory takes account—the diffusion o f gases, the
viscosity o f gases, a n d the c o n d u c t i o n o f heat through a gas.
We have already described the k n o w n facts a b o u t the
interdiffusion o f t w o different gases. I t is o n l y w h e n the
g a s e s arc c h e m i c a l l y d i f f e r e n t t h a t w e c a n t r a c e the process
of d i f f u s i o n , b u t o n t h e m o l e c u l a r t h e o r y diffusion is a l w a y s
g o i n g o n , e v e n i n a s i n g l e g a s ; o n l y it is i m p o s s i b l e t o t r a c e
the progress of the molecules, because w e cannot tell one
from another.
The relation between diffusion and viscosity may be
e x p l a i n e d as f o l l o w s : C o n s i d e r t h e c a s e o f m o t i o n o f a m a s s
o f g a s , w h i c h has a l r e a d y b e e n d e s c r i b e d in C h a p t e r X X I . , i n
which the different h o r i z o n t a l layers o f the gas slide over
each other. In d i f f u s i o n t h e m o l e c u l e s pass, s o m e o f t h e m
upwards and some of them downwards, through any
Y
horizontal plane. I f t h e m e d i u m has d i f f e r e n t p r o p e r t i e s o f

any kind above and b e l o w this p l a n e , t h e n this i n t e r c h a n g e
o f m o l e c u l e s will t e n d t o assimilate the properties o f the t w o
portions o f the m e d i u m .
I n t h e c a s e o f o r d i n a r y diffusion, t h e p r o p o r t i o n s of the
two diffusing s u b s t a n c e s a r e d i f f e r e n t a b o v e a n d below, and
v a r y in the different horizontal layers according to their
height. I n the case o f internal friction, the m e a n horizontal
m o m e n t u m is d i f f e r e n t i n t h e different layers, a n d w h e n the
m o l e c u l e s pass through the p l a n e , carrying their momentum
w i t h t h e m , this e x c h a n g e of momentum b e t w e e n the upper
a n d l o w e r parts o f t h e m e d i u m c o n s t i t u t e s a f o r c e t e n d i n g t o
e q u a l i z e their v e l o c i t y , a n d this is the p h e n o m e n o n actually
o b s e r v e d i n t h e m o t i o n o f v i s c o u s fluids.
T h e coefficient o f viscosity, w h e n measured in the kine
m a t i c w a y , represents the rate at w h i c h the equalization o f
v e l o c i t y g o e s o n b y the e x c h a n g e o f the m o m e n t u m o f the
m o l e c u l e s , j u s t as t h e coefficient o f diffusion represents the
r a t e at w h i c h t h e e q u a l i z a t i o n o f c h e m i c a l c o m p o s i t i o n g o e s
o n b y the exchange o f the molecules themselves.
I t appears from the kinetic t h e o r y o f gases t h a t i f D is
the coefficient o f diffusion o f the gas into itself, and v the
viscosity measured kinematically,
v = 0-6479 D ( I S )
L 6
D = I'543S " ( )
T h e c o n d u c t i o n o f h e a t in a g a s , a c c o r d i n g t o t h e k i n e t i c
t h e o r y , is s i m p l y t h e d i f f u s i o n o f t h e e n e r g y o f t h e m o l e c u l e s
by their m o v i n g about in the medium and c a r r y i n g their
e n e r g y w i t h t h e m till t h e y e n c o u n t e r o t h e r m o l e c u l e s , w h e n
the e n e r g y is r e d i s t r i b u t e d . T h e relation o f the conduc
tivity K, m e a s u r e d thermometrically, to the viscosity v,
m e a s u r e d k i n e m a t i c a l l y , is
I t a p p e a r s , t h e r e f o r e , t h a t diffusion, v i s c o s i t y , a n d conduc-

