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O F SO LI D S
J
SECOND EDm ON
f
l
f . A WtLBY·INTiiRSCIBNCB PUBU CAllO N
(
1
I JOH N WILEY & SON S, New York • London • Sydney
• Toronto
I
(
WILEY SER IES ON THE SCIENCE AND TECHNOLOG
Y OF MAT ERIA lS
Adoi.Jory Edito n: E. Burke. B. Cbal men, Jame s A. Knon
baDsl
TIIER .MoDY NA.NI CS or Souo s, SacoN D EDm
oN
Rldtt lrd A. Swalilr
THE SUPUlAl.LOYS
CMst er T. Sinu GJtd William C. HDGel, editor~
X-RA Y DIFFa AC'nO N METHODS IN Pot.V Nn
SCI.ENCE
L. E. AleJUIItder
PHYs iCAL hOPE :RnES OF MOLE CULA~ CkYS
TAU, LIQUIDS, AND GLASS£5
A . .&nd i
FRAC lURE OF STRU CTUR AL MATEJUALS
A. S . Teulm an turd A. J. Mc& ily, Jr.
ORGA NIC SEMICONDUCTORS
F. GMtm tUUI tutd L . E. Lyon s
!NT£R META LUC COMPOUNDS
J. H. Wutb rook , editor
THE PHY31CAL PRJNCJPLES OF MAGN EnSM
Allml H. Morrislt
HAND BOOIC OF EuCT RON B~t.t WELD INO
R . Bokish tutd S . S . Wlrite
Pu'YslC:S Of M AONETISM
sosJri11 CJUJcazu.nU
PHYS ICS Of lU-V CoMP OUND S
Otfri ed Made lunc (translation by D. Mqer hofer )
PRINCI PLES OF SoUO IFICATION
Bruce CM/m n-s
THE MECH ANICAL PROPERTIES OF MAT'J"'iR
A. H. Cottr ell
THE ART AND SelE Na OF GROW JNG CRYSTALS
~ J. J. GilmtUt, ~itor
v
SELEC TED A.LUES OF THEllMOOYNAMIC PROPE
RTIES OF META LS AND ALLO YS
Ralph Hultp-e~t, Raym ond L. 0", Philip D. Anderson tutd
K£nneth K. Kelly
PROCESSES OF CltEEP AND FAnG uE IN M6T.u
..s
A . J. XelfMdy
CoLU MBIU N AND TANT ALUM
FrturJc T. Sisco llltd Ed•w d EpremiQII, editors
TRANSMISSION El.EcT RON MlatO SCOP Y OF
METALS
Gant la TltolftiiS
Pl.As naTY AND Ck£61" OF M6TALS
J. D. Lllbalua GJtd R. P. Fetcar
IN'r'RooUC110N ro Cn.u cacs
W. D. Ki'r" Y
PHYSICAL. NETALLUitOY
Bnl«~
ZoNE Mm.11NO, SECO ND EDm oN
Willia m G. Pftllflf
..
Preface
The statement of intent that constituted the Preface to the first edition
basically still applies. This second edition hopefully has benefited from the
suggestions from numerous readers of the first edition. In addition, before
undertaking the revision, I contacted many colleagues in various laboratories
and received many helpful suggestions. Particular thanks are due to numerous
graduate and undergraduate students, to the translators of foreign editions,
and to Professor C. A. Wert at the University of Illinois for many thoughtful
comments.
In this second edition, more material is included that pertains to the
physical and magnetic properties of solids. The treatment of the first and
second Jaws of thermodynamics is somewhat expanded. In discussion of
the properties of intermediate phases, more emphasis is placed on recent
developments that concern our understanding of nonstoichiometric crystals.
The intent of the entire treatment is to give the reader a familiarity with
the fundamentals associated with thermodynamic properties of solids, to
permit him to make reasonable estimates of thermodynamic properties for
unstudied but perhaps important systems.
RICHARD A. SwAUN
MilrNapolis.. Milllresota
April, 1972
Data ... ~.C..../...~-~-·;.j ·/ 10
·\ .. -···
\\\' \ ~~ ····· ·· r\ \..~·~·
Proc. ···········t\·,t··· ~ -~~
~~o_, ... -·····
Errp........ -~ -.. -~
· ~ . ·········••
U v. ... · ~
~
cr........ .~ C\.
.\~
"lO · ········
N F .............~ ..lJ , · ····•····•··•••••·
Sc 1 i.: . . ~ t .,,~~ ....~J....--...- -_
~- ... ·- - ~~ .....-.
Swalin, Richard A
1bermodyua.mics of solids.
(Wiley series on the science and U:chnology of materials)
Includes bibliogra phical references.
J. Crystallo graphy. 2. Solids. 3. Thermod ynamics.
I. Title.
QD937.S9S 1972 548'.8 72~~
ISBN 0-47l..a3854-3
Printed in the United States of America
1~9 8 7 6 s• 3 2 1
-
..,
- • r
.
Thermodynamics of Solids
.,_.,..,..
.
~,....
-
. .
·.
' ..
l
")
)
Preface to Flnt Edltioa
,
processes. much thermodynamic information may be gleaned from theae )
diagrams. The emphasis here is not upon the use of thermodynamics. to
assist phase diagram construction but upon the use of phase diagrams to
obtain thermodynamic quantities. The last part of the book is concerned
with the thermodynamics of defects and defect interactions in metals,
elemental semiconductors, and compounds. The reason for this emphasis
f
t
hardly needs explanation since it is well known that a great many of the ,
important properties of crystals are dependent upon these def~. Con- -:--)
siderable emphasis is placed upon the electrical properties of oxide semicon-
)
ductors. Two reasons exist for this. In the first place, oxide semiconductors
are becoming of great importance in technological applications such as the
maser and optical maser, to cite only two. In the second place there is a
dearth of information concerning the relation of defect structure to other
properties in these materials. There is no question that such effects will be
found. however, by investigators in the future .
•
RICHARD A. SWAUN
Mirwapolis, MiMesota
D~umber, 1961
( ·
•
Conten ts
1 Introduction 1
ix
X Coateat.
. ""
7.2
-7.3
Application to Ideal and Regular Solutions
Nonreg ular Solutions
145
148
.
I
7.4 Order- Disorde r Transiti ons in Solids 153 .I
7.5 Some General Conside rations of Alloy Systems 160
t
8 Equilibrium Between Phases of Variable Composition 165
.
I
8.1 Gibbs Phase Rule 165 1 .I
.
8.2 'Calculation of Thermo dynami c Quantities from Simple
Phase Diagrams 168 i
8.3 Effect of Pressure on Solubility 178
8.4 Solubility of Small Particles 180
8.5 Equilibrium Between a Solid Solution and a Liquid Alloy 184
8.6 Solubility of a Metasta ble Phase 186
J
I
Cooteaa
Appendix 370
'
-)
I
.tI
.' ~
:.j
) '
)
s a power-
The application of thermodynamics to the study of crystals offer
. With the
ful quantitative tool for the investigation of important properties
structure of
aid of thermodynamics, for example, one is able to control the
the crystals.
a material without the necessity of knowing atomic details of
not need to
One of the principal reasons for this power is that one does
ing the three
postulate any specific model of the cryst al Rather, by apply
ematical
laws of thermodynamics in conjunction with standard math
can be
techniques many macroscopic or phenomenological properties
amics, by
obtained unambiguously. The application of classical thermodyn
rality and
itself, is rather incomplete, however, since because of its gene
ip amon g
simplicity, virtually nothing is learned abou t the detailed relationsh
erning these
atoms and defects in crystals. In orde r to obtain insight conc
the aid of
quantities appeal must be made to statistical mechanics. With
interprer
statistical mechanics, the investigator is able to obtain atomistic
of both
tations of properties of atoms and defects in crystals. Knowledge
, therefore, a
classical thermodynamics and statistical mechanics represents
powerful combination in the study of crystals.
amically.