Evaporation and Condensation. 323
tivity in gases are related to each other in a very simple

way, b e i n g the rate o f e q u a l i z a t i o n o f three p r o p e r t i e s o f the
m e d i u m — t h e p r o p o r t i o n o f its i n g r e d i e n t s , its v e l o c i t y , a n d
its t e m p e r a t u r e . The e q u a l i z a t i o n is e f f e c t e d b y t h e same
a g e n c y in each c a s e — n a m e l y , the agitation of the molecules.
I n each case, i f t h e d e n s i t y r e m a i n s the same, the rate o f
e q u a l i z a t i o n is p r o p o r t i o n a l t o the absolute temperature;
and if the temperature remains the same, the rate o f equal
i z a t i o n is inversely proportional to the density. Hence,
if w e c o n s i d e r t h e t e m p e r a t u r e a n d t h e p r e s s u r e as d e f i n i n g
t h e s t a t e o f t h e g a s , t h e q u a n t i t i e s D, V, a n d K v a r y d i r e c t l y
as t h e s q u a r e o f the absolute temperature a n d i n v e r s e l y as
the pressure.
MOLECULAR THEORY O F EVAPORATION A N D CONDENSATION.

The mathematical difficulties arising in the investigation
o f t h e m o t i o n s o f m o l e c u l e s a r e so g r e a t t h a t i t is n o t t o b e
w o n d e r e d at t h a t m o s t o f t h e n u m e r i c a l r e s u l t s a r e c o n f i n e d
to the p h e n o m e n a o f gases. T h e general character, h o w e v e r ,
of the e x p l a n a t i o n o f m a n y o t h e r p h e n o m e n a b y the m o l e
c u l a r t h e o r y has b e e n p o i n t e d o u t b y C l a u s i u s a n d o t h e r s .
W e h a v e s e e n that i n t h e c a s e o f a g a s s o m e o f t h e m o l e
c u l e s h a v e a m u c h g r e a t e r v e l o c i t y t h a n o t h e r s , s o t h a t it is
o n l y t o t h e a v e r a g e v e l o c i t y o f a l l t h e m o l e c u l e s that w e c a n
ascribe a definite value. I t is p r o b a b l e t h a t this is a l s o t r u e
o f t h e m o t i o n s o f t h e m o l e c u l e s o f a l i q u i d , s o that, t h o u g h
the a v e r a g e v e l o c i t y m a y b e m u c h smaller than in the v a p o u r
of that liquid, s o m e o f the m o l e c u l e s in the l i q u i d m a y h a v e
velocities equal to or greater than the average v e l o c i t y in
the vapour. I f a n y o f t h e m o l e c u l e s a t t h e surface of the
l i q u i d h a v e s u c h v e l o c i t i e s , a n d i f t h e y a r e moving from the
l i q u i d , they will escape f r o m t h o s e forces w h i c h retain the
o t h e r m o l e c u l e s as c o n s t i t u e n t s o f the liquid, and w i l l fly
about as v a p o u r in the space outside the liquid. T h i s is
the m o l e c u l a r t h e o r y o f e v a p o r a t i o n . A t the s a m e t i m e , a
molecule of the v a p o u r striking the liquid may become
Y 2

3 42
Molecular Tlwory.
e n t a n g l e d a m o n g t h e m o l e c u l e s o f t h e l i q u i d , a n d m a y thus
b e c o m e part o f the liquid. T h i s is t h e m o l e c u l a r e x p l a n a t i o n
o f condensation. T h e n u m b e r o f m o l e c u l e s w h i c h pass f r o m
the liquid t o the v a p o u r d e p e n d s o n the temperature o f the
liquid. The number o f molecules which pass from the
v a p o u r to t h e liquid d e p e n d s upon the density o f the v a p o u r
as w e l l as its t e m p e r a t u r e . I f the t e m p e r a t u r e o f t h e v a p o u r
i s t h e s a m e as t h a t o f t h e l i q u i d , e v a p o r a t i o n w i l l t a k e p l a c e
as l o n g as m o r e m o l e c u l e s a r e e v a p o r a t e d t h a n condensed;
b u t w h e n t h e d e n s i t y o f t h e v a p o u r has i n c r e a s e d t o such a
v a l u e t h a t as m a n y m o l e c u l e s a r e c o n d e n s e d as e v a p o r a t e d ,
t h e n t h e v a p o u r has a t t a i n e d its m a x i m u m density. I t is
t h e n said t o b e s a t u r a t e d , a n d i t is c o m m o n l y s u p p o s e d that
evaporation ceases. According to the molecular theory,
h o w e v e r , e v a p o r a t i o n is still g o i n g o n as fast as e v e r ; o n l y ,
condensation is a l s o g o i n g o n at a n e q u a l rate, since the
proportions o f liquid and o f gas remain unchanged.
A similar e x p l a n a t i o n applies t o cases in w h i c h the v a p o u r
o r g a s is a b s o r b e d b y a l i q u i d o f a d i f f e r e n t k i n d , as w h e n
o x y g e n o r c a r b o n i c a c i d is a b s o r b e d b y w a t e r o r a l c o h o l . In
s u c h c a s e s a ' m o v a b l e e q u i l i b r i u m ' is a t t a i n e d when the
l i q u i d h a s a b s o r b e d a q u a n t i t y o f t h e g a s w h o s e v o l u m e at
the d e n s i t y o f t h e u n a b s o r b e d g a s is a c e r t a i n multiple or
f r a c t i o n o f t h e v o l u m e o f t h e l i q u i d ; or, i n o t h e r w o r d s , t h e
d e n s i t y o f t h e g a s in t h e l i q u i d a n d o u t s i d e t h e l i q u i d s t a n d
in a certain numerical ratio to each other. T h i s s u b j e c t is
t r e a t e d v e r y fully i n D u n s e n ' s ' G a s o m e t r y . '
T h e a m o u n t o f v a p o u r o f a l i q u i d diffused i n t o a gas o f a
d i f f e r e n t k i n d is g e n e r a l l y i n d e p e n d e n t o f t h e n a t u r e o f t h e
gas, e x c e p t w h e n t h e g a s a c t s c h e m i c a l l y o n t h e v a p o u r .
D r . A n d r e w s has s h o w n ( ' P r o c . R . S . ' 1875) t h a t b y m i x
ing nitrogen with carbonic acid, the c r i t i c a l t e m p e r a t u r e is
lowered, and that D a l t o n ' s l a w o f the density of mixed
vapours o n l y h o l d s at l o w pressures and at temperatures
greatly a b o v e their critical points.

Electrolysis. 325
MOLECULAR THEORY OF ELECTROLYSIS.
A v e r y interesting part o f m o l e c u l a r science w h i c h has not

been thoroughly w o r k e d out, b u t w h i c h h a r d l y b e l o n g s t o a
treatise o n H e a t , is the theory of electrolysis. Here an
electromotive force acting on a liquid electrolyte causes
the molecules of one o f its c o m p o n e n t s t o b e u r g e d i n o n e
direction, while those o f the other c o m p o n e n t are urged in
the opposite direction. N o w these c o m p o n e n t s are j o i n e d
t o g e t h e r in pairs b y c h e m i c a l f o r c e s o f g r e a t p o w e r , so that
we might e x p e c t that n o electrolytic effect c o u l d take p l a c e
unless the e l e c t r o m o t i v e f o r c e w e r e so s t r o n g as t o b e a b l e
to tear these couples asunder. But, a c c o r d i n g t o Clausius, in
t h e d a n c e o f m o l e c u l e s w h i c h is a l w a y s g o i n g o n , s o m e o f t h e
l i n k e d p a i r s o f m o l e c u l e s a c q u i r e such v e l o c i t i e s t h a t when
they h a v e an e n c o u n t e r with a pair also in v i o l e n t motion
the m o l e c u l e s composing one or both o f the pairs are torn
asunder, a n d wander about seeking n e w partners. If the
t e m p e r a t u r e is so h i g h t h a t t h e g e n e r a l a g i t a t i o n is s o v i o l e n t
that m o r e pairs o f m o l e c u l e s are torn asunder than can pair
again in an equal time, we have the phenomenon of
Dissociation, studied b y M . Ste.-Claire D e v i l l e . If, o n the
other hand, the separated m o l e c u l e s can always find partners
before they are e j e c t e d from the system, the c o m p o s i t i o n o f
the system remains apparently the same.
N o w Professor Clausius considers t h a t it is d u r i n g these