Properties of crys1als on two levels are of interest to us thermodyn
ivity of one
First, there are the gross properties such as chemical react
reaction
species with another and consideration of the extent to which a given
will proceed. Secondly, there are the fine scale properties
such as the con-
By defect is
centration of various types of defects and defect interactions.
conductors,
meant lattice vacancies, electrons in the conduction band of semi
lated, how-
dislocations, impurity atoms, etc. These two levels are not unre
al may be
ever, since the concentration of various types of defects in a cryst
onments.
markedly influenced by exposure of the crystal to various envir
uctivity of a
By appropriate equilibration for example, the electrical cond
magnitude.
compound semiconductor may be changed by several orders of
1
"'i\.
)
lntroductio ll -~
l
Following this philosophy, both the gross and atomistic features of crystals .)
are discussed in the following chapters.
·~
Generally speaking the International System of Units, designated as Sl, . I
newton (N), the unit of mass is the kilogram (kg), the unit of pressure is
newton per square meter (N/m'), and the unit of length is the meter (m), for
Table 1.1 Units in SI System
Elemental Units
Length meter m • I
'
I
Mass kilogram kg
Time second s
A
-~-
Electric current ampere
Temperat ure degree Kelvin OK
Derived Units
Area meter rnt
Volume meter ms
Density kilogram/m eter kg/m3
Force newton N (kg · m/s2 )
Pressure newton/m eter N/m1
Energy, work joule J (N · m)
Power watt w '
Frequency
Acceleration
Hertz
meter/scco nd1
coulomb
Hz (s-
m/s1
C (A· s)
1)
•
Electric charge
Voltage volt V(W/A)
J;Jectric resistance ohm O(V/A)
Magnetic flux weber Wb (V · s)
Magnetic flux density tes1a T(Wb/m1 )
Conversion Factors
To convert from to multiply by
atmosphere newton/m eter • 1.01 X 105 .
bar newton/m eter 1 X 105
BTU joule 1.05 X 103
calorie (l5°C} joule 4.185 .
centimete r of Hg (0°C) newton/m eter 1.333 X lOS
electron volt joule 1.602 X 1o-11
erg joule 1 x to-'
torr (0°C} newton/m eter 1.333 X lOS
gram/cent imeter kilograrn/metw 1 X 101
dyne newton t x to- s
Introductioa 3
example. Much of the presen t literature as well as most of the past literature
employ other units, however, so the reader should be familia r and com-
fortabl e with several systems. For example, the standa rd unit of energy that
has been historically employed by Gthe· chemist is the 15°C calorie. Con-
sequently much of the literatu re concerned with _gross thermo dynam ic
properties of substances employs this unit. The physicist has traditionally
employed the electron volt as the unit of energy. Conseq uently much of the
literature that deals with crystal defects and electronic proper ties employs
this unit. In order to familiarize the reader with different unit systems,
figures obtaine d from the literatu re are generally left in the origina l units.
Some convenient conversions between the SI system and other unit
systems are listed in Table 1.1 and some useful general physical consta nts
are tabulated in Table 1.2.
Table 1.2 General Physical Constants
Unit
I
~Ins ulation
A B
- J
.}
Te < Ta' < TA·<TA ·~
....;
TA· Te'
Heat Y-
A B
Shott time C)
78< T<TA
-
~
l:·::c:J
(/)
.f'-1
~
Lone time · ~
.........
Pia. 2..1 Heat flow between bodies at different temperature.
..
?- .~. ..
l.l CakulatJoas of Work
'
Experience has shown that there are several ways of changing the tem-
perature of a substance. Among these are effects due to mechanical, electrical.
and radiation processes. Thus one speab of the transfer of mechanical
~n~rgy. electrical energy, or radiant energy, for example. AI an illustration,
imagine an object that is traveling through space with a certain velocity.
This object strikes in an inelastic fashion another .object and is brought to
rest The kinetic energy which was associated with the moving object ia
translated into thermal energy. It is said that one object (the moving object
in this case) has performed WC!rk on the other one. In this .illustration, the .
moving object performed an amount of work, W, on the stationary object.
The stationary system (including both objects) had its temperature increaSed.
If a quantity of beat Q is allowed to flow from the system to the surroundings,
the temperature could be returned to its original value.
This leads to the statement of the first law of thermodynamics. A system
that performs an amount of work W on its surroundings and r~ives an
amount of heat Q is defined to have undergone a change in internal energy
liU. Thus in algebraic terms ,
l:l. U = Q - W (2.1)
Mechanical Work
The term D W is very general and may refer to electrical work, gravitatioilaJ · --::: ~~
work, mechanical work, work against a magnetic field, etc. Let us conside_!"
The First Law of Thermoci)'IUllllks .
'
first mechanical work. Suppose a system extends a force F, through a path s.
J
)
The work done by the system ia
(2.3)
I t
I
System = P- dP
:Pr-e-ss-ur-e~
Pressure= P I
I
I
I
>~
Fag. 2.2 ntustration of mechanical work.
recalled tltat W is defined to be positive in sign when the system does work
I ~
I
dU = DQ - p dV I -~ (2.5)
and
W = nRT
! 00' y
nRT In Y
101 -
- 'f:-
t:...
v, ; ,.
•
! •
W = (I mole) (8.3 Jfmol·K)(500;x.}(2.3 )(-I) ": ~ . :.._
I
. ""-"'" ...
I
- .. .
- ~
J
Surfa ce Work
surface
Let us now consider the work done in increasing the area of a
ce tensi on of a
(shown in Fig. 2.3). This system has an area of A and a surfa
I
I
r
_., 1-+- dr
Surface I
area, A I
I .
crL I F
L I
I
I
I
L
Fig. 2.3 lllust ration of surface work.
I
I
I
DW = - 'di dx = -u dA (26)
Electrical Work
ric poten tial
If electricaJ work is being perfo rmed rever sibly , i.e., if the elect
surro undi np,
of the system, 8, is only infinitesimally larger than that of the
DW = (electric potential) x (charge)
8 Tbe First Law of Tbermodynamlca
Thus
DW=IdZ (2.7)
Magn~tic Work
Ring of magnetic
material
• M . W. Zananslcy, Heat and Thermodynamics~ 4th ed., McGraw-~ New Yor~ 1951.
2.2 CaJculatlout of WOJ'k
,._';
_,The quant
emf E. itativ e relati on is expressed as
dB
E = -NA -
dt
' and since
Durin g the period dt, the work done by the system is given by 2.8
I= Fdnfdt
• dW ::::: - N Ai dB
H = 4.,NA i
v
and upon subst itutio n
DW = - - HdB
v
4.,
B= H + 4.,M
v
and theref ore
v (2.9)
DW = - - HdH - HdM
4.,
rtiona l
The magnetization of a diam agnet ic or param agnet ic material is propo
toH
M=x~
em.
lfH is measured in oerste ds (dyne /unit pole) and M is meas ured in pole
the work is expressed in ergs. Comp ariso n of 2.10 with 2.4 indica tes
that the
yed
H term is analo gous to p.and M is analo gous to V. Equa tion 2.10 is emplo
ymen t
in deter minat ion of the magn etic susceptibility of mater ials by emplo
n A is
of the Go,uy technique. In this meth od, a long thin rod of cross sectio
lie in the
suspe nded vertically in a magn etic field in which the lines of flux
10 The FIJ"St Law of Thermodyna mics
--
--
,.,.-
...--- -----
----
-........