temporary separations that the electromotive force comes
into play as a d i r e c t i n g p o w e r , causing the molecules of
one component to m o v e o n the w h o l e o n e way, and those
o f the other the o p p o s i t e w a y . T h u s the c o m p o n e n t m o l e
cules are always changing p a r t n e r s , e v e n w h e n 110 e l e c t r o
m o t i v e f o r c e is in a c t i o n , a n d t h e o n l y e f f e c t o f t h i s f o r c e is t o
g i v e d i r e c t i o n to t h o s e m o v e m e n t s w h i c h are a l r e a d y g o i n g o n .
P r o f e s s o r W i e d e m a n n , w h o has also taken this v i e w o f
electrolysis, c o m p a r e s the p h e n o m e n o n with that o f diffusion,
a n d s h o w s that t h e e l e c t r i c c o n d u c t i v i t y o f an e l e c t r o l y t e m a y

b e c o n s i d e r e d as d e p e n d i n g o n t h e c o e f f i c i e n t o f d i f f u s i o n o f
the c o m p o n e n t s through each other.
MOLECULAR THEORY OF R A D I A T I O N .
T h e phenomena already described are explained on the

molecular theory b y the m o t i o n o f agitation o f the m o l e c u l e s ,
a m o t i o n w h i c h is e x c e e d i n g l y i r r e g u l a r , t h e i n t e r v a l s b e t w e e n
successive encounters and the velocities of a molecule
during successive free paths not b e i n g subject to a n y law
which w e can express. The internal motion o f a single
m o l e c u l e is o f a v e r y different kind. I f the parts o f the
molecule are capable o f relative morion without being
a l t o g e t h e r torn asunder, this r e l a t i v e m o t i o n will be some
kind o f vibration. T h e s m a l l v i b r a t i o n s o f a c o n n e c t e d sys
tem m a y b e resolved into a number o f simple vibrations, the
l a w o f e a c h o f w h i c h is s i m i l a r t o t h a t o f a p e n d u l u m . I t is
p r o b a b l e that i n gases the m o l e c u l e s m a y e x e c u t e m a n y o f
s u c h v i b r a t i o n s in t h e i n t e r v a l b e t w e e n s u c c e s s i v e e n c o u n t e r s .
A t each encounter the w h o l e m o l e c u l e is r o u g h l y s h a k e n .
D u r i n g its f r e e p a t h it v i b r a t e s a c c o r d i n g t o its o w n l a w s ,
the amplitudes o f the different s i m p l e v i b r a t i o n s b e i n g deter
mined b y the nature o f the collision, but their periods
depending only on the constitution o f the m o l e c u l e itself.
I f t h e m o l e c u l e is c a p a b l e o f c o m m u n i c a t i n g t h e s e v i b r a t i o n s
t o t h e m e d i u m in w h i c h radiations are propagated, it will
send forth radiations o f certain definite kinds, a n d if these
b e l o n g t o the luminous part o f the spectrum, they will be
v i s i b l e as l i g h t o f d e f i n i t e r e f r a n g i b i l i t y . T h i s , t h e n , is the
explanation, on the molecular theory, o f the bright lines
o b s e r v e d in t h e s p e c t r a o f i n c a n d e s c e n t g a s e s . T h e y repre
sent the disturbance communicated to the luminiferous
medium b y molecules vibrating in a regular and periodic
manner during their free paths. I f the f r e e p a t h is l o n g ,
the m o l e c u l e , b y c o m m u n i c a t i n g its v i b r a t i o n s t o t h e ether,
w i l l c e a s e t o v i b r a t e till i t e n c o u n t e r s s o m e o t h e r m o l e c u l e .
By raising the temperature we increase the velocity of

Radiation. 32/
the m o t i o n o f agitation and the force o f each encounter.
T h e higher the temperature the greater will b e the ampli
tude o f the internal vibrations o f all kinds, and the more
l i k e l i h o o d w i l l t h e r e b e that, v i b r a t i o n s o f short p e r i o d will
b e e x c i t e d , as w e l l as those fundamental vibrations which
are m o s t easily p r o d u c e d . B y increasing the density we
diminish the l e n g t h o f the free path o f each molecule, and
thus allow less time for the v i b r a t i o n s e x c i t e d at each
encounter t o s u b s i d e , a n d , s i n c e e a c h fresh encounter dis
turbs t h e r e g u l a r i t y o f t h e series o f v i b r a t i o n s , t h e r a d i a t i o n
will no longer be capable of complete resolution into a
s e r i e s o f v i b r a t i o n s o f r e g u l a r p e r i o d s , but will b e analysed
into a spectrum showing the bright bands due to the regular
vibrations, along with a ground o f diffused light, f o r m i n g a
continuous spectrum due to the irregular m o t i o n i n t r o d u c e d
at e a c h encounter.
H e n c e w h e n a g a s is r a r e t h e b r i g h t l i n e s o f its spectrum
are narrow and distinct, a n d the spaces between them are
dark. A s the d e n s i t y o f the g a s increases, the bright lines
become broader and the spaces between them more
luminous.
T h e r e is a n o t h e r r e a s o n f o r t h e b r o a d e n i n g o f t h e bright
lines and the luminosity o f the w h o l e spectrum in dense
gases, which w e have already stated at p . 245. T h e r e is
this d i f f e r e n c e , h o w e v e r , b e t w e e n t h e e f f e c t t h e r e m e n t i o n e d
and that described here. A t p. 2 4 5 the light from a
certain stratum o f incandescent gas was supposed to pene
t r a t e t h r o u g h o t h e r strata, w h i c h a b s o r b e d t h e b r i g h t e r rays
faster t h a n t h e less luminous ones. T h i s effect depends
o n l y o n the total quantity o f gas through w h i c h the rays
pass, and will be the s a m e w h e t h e r i t is a m i l e o f g a s at
t h i r t y i n c h e s p r e s s u r e , o r t h i r t y m i l e s at o n e i n c h pressure.
The effect w h i c h w e are n o w c o n s i d e r i n g depends on the
a b s o l u t e d e n s i t y , s o t h a t i t is b y n o m e a n s t h e s a m e w h e t h e r
a s t r a t u m c o n t a i n i n g a g i v e n q u a n t i t y o f g a s is o n e m i l e or
thirty miles thick.

3 28 Molecular Theory.
When t h e g a s is s o far c o n d e n s e d that it assumes the

liquid or s o l i d f o r m , t h e n , as t h e m o l e c u l e s h a v e n o free
path, they h a v e no regular vibrations, and no bright lines
are c o m m o n l y o b s e r v e d in incandescent liquids or solids.
Mr. H u g g i n s , h o w e v e r , has observed bright lines in the
spectrum o f incandescent erbia and lime, which appear to
be d u e t o t h e s o l i d m a t t e r , a n d n o t t o its v a p o u r .
LIMITATION O F T H E S E C O N D L A WO F T H E R M O D Y N A M I C S .
B e f o r e I conclude, I wish to direct attention to an aspect

of the molecular theory which deserves consideration.
One o f the best established facts i n t h e r m o d y n a m i c s is
t h a t i t is i m p o s s i b l e i n a s y s t e m e n c l o s e d i n a n e n v e l o p e
which permits neither change o f v o l u m e nor passage o f heat,
a n d in w h i c h b o t h the t e m p e r a t u r e a n d the pressure are e v e r y
where the same, to produce any inequality o f temperature or
o f pressure without the expenditure of work. T h i s is t h e
second l a w o f t h e r m o d y n a m i c s , and i t is u n d o u b t e d l y true
as l o n g as w e c a n d e a l w i t h b o d i e s o n l y i n mass,- a n d have
n o p o w e r o f p e r c e i v i n g or handling the separate m o l e c u l e s
of w h i c h t h e y are m a d e up. But if w e c o n c e i v e a being
w h o s e faculties are so s h a r p e n e d that h e can f o l l o w every
m o l e c u l e i n its c o u r s e , s u c h a b e i n g , w h o s e a t t r i b u t e s a r e still
as e s s e n t i a l l y f i n i t e as o u r o w n , w o u l d b e a b l e t o d o w h a t is
at p r e s e n t i m p o s s i b l e t o us. F o r w e h a v e seen that the
m o l e c u l e s i n a v e s s e l full o f air at u n i f o r m t e m p e r a t u r e are
m o v i n g with velocities by no means uniform, though the
mean velocity of any great number o f them, arbitrarily
s e l e c t e d , is almost exactly uniform. N o w l e t us suppose
t h a t s u c h a v e s s e l is d i v i d e d i n t o t w o p o r t i o n s , A a n d E , by
a d i v i s i o n in w h i c h there is a small h o l e , a n d that a b e i n g ,
who c a n s e e t h e i n d i v i d u a l m o l e c u l e s , o p e n s a n d closes this
h o l e , s o as to allow only the swifter molecules to pass
f r o m A t o B, a n d o n l y t h e s l o w e r o n e s t o p a s s f r o m p t o A.
He w i l l thus, w i t h o u t e x p e n d i t u r e o f w o r k , raise the tem-