-----
H2
--- l
•
I
I
.l
11
at Cap aci ty
l.3 1be Enthalpy Fuoctioo and He
-.
•
(2.16)
dH = dU + p dV + V dp
o 2.16·
and , if equation 2.5 is substituted int
dH = DQ + Vd p
Dividing by dT,
dH _ DQ Vd p
dT - dT + dT
(2.17)
b on the rig ht- han d sid e of equ atio n 2.17 is the hea t capacity defined
The ten
nt pressure. Th us
by 2.13, wit h the restriction of consta
(2.1 8)
n tha t, for a sys tem und er con sta nt pressure, the heat inp ut is equal
lt is see y, one
the ent hal py cha nge dH . In dea lin g with solic:fs experimentaiJ
to
lly wo rks wit h sys ten :tS itC On sta nt pressure, and hence enthalpy
·genera
rgy changes.
changes are easier to measure than ene
12 1be First Law of Thermod ynamics
.. \
,
The heat capacity of a substan ce is generally strongly depende nt on I
tempera ture. As we shall see in a later section, c. - Cv -+ 0 at T-+ 0.
For many solid elements, on the other hand, c. approac hes a value of about ~
II
25 Jfmol · K or 3R at high tempera tures. For the investig ator interested I
in the detailed nature of substan ces, knowledge of the heat capacity is impor- ' I
tant since, from the tempera ture depende nce of the heat capacity , informa tion I
about the mechanism of the manner in which energy is absorbe d by the
I
predomi nate since it is decreasi ng linearly with T, whereas the first term is
decreasing as 'P. From a practica l standpo int the second term is normally
importa nt below about 4°K. One may obtain y and () for a particul ar sub-
stance from low tempera ture measure ments. Dividing both sides of equation
2.19 by T yields
C, Cv ~ 2
- ~- = K8 T + y
T- T
(2.20)
.. . - -.. ••• •• .• .• . • • •
1.45 Fe 5.0
AI
0.75 Ga 6.0
Au
2.72 Li 1.75
Ba
2.99 Nb 7.5
Ca
5.0 Pd 9.45
Co
0.69 Rh 5.5
Cu
modynamic Prop ertiu of Metals and
• From R. Hultgren et al., &l~cted Values of Ther
Alloys, Wiley, New York . 1963.
35
30
Constant H;...-1-----f----"
---~
~
- ~
Constant volum e
3R
I
{ Copper
.
10
0
)
900 1000 1100 1200
0 100 200 300 400 500 600 700 800
Temperature rK) --+
y, b .....JI
and Cy for cop per. Fro mM . W. Zemansk
1'11- 2.7 Tem pera ture vari atio n of c_ ission of
-Hil l, New Yor k. 1968 . Use d with perm
tDtt1 Tlt<-rmtX/ynlltnics, Sth ed .• McG raw
McG raw -Hil l Boo k Company.
l..C Heats of Formadoa 15
term is very small. The principal interest in these terms is as an aid in providin& '
fundamenta l understanding about the nature of materials themselves. In ·
addition, for designers of cryogenic systems, the terms themselves may have
considerable design iiiiportance.
Subst ance llH1° (kJ/m ol) Substa nce llH1° (kJ/m ol)
ons. The
to one atmos phere pressu re for all quant ities involved in the reacti
e at 298°K
heat of forma tion of an element which is therm odyna mically .stabl
tin
will, of cours e, be equal to zero , as show n in Table 2.4 for both white
and graph ite. A negative value for ll.Ht refers to an exoth ermic
proce ss,
where as a positive value of ll.H,O refers to an endothermic proce ss.
dH 0 = C,dT
To find the cha nge in enthalpy o r the su bstaucc between 29~" K a nd 1',
integra te between 298° K a nd T. T hus
H 1'
0
- /1 ~ 08 =
l TdH 0 =
2118
i2'
:.!98
C 1, dT
~
1.
,
Tile First Law of Thermodynamics ~~
18
Illust ratio n 2
Problem. Find th e following enth alpy of reaction at 8001) K.
II
MnSiOa(s, 800) = MnO (s, 800) + Si0 2 (q uartz , 800)
react ion at 298°K
Solution. To solve this prob lem, find the enth alpy of
from the heats o f forma lion as in Illus tratio n I .
( l) MnS i03 (s, 298) = MnO (s, 298) + Si0 (qua rtz, 298)
2 !::. ~-~ ~98
298
(Cv)4 dT
and
!:ll/ 1 ,o = f:lN~ 98 + 6..a
1
800
298
d?' + ~b
i 800
298
T dT + 6..c:
298
2
dT
.I
•
'i
= 6.H~9s + D.a(800 -
2
6.H To 298) + 6.b ((800) 2
- (298) j
2
-I J ·I
i
D.c - I .I
[ 800 298
From Tabl e 2.2
,j
D.a = - 17. 1
I0
j
6.b = 26.2 X 3
0
6.c = I 0. 8 X l 05 I
Subs titut ion yields 6. /f:1, •
:!
19
2.5 Heats of Reaction
transformation tempera ture, and the heal capacity of the high tempera ture
modificatio n would be used between the tran ~i Lion tempera ture and Lhe
tempera ture of in terest. Another term would also be needed for the enthalpy
change of the phase change at the transitio n tempera ture.
Ulustra tion 3
Problem . Calculate the enthalpy change of the followin g reacti o n at
J300°K.
Ag(/, 1300) + k Cl 2 (g, 1300, I atm) = A gCI(/, 1300)
Solution . From Table 2.4, we lim.l the heal f'o r111ati o n al 29tf' K
-( ll ~aoo - fl ~us) = i
1
I:JOO
Cv dT
Additio n of reacti ons I through 8 gives us the desi red reactio n and, upon
substitutio n of the appro priate heat capacities and hea ls o r fusion, 1:1 11"
the desired heat of reactio n is obtained at 1300° K.
Jn the above illustrati o ns, analytic function s of the heat capacity as a
function of temperature for various suhstnn ccs were uvailahle and conse-
quently rather accurate values of entha lpics could be calculated . For ma11y
purposes cruder estimates of /:1.// are a ll that are needed. l n these instances,
mean values of the heat capacities for the s ub~ta nces involved may be
employed. Consequently in calculating the enthalpy change associated with
20 The First Law of Ther mod ynam ics
PRO BLE MS
728 kg/m3 , respectively.
.t
..,..,.
J. Gray tin and white tin have densities of 575 and ~e
l'f
Calculate the work done by our system upon the
tin transforms to gray tin at 286° K and I atm press
surroundings when
ure. Express answer in -lIf 'ft,,
gray tin is in a lower energy state. At 298° K, ho wever, white tin is round to
exist as the stable form. lt is clear, therefore, that some other criterion is
necessary for predicting stability. The criterion that has been found to be
satisfactory is a quantity termed e11tropr- This quantity has some very inter-
esting properties , as we shall see later. In order to illustrate, consider both
a system of interest and the surroundings of the system. A process of some
type is occurring within the system and heat may be exchanged with the
surroundings. For an infinitesimal amount of process completion the total
entropy change, dS, associated with this process consists of two terms,
dSHYIJt- of the system and dSJ<urr of the surroundings.
The entropy change dS has the interestin g property thal for a reversible
process dS = 0 and for an irreversible process ciS > 0, according to the
second law of thermody namics. The above statement is in a sense a state-
ment of the second law. According lo the Carnot-C iausius theorem, the
21
22
'
The Second Law of Thcrmodyoami s
I
dU = (au)
ar vdT + (au)
av c~v 1·
(3.6)
DQ = CvdT + RT dV (3.8)
v
The right-hand side of equation 3.8 is an inexact differen tial. By dividing
through by T , we obtain
DQ = C dT + R dV (3.9)
T v T V
Thus the right-hand side is converted into an exact differen tial and therefore
the quantity DQ/ T or dS must be an exact differential. As a result the
quantity dS depends only upon the state of the system and is independent
of the path. Rearranging equation 3.2 and substitu ting 3.5 gives a useful
form of the first Ia w for a reversible process:
dU = TdS- pdV (3. 10)
Even though the calculation was performed for an ideal gas as an illustration,
the entropy is a state property for any type of substance.
23
3, 1 OefinHi on of Entr opy
rese rvoi rs at temp eratu re
· As a furth er illus tra tio n co nsider two large heat
T1 and T 2 with T 2 > T 1• Fo r a bri~f mom ent the hea
t reservoirs are brough t
perm itted to now from T 2
into cont act a nd a small quan tity of heat DQ is
that no perce pti ble change
to T 1• (Jt is assumed that the reservoi rs are so large
in calc ulating the entr opy
in temp eratu re of eith er occu rs.) We are interested
si nce the process is ir-
chan ge of th e reservoirs but ca nn ot do so dire ctly
d fo r reversible processes
reversible and conseque ntly the equa tions develope
rsible process which will
e<tnnot be used. Thu s we need . ~ o co nstru ct a reve
entr opy is a state prop erty ,
yield the entr opy chan ge of the rese rvoi rs. Since the
ts the criterion o f rever-
the path chos en is not impo rtan t as long as it mee
tity o f ideal gas in cont act
sibility. As a tho ught expe rime nt, place a quan
nd isoth erma lly, thereby
with rese rvoir 2 at temp erat ure T 2 • Allo w it to expa
r. The expa nded gas is
rem oving a quan tity of hea t DQ from the rese rvoi
era ture drop s to T 1• T he
then isolated and expa nded reve rsibl y until its temp
Step 2\
2
3 -DQ /T1
4
24 T he Second Law of T hermodynamics
From the Carnot cycle we see that the entropy change o f the reservoirs
themselves is
dS = DQ _ DQ = DQ(T2 - T1)
T1 T2 T1 T2
Since T 2 > T 1 , dS > 0 as required by the second law for a n irreversible
process. On the other hand, for our reversible thought experiment, which J
'
includes gas and reservoirs, dS = 0 as required by the second law. I
Some other calculations wiJI be presented in the next secti on.
where Lt represents the enthalpy cha nge associa ted with the transformation.
For the reaction
Sn(gray, 286) = So(whitc, 286)
•)
L, has been measured as 2. 1 kJ/mol and hence !J.S, is 7.3 Jf moi·K .
esses 25
3.2 Entropy Ca lculations for Various Proc
ch con sist s of tin . It is of inte rest
Thi s entr opy is gain ed by the syst em whi
und ings . Sin ce 2. 1 kJ ente red the
to conside r wha t hap pen s to the s urro
2. 1 kJ had to leav e the s urro u ndin gs
syst em o n tran sfo rma tion of a mol e of tin,
oun din gs mu s t be at the sam e.
Sinc e the process is isot herm al, the surr
tem pera ture a nd ther efo re
Lt
(6S )aur r = -- = -7. 3 J f mol ·K
T
con sist ing o f our system plus its
The tota l entropy cha nge o f the univ erse
ies:
surroun ding s is the s um o f the two en trop
6St + 6S urr = 7.3 -
8
7.3 =0
nges
Entropy Cal culation when Tem pera ture Cha
ons of reve rsib ility and con stan t
As in the last illus tra tio n , the restricti
s
pres sure wi ll be plac ed on the proc ess. Thu
dS = DQ
T -
26 The Second Law of Thermodynamics
The entrop y of the reactio n of interest equals (/J.Sl + /J.S2 + 6.S3). Using
the equatio ns of the last section, it is seen that
Thus
-i7'm·v· ((C,), -
6.Ssyt~t.-
,
(Cp)•) dT- -L-
7'a T Tm.p.
Consider now the surroundings. As was pointed out, the irreversible process
is able to transfe r heat reversibly to the isothermal reservo ir. The entropy
change of the reservo ir is simply equal to
!J.Ssurr = L ,
~
1' s
,. and
6. 1/a =
ITm . p
(C,,). dT
28 The Second Law of T hermodynamics
lllustration
Calculate the entropy cha nges of system and surroundings fo r the case
of the freezing o f supercooled liquid silver a t 1073°K. The melting point of
silver is 1234°K and the heat o f fusion is 11 .2 kJf mol.
From Table 2.2 the constants for the heat capacities of li quid and solid
silver are obtained. Examination of the data shows that CJI for liquid silver
is indicated to be valid from the melting point to 1600°K, whereas we are
interested in C 11 fo r supercooled liquid . The best approach in this case is to
extrapola te the cf) data for the liquid determined a t high tempera ture to the
lower temperature. From the above eq ua tions we may wri te ror the reaction
Ag(l, 1073) = Ag(s, 1073) tiS
1234A J:l234 J:il34A 1) 200
I::!S = ~ dT + fib dT + ~3 dT - ~·-
J:1073 T 1073 1073 T 1234
1234 12:14 1 1234
~S = ~a In T + ~bT -~fie - -9.11 1 •
1o13 1o13 T2 1o13
Substitution yields
~SAg= -9.2 Jfmol·K
To evaluate I::!Saurr• evaluate L 1 by the method discussed. Thus
1234 i l231 112346
-L1 = !:ia dT + fibT dT + ~ dT - 11,200
i 1o1s 1o1a 1o1a T 2
or
av)T + P] ar ,
c11 = Cp + [(au (av) (3. 17)
Expe rimen tally , one ca n meas ure p and (oVfo T),, quite easily , but it is
energ y with volume
gener ally more diffic ult to obtai n the chan ge of inter nal
at cons tant T, (au;av)T· Therefore , let us attem pt to express this quan tity
in g U = f( T, V) we
in terms of more readily avail able quan tities. 13y ex press
find
dU = (aU) dT + (au) dV (3.18)
aT v av ']'
For a reversible proce ss dU = TdS - pdV (3. 19)
(as)
arv=
1 (au)
T aT v
(3.22)
and
(as)
avT-
__!_[(au)
r av
+ J
P T
(3.23)
and
lr avo•uar-_l[ o•u + (opar ) J_..!..[
r ar av T2 av v
(ou) + J T P
Thus
I
dV = (aV\ dp + (av)
ar ,,
dT
ap J1,
! 3.3 Some Useful Relations Obtained from the Second Law 31
0- (~;)J~~), + (~i).
or
(:~t = - (~i)j (~;),.