Statistical Knowledge of Bodies. 329
perature o f E and l o w e r that o f A , in contradiction to the
second law of thermodynamics.
T h i s is o n l y o n e o f t h e instances in w h i c h conclusions
which w e have d r a w n from our e x p e r i e n c e o f b o d i e s c o n
sisting o f a n i m m e n s e n u m b e r o f molecules may be found
not to b e applicable to the m o r e delicate observations and
experiments which w e m a y suppose m a d e b y o n e w h o can
p e r c e i v e a n d handle the individual molecules w h i c h w e deal
with o n l y in large masses.
I n dealing with masses o f matter, while w e do not perceive
the i n d i v i d u a l m o l e c u l e s , w e are c o m p e l l e d to a d o p t w h a t I
h a v e d e s c r i b e d as t h e s t a t i s t i c a l method o f calculation, and
t o a b a n d o n t h e strict d y n a m i c a l m e t h o d , i n w h i c h w e f o l l o w
every m o t i o n b y the calculus.
It would be interesting t o e n q u i r e h o w far t h o s e ideas
about the nature a n d methods o f science which have been
derived from e x a m p l e s o f scientific investigation in which
the dynamical method is f o l l o w e d are applicable to our
a c t u a l k n o w l e d g e o f c o n c r e t e t h i n g s , w h i c h , as w e h a v e s e e n ,
is o f an essentially statistical nature, because no one has
yet discovered any practical method o f tracing the path
o f a m o l e c u l e , o r o f i d e n t i f y i n g it at d i f f e r e n t t i m e s .
I d o not think, h o w e v e r , that the perfect identity which
w e o b s e r v e b e t w e e n different portions o f the same kind o f
matter can b e explained 0 1 1 the statistical principle o f the
stability o f the averages o f large numbers of quantities
each o f which m a y differ from the mean. For if of the
m o l e c u l e s o f s o m e s u b s t a n c e s u c h as h y d r o g e n , s o m e w e r e
of sensibly greater mass than others, w e have the means
of producing a separation b e t w e e n m o l e c u l e s o f different
masses, and in this w a y w e should b e a b l e to p r o d u c e t w o
kinds o f hydrogen, one o f which w o u l d be somewhat denser
than the other. A s this c a n n o t b e d o n e , w e m u s t a d m i t t h a t
the equality w h i c h w e assert t o exist b e t w e e n the molecules
of hydrogen applies to each individual molecule, and not
merely to the average o f groups o f millions o f molecules.

33° Molecular Theory.
NATURE A N D ORIGIN OF MOLECULES.
W e h a v e thus t e e n l e d b y o u r s t u d y o f v i s i b l e t h i n g s t o a
theory that they are m a d e up of a finite n u m b e r o f parts or
m o l e c u l e s , e a c h o f w h i c h has a definite mass, a n d possesses
other properties. T h e molecules o f the same substance are
all e x a c t l y a l i k e , b u t d i f f e r e n t f r o m t h o s e o f o t h e r s u b s t a n c e s .
T h e r e is n o t a regular gradation in the mass o f m o l e c u l e s
f r o m t h a t o f h y d r o g e n , w h i c h is t h e l e a s t o f t h o s e k n o w n to
us, to that o f bismuth ; but they a l l fall into a limited
number of classes or species, the individuals of each
species b e i n g exactly similar t o each other, and n o inter
mediate links are found to connect one species with
another b y a uniform gradation.
We are here r e m i n d e d o f certain speculations concerning