Since the volume thermal expansion coefficient, ex., of a substance is defined
as
<X= ~ (~~),.
and the compressibility {J is defined as
fJ = _ J..v (av)
op 1·
we have
(op) ex.
oT r, = p
(3.26)
v Ct. fJ
(units or (units of (units of c., C'/)- C11 c,.
T {° K) 10- 6 m 3 /mol) 10- s oK- 1) J0- 11 m:t/N) (J/moi·K ) (Jfmoi·K) (J/moi ·K)
0 .-.7.0 0 -.-Q.7 10 0 0 0
.......7.002 ,.._, 11 .5 -.-Q.7 12 5.77 0.00644 5.76
50
.......7.008 31.5 0.72 1 16.2 0.0960 16. 1
100
200 r-J7.029 45.6 0.748 22.6 0.390 22.2
7.043 48.0 0.762 2) .(1 0.53 1 23. 1
250
7.256 60.7 0.922 28.0 2.32 25 .7
800
7.452 69.7 1.030 30.7 4. 19 26.3
1200
Based on a table fro m M. W . Zemans ky, H C'a t nm/71,erm odynamiC':;, 4 th cd. , McG raw-
0
At cons tant T
- dV = (av\ dp -pv dp
=
()p. JT
Ther efor e
w= -1 v 71
f3 p d p
iipp2
W =- -
2
m 2) 2
I0- 5 m3 / mol) (3.8 4 x I0- m /N)( l0 x 9.80 N /
11 2 7
W= -H1 .47 X
= -2.7 Jfm ol
's eq ua ti ons that
We shal l show later whe n co nsid ering Max well
dS = - (av )cip
()T v
= -«V dp
As the term thermo elastic implie s, this pheno menon relates a tempe rature
ted
cha nge of a system to mecha nical stress. Consi der a system well insula
is
from its s urroun dings so that there is no heat fl ow to the system . This
called an adiaba tic system . Let us now apply a hydro static press ure p
to the
to
system . Since reversibility is the basic restric tion we must place in order
treat the sys tem therm ody namic ally, the press ure p mu st be applie d in
such
e
u manne r that the system is straine d elastic ally and not plastic ally. A chang
the
in tempe rature ciT will now result from u chaugc in pressu re dp. Since
we
process is perfor med adiaba tically , DQ is zero and Q is co nsta nt. Thus
need an expres sion for (artap)
0 . It seems reaso nable
to begin with a state-
ment of the first law :
dU = DQ- pdV
ngi ng
Dividi ng throug h equati on 3.28 by dp, holdin g Q co nstant ,. and rearra
terms, we have
c (ar) _ [(au) + P] (av)
ap o
(3.29)
v apQ- - av r
The term [(oUf oVJJ. + p] is equal to (apta T),T as shown by equati
on
, we
3.25, and (aptaT )v is equal to rx/{3 as expres sed by 3.26. Substi tuting
have
(aaT)
pQ= -
Trx (a
c vf3 ap
v) (J
(3.30)
-
The term (o Vfap)Q is not readily obtain able experir11entally so it is worth
more
while to invest igate wheth er o r not it can be elimin ated in favor of
easily obtain able quanti ties, such as rx and (1. T o obtain this term as f(rx,
{3)
'
34 T he Second Law of Thermodyn amics
dV = (av)
ar, dT + (av)
op r dp
or ...
c/V = Vex d"J"- Vfl clp (3.3 1)
Dividing through by dp, and holding Q constant,
(av)
op Q
= vex(oT) _ vp
op Q
(3.32)
oT)
(op VTex
(3.33)
Q= [Cv + VTex 2j{JJ
The term in brackets in equation 3.33 is equal to C 11 , as found in the lcw; t
section, a nd thus
()T) = VTex
( (3.34)
op () C,
From equation 3.34, since aiL quantities on the right-hand side are positive,
we find that application of external pressure to a system results in a tempera- I
J •
ture rise.
lllustr·a tion
Problem. Suppose that a particular materials applicatio n calls for a
specific tensile stress to be applied to a well insulated crystal at 300°K.
This system is subjected to tensile stress nuctuations 6.u. JL is suggested I
I \
dT = _ Vat: da
T 3C11
Lf it is assum ed that ex and C., are little affected by the strain, then upon
integration
In (T + 6. T) = _ Va: ll a
T 3C1'
«
If llT T , In [(T + llT)/ T] may be expanded in a n infinite series and high
order terms neglected . Doing this and using the relation
V=M
p
where M is the molecular weight and p is the density, we find
lla = _ 3C11 6. Tp
(3.35)
MTa.
Substituting the appro priate physical quanti ties, we ftnd lla = ±6.8 x JOS
J/m3 • Or lla = ± 6.94 x 1()4 kg/m2 • From 3.35 it is seen that a tensile stress
causes a temperature decrease, whereas the opposite occurs fo r a compressive
stress.
Boltzmann's Definition
Entropy is one of the most impor tant conce pts of therm odynamics, and
one of the least understood. As a result, individuals often memorize the
appro priate definitions without really understandin g the physical basis for
them. In later chapters we shall often need the entropy concept as a working
tool in the study of crysta l properties, so it should be properly unders tood .
I According to Boltzma nn, there is a relatio nship betwee n the entrop y of a
system in a given state and the probability of existence of the given state. He
sugges ted that it might be possible to calculate the probability of different
states of a system from analysis of the variou s distributions possible. Planck*
\. expressed Boltzmann's statement mathematically as
S =k In ir + const (3.36)
c2 =_ §_ !_ =6 x5 = 15
2! 4!
0
2
fo ur ob jec ts left an d
Sim ila rly for box 3, we hav e
C -~-4x3_ 6
4 2 -2 !2 !- 2 -
are left
Fo r bo x 4, since tw o ob jec ts
c _2!
_1_1__
0! -
1
2 z-
re o f
dy to an sw er the qu est io n : ho w ma ny wa ys are the
No w we are rea s
ts in bo x I, tw o ob jec ts in bo x 2, etc .? To ob tai n thi
pu ttin g tw o ob jec tio ns. Th e nu mb er of wa ys is
mu ltip ly the ab ov e co mb ina
an sw er we need to
I equ al to 8!
I N!
'
aCz x ,c2x 2C2 = = - -), = 2s2o
I!
ir = 8C2 x llt !ll 2 !n 3 !n ,l (2!
bo xe s
an sw er the qu est ion : if the ob jec ts are be ing pu t int o the
No w let us ble , wh at is
do m fas hio n , so tha t an y co mp lex ion is eq ua lly pro ba
in a ran two ob jec ts
ba bil ity of ach iev ing the sta tistica l sta te in wh ich we ha ve
the pro ions ass oc iat ed
h bo x? As we hav e jus t cal cu lated . the re are 25 20 co mp lex8
in eac 4 co mp lexio ns.
thi s sta te. Ea rlie r we fou nd tha-t the re is a tot al of
with
I
·I
38 The Second Law of Thermodynamics
2520
p= -
48
Interestingly enough, it will be found that the probabili ty of the statistical
state just described, where we have an equal d istributio n of objects, is
larger than the probability of any other statistical state. As a generalization
we will find that the number of ways of a rra nging N objects so that we have
n1 objects in the first cell (or box) , n 2 in the second, etc., is
ifi"=-_N_! __ (3.38)
nl! n2! n3! ...
As just discussed the statistical state with the highest probability or largest
value of if/' is one in which the objects are distributed uniformly. This state,
then, is the one that wi II occur most often and hence represe nts the nwst
probable state. F rom equation 3.36 we find further that since the "'ost
probable state has the largest value of ·if!, it also has the highest va lue of
entropy of any state. As a result, if a system goes from a given statistical
state to a more probable statistical state, if/' increases, and hence, from
application of equation 3.36, the entropy increases. Since such a process
would be expected to be spontaneous, the entropy of the process shoultl
increase in agreem~nl with the second law.
In c).~aling· with' ~ntropy calculations, we shall be interested in values of
In if/' and hence be concerned with the logarithm of factorials. There is a
convenient approximation, useful for this si tuation , known as Stirling's
formula which is applicable only when N is very large. In most of the cases
o( interest to us, N """ I 0 2~ atoms or molecules and thus this criterion is meL
J
In this case Stirling's approximation is given by
In N! r-..- N In N - N (3.39)
Let us now consider the case of a molar volume of crystal contaj ning N 0
lattice sites. . . , .. " ·\•>
Let us calculate the entropy change ~S, associated with the rantlom
mixing of n atoms of type B and (N0 - n) atoms of type A on these N 0
sites (see Fig. 3.2). The entropy to be calculated will be the entropy of the
following reactions.
Component A Component B
(No - n) atoms n atoms
/
Soluhon
N atoms
,1
Acco rding to the Boltzm a nn equatio n
I
llSm = k(ln if/'.A..n- In trA- In il'u)
Let us now consider if! A.R• the numbe r o f ways of arrangi ng (N0 - n) A
atoms a nd " B atoms o n N 0 si tes. Accord ing to o ur previo us derjvat ions, ,
let us co nsider:. that the crystal con sists of N0 cells which will hold one atom.
l f we are able to disting uish one ato m from a nother
I 'if/' = _ _ _N---=o'--!_ _ _
·t nl ! n 2l n3! · · · nN!
I Since each of the N si tes can hold only o ne ato m, ntt n 2 , etc., equals one
I and therefo re
I T his si tuatio n is not really applica ble to our case since we ca nn ot distinguish
one A atom from a nother, but we ca n disting uish an A atom from a B atom .
T he approp riate val ue of ir' will therefo re be less than N0 !, since this
includes the numbe r of ways of arrangi ng disting uishabl e A atoms among
(N0 - n) sites a nd disting uishable B atoms a mo ng n sites. The num ber of
t
I
ways of a rrangin g (N11 - 11) atoms o n (N 0 - 11 ) s ites and " B atoms on B ,
I sites will be (N0 - n)! and n!, respecti vely. Theref ore the numbe r o f ways
of mi xin g indistin guishab le A atoms with ind istingui shable B atoms will be
reduced by the factor
and thus
ir = No! (3.40)
n! (N0 - n)!
For a system consisting of nA atoms of component A, "u atoms of com-
ponent B, etc.,
il' = ___N.. :o:.. _l_ _ (3.4 1)
nA! n 8 !n 0 1· ··
The mixing entropies of the pure crystals A and 13 are obtained in the
same way. "'f/ A and il' 8 would be equal to (N0 - n)! and n! for distinguish- )
able atoms, but since they are indistinguishabl e, these values are divided
by (N- n)! and n! , respectively, to give
Thus
llS = k ln No!
m nl(N 0 -11)l
Applying Stirling's approximation
because of the size difference, it would be difficult to pack the atoms into a
3.4 The Statistical Interpretation of Entropy 41
Fig. 3.3 Bubble-raft model of an impurity atom in a c rystal. From L. Bragg and J . r.
Nye, Proc. Roy. Soc. (London), Ser. A, 190, 474 (1947).
perfect array. The situation would appear similar to that shown in Fig. 3.3.
Therefore, in addition to the mixing entropy contributio n to randomness ,
there will be a vibrational contribution randomness associated with the
process, since clearly the amplitude available for vibration is greater than
that in the perfect regions of the crystal. This will be discussed in more
detail in a later section.
f4 ------------ ---------
ta---------- -----------
f2---------- -----------
i
u
fl---------- -----------
to---------------------
Fig. 3.4 Quantized energy levels.
are distinguishable from one another and the atoms occupying state Eo are
I
distinguishable from those in state E 1 , etc. If all the atoms were in state E 0 ,
the number of ways of mix.jng i f/" would be equal to one and hence S would
be equal to zero. As we determined previously 1 the equilibrium state corre-
sponds to a maximum value of Sand hence leads to an occupancy of states
of higher energy than E 0 . Consider that in levels E 0 , Ett E 2 Er there are
1 ••• ,
S = kIn if!" ·
or
S = k In ____N~o!_ __ (3.43)
n0 I• n 1 I· n 2 I• · · · 11r I•
1
Applying Stirling's approximation to the case for large values of nil we find
l
r n.
S = -k I 11 1 In - ' (3.44)
t-o N0
The total energy of the system is expressed as
(3.45)
dS 0
= = -k ±(1 + In ~)
t- o N0
dni (3.47)
(3.48)
and
r
·0 = 2 dtti (3.49)
From equation 3.50 we see that the maximum S depends on several variables
(n0 , nh n 2, . . . , nr), ·but these variables a re connected by equations 3.46 and
3.49. Such a condition is called a constrain ed maximum , and techniques
for the mathema tical treatment of constrained maxima have been developed
by Lagrange. Application of these technique s as shown in Appendix A
indicates that the fraction of particles that occupy energy state t t is given by
1£ = L exp (-
i
.!1_)
kT
(3.52)
~= It exp ( - .!i.)
kT
= r exp ( -
Jo
00
.Y_)
kT
dU = kT
flU
~-------1------~
Oista nce-
Flg. 3.5 Illustra tio n of nn activate d stale process .
be able to move over the barrier, but those with any higher energy as weJI.
Assum ing the energy to be a contin uum, the probab ility that an atom will
have an energy betwee n U and U + dU is given by 3.51 as
Thus the proba bility that it will have an energy between U2 and U = oo
is
reo
Cl) Jc exp (- U/kT) dU
f(U > U2) = fu f(U) dU = J:u;
1
exp (- UfkT) dU
0
and
(3.53)
f (U > U1)
co
= L
exp ( -U/k T) d U
f(U) dU =
fiu~
1
exp( - U/kT )dU
u .'
and
(3.54) ).I
of
The energy U 1 correspo nds to the gro und state of the a tom. The fraction
I
atoms in the excited state, f*, corres ponds to U > U2 , and will be given
by
the ratio of 3.53 to 3.54, or
e of
Earlier in this chapter it was shown that the sum of the entropy chang
ter tha n
system and surroundings is zero for a revers ible process a nd is grea
calculate
zero for a spont aneous process. It is not partic ularly conve nient to
more
S for both the system a nd surroundings in many cases, so it would be
indica te
convenient if some functi on existed for the system alone which would
functi on
whether or not a given process is potentia lly spont aneousr Such a
that a
does exist and is kn own as the free energy function. In order to show
for a
fu nction with the desired prope rties exists , consider the criterion
spontaneous process according to the second law, na mely,
trans-
Even thoug h u process itself is proccctl ing irrcvcrsihly. heal may be
ding
formed to the surroundings in a reversi ble fashion , however, so that accor
to the second law
DQ DQ
dSilurr = - (to surr) =- - (from surr to syst)
T T
s, McG raw-Hill , New
• See, for example, J. C. Slater, Introduction to Chemical Physic
York, 1939.