the relations b e t w e e n the species o f l i v i n g things. We find
that i n t h e s e a l s o t h e i n d i v i d u a l s a r e n a t u r a l l y g r o u p e d i n t o
species, and that intermediate links b e t w e e n the species are
wanting. But in each species variations occur, and t h e r e is
a perpetual generation a n d destruction o f the individuals o f
w h i c h the species consist.
H e n c e it is p o s s i b l e t o f r a m e a t h e o r y t o a c c o u n t f o r t h e
present state o f things b y means o f generation, variation,
and discriminative destruction.
I n the case o f the molecules, h o w e v e r , each i n d i v i d u a l is
permanent; there is no generation or destruction, and no
variation, or rather n o difference, b e t w e e n the individuals o f
each species.
Hence the kind of speculation with which we have
b e c o m e so f a m i l i a r u n d e r t h e n a m e o f theories o f evolution
is q u i t e i n a p p l i c a b l e t o t h e c a s e o f m o l e c u l e s .
It is t r u e that Descartes, w h o s e inventiveness knew no
bounds, has g i v e n a theory o f the e v o l u t i o n o f molecules.
He supposes that the m o l e c u l e s with which the heavens
are nearly filled have received a spherical form from the
long-continued grinding o f t h e i r p r o j e c t i n g p a r t s , so that,

Equality and Permanence of Molecides. 331
l i k e m a r b l e s in a m i l l , t h e y h a v e ' r u b b e d e a c h o t h e r ' s a n g l e s
down.' T h e result o f this a t t r i t i o n f o r m s t h e finest k i n d o f
m o l e c u l e s , with w h i c h the interstices between the globular
m o l e c u l e s are filled. But, b e s i d e s these, h e describes another
elongated kind o f m o l e c u l e s , t h e partícula striata, which
have received their form from their often threading the
interstices b e t w e e n three spheres in contact. T h e y h a v e thus
acquired three longitudinal ridges, and, since s o m e of them
during their passage are rotating on their axes, these ridges
are n o t i n general parallel to the axis, but are twisted like
the threads o f a screw. B y means o f these little screws
he most ingeniously attempts to explain the p h e n o m e n a o f
magnetism.
B u t it i s e v i d e n t t h a t his m o l e c u l e s a r e v e r y d i f f e r e n t f r o m
ours. H i s seem to be produced b y some general break-up
o f his s o l i d s p a c e , a n d t o b e g r o u n d d o w n in the course o f
a g e s , a n d , t h o u g h t h e i r r e l a t i v e m a g n i t u d e is i n s o m e d e g r e e
determinate, there is nothing to determine the absolute
magnitude o f any o f them.
O u r m o l e c u l e s , o n the other hand, are unalterable b y any
o f t h e p r o c e s s e s w h i c h g o o n i n t h e p r e s e n t state o f t h i n g s ,
a n d e v e r y i n d i v i d u a l o f e a c h s p e c i e s is o f e x a c t l y t h e s a m e
m a g n i t u d e , as though they h a d all b e e n cast in the same
m o u l d , l i k e bullets, a n d not merely selected and grouped
a c c o r d i n g t o t h e i r s i z e , l i k e s m a l l shot.
T h e i n d i v i d u a l s o f e a c h s p e c i e s a l s o a g r e e in t h e n a t u r e o f
the light w h i c h t h e y e m i t — t h a t is, in their natural p e r i o d s o f
vibration. T h e y are therefore like tuning-forks all tuned to
c o n c e r t pitch, or l i k e watches regulated to solar time.
I n s p e c u l a t i n g o n t h e c a u s e o f this e q u a l i t y w e a r e d e b a r r e d
from i m a g i n i n g a n y cause o f equalization, on a c c o u n t o f the
i m m u t a b i l i t y o f e a c h i n d i v i d u a l m o l e c u l e . I t is difficult, o n t h e
other h a n d , t o c o n c e i v e o f selection a n d elimination o f inter
m e d i a t e varieties, for w h e r e can these e l i m i n a t e d m o l e c u l e s
h a v e g o n e t o if, as w e h a v e r e a s o n t o b e l i e v e , t h e h y d r o g e n ,
& c , o f the fixed stars is c o m p o s e d o f m o l e c u l e s i d e n t i c a l i n