46 The Second Law of Thermodynamics
As a conseq uence the qua ntity (dH - T dSaYI't.) can be used as an index as
to whether o r not a process is spontaneous, thus obviating the necessity of
considering the entropy cha nge of the surrounding. In the future, therefore,
we shall be co ncerned only with the entropy of the system and the use of
the subscdpts (surr) and (syst) will be discontinued. The relation (dH- T dS) ~
F = U - TS (3.62)
\
Some Useful Relations J
I
We now have enoug h equations to develop so me useful genera l th erm o-
dynamic relations. As a first step differentiate eq uation 3.61. We find
:·;
!
dG = dH - TdS- SdT I
r
J.S The Free Energy Function 47
ac)
(op T
= v (3.65)
..
Thus we see th a t if the Gibbs free energy is measu red as a fu ncti o n of
press u re, the slo pe of the res ulta nt line is equal to th e vol ume of the system
at the particular pressure chose n. SimJiarly fo r a reaction in which 11G is
evalua ted it may be show n that
11G) =
(oop !1V (3.66)
T
Since 11G refe rs to the difference in free energy o f products and reacti ons,
11 V refers to the difference in vol ume between prod ucts a nd reacta nts.
Another useful rela ti o n is obta ined if equatio n 3.63 is divided by dT and
the pressure is held co nstant:
aG) = -S
(ar, (3.67)
or
fiG)=
(aar ,,
-liS (3.68)
(aaF)
v1
= -p
1
(3.69 )
a nd
(-oF) - -S.
ar v
(3.70)
I
48 The Second Law of Thermodynamics 1
Since from an experimen tal standpoi nt external pressure is easier to co ntrol
than volume in the case of solids, the Gibbs function is much more useful
than the Helmholt z function. By studying the variation of the Gibbs free
energy of a system with pressure under isotherma l condition s and the
variation with temperatu re under isobaric condition s, the volume and
entropy may be obtained. These relations are useful in thermody namic
r
computat ions and are indispens able in the investigat ion of kinetics of
reactions.
J
There is a very useful relation between G and H wh ich will be derived
below. Let us start with equation 3.61. By dividing through by T, we I
I
obtain
G H
-=-- S
T T
Upon differentia tion with respect to temperatu re at consta nt pressure we
have
t
[
[o(H/T)J _ (iJS)
o(G/T)J = (3.71) 1
or , or , ar ,
The first term on the right-han d side can be expanded as follo~s:
.I
J
[acHoT/T>J , = .!.T(au)
oT
+ 11 [o< 1/T)J
oT
p J1 I
Substituti ng this expression into equation 3.71, we have 1,
By definition
f) f) 11 ll
I
(3.73) I
. ~
Also .
'
o(l/T>J = _ _!_ (3.74)
[ oT JJ T 1
I
3.5 The Free Energy Function 49
Substitution of 3.73, 3.74, a nd 3.76 into 3.72 yields
o(G/T)J = _ ·!!_
[ ar p T2
Multiplyi ng both sides hy T 2 gives
__l_ [o(G/T)J = H
2
I/T (}T ,
lncJusion of the T 2 term in brackets yields
[ o(G/T>J = II (3.77)
o< I/T> I'
[o(~G/ T)J = ~H
o( I/D ,
(3.78)
Maxl\'·ell's Equations
(3.80)
From the third equation
Examination of the last two relations indicates that (oSfo Vh· and (oS/op) 1 .,
which would be difficult to obtain in a direct experimental man ner, may be
calculated if one has knowledge of the thermal expansion coefficient artd
compressibility of the crystal.
One may derive similar relations in the case where, say, magnetic rather
than mechanical work is being considered. One could obtain relations
sim ilar to the Maxwell equations. ,For example one can readily show that
T
y
v
z
a:V
(:~)z X
T
y z
v
Ga
p p rr./fi
T s p C'Jl/T T s v C1l/T - o: 2 V/ p
T v p cp ~ a:pv T u v c1'- rr. 2 VT/P
T H p cp T H v C 1, - rr. 2 VT/fl + a:V/{1
T F p -a:pV- S T F v -s
T G p -s T G v rr.V/{1 - S
p v T -{IV T p s C11 /rr. VT
p s T -a:V T v s -{IC.,/rr.T + cxV
p u T {1pV-cx.VT T u s {JpC' 1,/rr.T- rr.pV
p H T V - cxVF T II .s· C 1,/rr.T
p F T PpV T F s PpCP/rr.T- cxpV- S
p G T v T G s C1l/cxT- S
4 From J. Lumsden, Thermodynamics of Alloys, Institute of Metals, London, 1952,
l· Problems 51
PROBLEMS
I. Calculate the entropies of fusion for K 2S04 , Ag, Ge, and MgO a t their
melting points.
2. From the statement (6Ssr>~t. + 6S11urr) > 0, cou pled with dS = DQ/ T for a
reversible process, derive 6S81 "t. > DQ/ T for a n irreversible process.
3. Derive equa tion 3.35. Wha t is the rela ti o n between t he volume thermal
expansion coefficient a nd linear expansion coefficient ?
4. One kg o f liquid U02 at 3100° K is m ixed wi th 5 kg of U0 2 at 3600° K . (a)
Find the temperature after mixing. (b) Find t he e n tropy c hange o f system
and su r round ings. (c) Is the process s pontunco uo; 'l Assume that C 11 = 100
Jfmol · K and is independent of temperature.
5. Calculate the entropy change for system a nd surro undings of the following
reaction :
6. Suppose that, in the Illus tration dealing with the thermoelastic effect, the
stress applied to the sys tem exceeded the yield point of the crysta l. Expla in
whether o r not equat ion 3.35 is a pplicable.
7. In the same lll ustrali(.)n, calculate the entro py c hange of sys tem and S,u rro un<.l-
ings. Is t he total in agreement with the second law of thermodynamics ?
8. Prove that, for a c hemical reaction such as
A+ H = C+ D
I, capacities of the two phases a re eq ua l. Do the values agree wit h the criterion
of spontaneity discussed in the chapter?
/.
52 The Second Law of Thennodynamics ics
11. Derive
12. Given two dice with faces labeled l through 6, calculate the probability that at
(a) 5 will appear on both dice after a throw, (b) the sum will be 9 after a a
throw, (c) both dice will have the same number.
13. What is the probability that two kings will be drawn in succession from a a
52-card deck ?
14. What is the probability that a 5 will appear at least once inn throws of a die ? :?
15. Consider a box of volume V divided in two by a partition. One one side of of
the partition are N gas molecules, and there is a vacuum o n the other side. e.
When the partition is removed , the gas molecules will distribute themselves :s
randomly. Calculate the entropy d ifference between the two states, using the 1e
Boltzmann relation.
16. Calculate the probability that upon filling six boxes at random with six IX
objects, one box will contain three, two wi ll contain none, and three boxes :s
will contain one each. •
17. It will be recalled that the second law states, for a spontaneous process, ;,
(6S818t + 6Saurr> > 0. What is 6Ssurr for the mixing process? What will be e
1
·)
'·
}
4
6.G = 6.H- T 6S
53
c Qua ntit ies
54 Som e Rel atio ns Between Thermodynami
ST =
io
TC
T
-.!! dT + S 0
(4.1)
The thiro law muy be readily checked ror various substances, then, if heat
capacity data are a~ilable from 0°K to T and if the heats of transformation
are available. Table ... 1 shows some data for a variety of substances and it is
observed thut 6S.,,11 (0° K) us culculuted from the :dwvc ClJlllllion is equal lo
7Cn.l within cxpcrintt·qtal litttils. ( 'nh:ulntiutts I"Pr suhsllltH:cs which ca11 he
COI\VCI'It'd II Jl~llll'Ollling f'ro111 lhc Jh.JIJid Slllll' (II lhl' glussy S(II(C show lhal
L\S.,, 11 (0" K) us rulc ullltcd l'rutll lite: uho w eq untiun is 1101 l..'lJIIal l u 1cro. 1:or
glycerol 6.S11 .p(O" K) = l'J.2 J/ nwi·K <trtd l'or akohol 6..':>·.,. 11 (0'' K) = II
Jfmoi·K. The reason is that the glassy form of a substance is not in internal
equilibrium. Consequently the third law must be used wilh caution.