all r e s p e c t s w i t h o u r o w n ? T h e time required to eliminate

from the w h o l e o f the v i s i b l e universe every molecule whose
m a s s differs f r o m that o f s o m e o n e o f our s o - c a l l e d e l e m e n t s ,
b y processes similar to Graham's method o f dialysis, w h i c h
is t h e only method w e can c o n c e i v e o f at present, w o u l d
exceed the utmost limits ever demanded by evolutionists
as m a n y t i m e s as t h e s e e x c e e d t h e p e r i o d o f v i b r a t i o n o f a
molecule.
But if w e suppose the molecules to b e m a d e at all, o r if
w e suppose them to consist o f something previously made,
w h y should w e e x p e c t a n y irregularity t o exist a m o n g t h e m ?
I f t h e y a r c , as w e b e l i e v e , t h e o n l y m a t e r i a l things which
still r e m a i n in the precise condition in which they first
began to exist, w h y should we not rather l o o k for some
indication o f that spirit o f order, our scientific confidence
i n w h i c h is n e v e r s h a k e n b y the difficulty w h i c h w e e x p e -
rience in tracing it i n the c o m p l e x arrangements o f visible
things, a n d o f which our m o r a l estimation is s h o w n in all
our a t t e m p t s t o t h i n k a n d s p e a k t h e truth, a n d to ascertain
the exact principles o f distributive justice ?
APPENDIX.
TABLE OF TKE COEFFICIENTS OF I?ITERDIFFUS

PROFESSOR LOSCHMIDT {SEE P. SQUARE 2
79)j ¿ «
Carbonic acid
V) . A i r . • T 4 2 3
— H y d r o g e n - -5614
O x y g e n . -1409
Marsh gas . -1586
Carbonic oxide , T 4 0 6
Nitrous oxide . •0982
O x y g e n H y d r o g e n • 7 2 ,
4
Carbonic oxide . -1802
H y d r o g e n •6422
Carbonic oxide
H y d r o g e n •4800
Sulphurous acid

Appendix. 333
Professor J. Stefan, also of Vienna, has undertaken a series of very
delicate experiments to determine the thermal conductivity cf air and other
gases. H e finds the thermometrie conductivity, K, of air 0-256 square
centimetres per second. The rate of propagation of thermal effects in
still air is therefore intermediate between the rate in iron, for which
a n M
« = 0-183, ^ - copper, for which «=1-077. Stefan finds it inter
mediate between iron and zinc.
r
The calorimetrie conductivity, &, is o oooo558 for air, or about 20,00a
times less than that of copper and 3,360 times less than that of iron.
?
As calculated from the coefficient of viscosity by the writer

k — O •000054.
Stefan has also found that the calorimetrie conductivity is inde
pendent of the pressure, and that it is seven times greater for hy
drogen than for air. Both these results had been predicted by the
(
molecular theory. See Maxwell O n the Dynamical Theory of Gases,*
Phil. Trans. 1867, p. 88.

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TEXT-BOOKS OF SCIENCE

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AND PARLIAMENT STREET

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J. CLERK MAXWELL, M.A.

Honorary Fellow of Trinity College aud Professor of Experimental Physics

in tlie University of Cambridge.

LUNliMA tfS, G R E E N , iftrN IV" CO,

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T H E A I M of this book is to exhibit the scientific

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subjects of the next division of the book. T h e last

THERMOMETRY, OR THE REGISTRATION OF TEMPERATURE.

Definition of Higher and Lower Temperature . . . . 32

CALORIMETRY, OR THE MEASUREMENT OF HEAT.

Selection of a Unit of Heat . . . . . . . 54

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Carnot's Engine , . . . . . , . ,138

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Principle of the Barometer . . . . . . ,217

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Waves of Permanent Type . . . . . . .223

Definition of Radiation . . . . . . . . 230

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Conduction through a Plate . . . . . . .2^3

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THE DISTINCTION between hot bodies and cold ones is

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temperatures. W e may give names to any number of

' ' Scientifick, a d j . P r o d u c i n g d e m o n s t r a t i v e knowledge.'—Johnson's

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T h e v o l u m e of m o s t substances increases continuously

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THE MERCURIAL THERMOMETER.

T h i s t h e r m o m e t e r consists of a glass t u b e terminating in

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would remain at the same temperature. Take another

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ultimately v a p o r i s i n g them, c o m b i n i n g w i t h b o d i e s in definite

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place tend to b e c o m e e q u a l . W e shall not at present discuss

We shall s e e that t h e p h r a s e s r a d i a t i o n o f heat and ra

The air t h e r m o m e t e r is first sur