We are in a position now to make some other important deductions from
the third law. First, let us consider heat capacity.
tities
56 Som e Rela tions Between T herm odyn amic Quan
4
Tabl e 4.1 Thir d Law CaJc ulati ons
L,
Transform ation T,(° K) T (J /mol ) 6Sa,lf(0° K) {J/m ol ·K)
Subs tance
t
ar~J, =
r(06 o
_(o6.G) = 6.S
ar 7J
find that
which is zero at T = 0 according to the third law, we
6.C11 = 0 at T = 0
·.
citie s 57
4.2 The Tem pera ture Depe nden ce of Heat Capa
(oS) = 0 at T= 0°K
Op T
From one of Max well 's relat i o ns
and since
nt.
whe re« is the volu me ther mal expa nsio n coc nicie
« = 0 at T = 0°K (4.3)
Cv wjth temper ature diminis hes until a val ue for Cr, o f about 3R fo r many
substan ces is reached .
A s mentio ned in the last chap ter , the re a re two ways in wh ic h a crystal
may absorb energy . One way is due to the electro ns in the crystal a nd the
other is due to increas ed energy of la ttice vibratio ns. Quantu m theo ry
indicat es that the electro nic contrib ution is very small since o nly the few
electro ns with energy near the Fermi level may be excited . Conseq uen tly
the principa l mechan ism of heat abso rpti on is throu gh excitat ion o f lattice
vibrati onal modes.
Let us assume that a crystal is compo sed of a system o f atoms which
vibrate as harmon ic oscilla tors all with the same frequen cy v. Follow ing
Einstei n , we s hall assume th a t each oscillat or has three degrees of freedom
with regard to its directio n of vibra tion. Thus a system of N 0 osci ll ato rs in
a t hree-di mensio nal crysta l · corresp onds to 3~linear oscilla tors. From
quantu m theo ry we find that the energy of an oscilla tor of frequen cy v is
Ei = (n + f)hv , ..(4.5)
\
where n is an integer and h is Planck 's constan t. The heat capacit y of the
crystal Cp is given by (oUfoT )v, a nd the total energy of the system of 3N
osciiJa tors mus t be determ ined. This is given by
(4.6)
!Z = 2:~ ex p ( - 2)
kT
(4.7)
1
1- X
Therefore
!r = exp ( - hv/2kT)
(4.8)
1 - ex p ( - lwfkT)
The a na lysis of the problem may be sim plified by consideration of th e
rel ation between the partitio n function and the Helmholtz free energy F.
By definition , ·· -·--
F= U- TS
ni
F = L ni€i + k T L 11 i In - (4.9)
') No
The relation between 11 1 a nd €1 may be obtained from equation A . l3. Solving
for € 1
t 11 {
\_€i = -kT In - - kT In !r .--~
No .._ .
- s -_ (aar,
F)
Upon substitution o f eq ua tion 4.10 we find
= k ln !£ + -kr(a~)
--
Also since
S
!£ ar v (4. LJ )
U = F + TS
we have
(4.12)
I
I
wh ere
ltll
x= -
kT
n.
n and is kno wn as the Einstein functio
Th is equ atio n was der ive d by Einstei
atu re acc ord ing to this equ atio n , as
Cv, plo tted as a fun ctio n of tem per
ent al C~ dat a for dia mo nd.
sho wn in Fig . 4.2 alo ng wit h exp erim
5
.... .,..
.,... .... ... - ---
0
1-
P-- t-.2 -
-- --
-Ill 4 /
0
E
o)
/
";;3
~
c/
v --
1
c~~
o/
.,.. ~
0
0.4 0.5 0.6 0.7 0.8 0.9 1.0
0 0.1 0.2 0.3
T/8£
(4.1 5)
where
ltv hl'm
y =- and x= -
kT kT
At low temperatures equation 4. LS simplifies to
(4.16)
(} = hvm
k
If the Debye picture was completely accurate, values of C obtained from
equation 4.15 using expe rimental heat capacity data s hould be constant for
a given substance. This is not found to be true, however, for most materials,
but rather the calculated Debye temperature 0 varies to some extent with
the temperature of the expe riment. Nonetheless this model appears to be a
reasonable approximation toward analysis of the vibrational spectrum in
solids. From our point of view the important thing is that the mai n featu res
of Ute temperature dependence o f the heat capacity are explained on the basis
of a rather simple sta tistical model. Some representative values of 0 for
various substances are listed in Table 4.2.
~
62 Some Relatio ns Between Thermodynamic Quantit ies )
Table 4.2 Oebyc Temper ature of Various Solids
)
Solid 0(° K) Solid 0 (° K) Solid 0 (° K )
I )
A 93 Co 445 Pb 95 \
Be 11 60 In 109 Tl 89 f
c 1860 La 132
!
~
(diamond)
Cu 339 Mg
Ni
406
456
v
NaCI
Ca F
273
28 1
474 :
'
)
j I )
,
)
The Debye frequen cy is pro po rtio na l to the maxim um vibrati o na l f~e
quency of the crystal . This in turn is approx imately rela ted to the melting
I
J
point, molecu lar weight , and atomic volume . The followi ng rel ation has
been derived and is known as the Lindem ann equatio n :
I )
1
This eq uation holds rather well for a variety of substa nces as shown in Fig. .) i
4.3. I
• I )
t
I
I
)
I)
F~
0
I
l )
I
l
I
Gruneisen deri ved a n important rela tion which relates the co mpressibility ,
thermal expansion coellicient, and heat capaci ty of a crystal th ro ugh a
temperature independent constant y. Gruneiscn assumed that the vibrational
frequency of a so lid depends upon volume through a rela tion of the following
type
8 = consta nt X V- y
In order to derive th is relatio nship co nsider a crystal at 0(1 1< , * where the
crystal will have an energy U0 . As we increase lhc tempera ture, energy is
absorbed and the entropy associated with the oscilla tors increases. Let us
ass ume, th erefo re , that the increase· in. te mperature results in a n inc rease in
free energy Fv which is due solely to the oscilla tors. At 0°K
At temperature T
F = U0 + F"
f-rom a previous deriva tion we may see that
U = [()([_JT)J ( 4.1 7)
v o( 1/ T ) r
a nd
p- oF)
- - (-av 1 ·
It follows, the refore, that
(4 . 18)
( 4.20)
• C. Kittel, Int roduction to Solid State Physics, 4th .ec.l ., Wiley, New York, 1970.
64 Some Relations Between T hermody namic Quantil ies
atno) v(ao) I
= - (oIn V '1' = - 0 oV
(4.22)
y 1'
Upon substitution of 4.22 and 4.2 l into 4.18 we obtain for an equation of
state
p = - (Qu 0) + u 11 y
oV T V
(op) = y Cv
ar v v
Since ,,
(op ) ex
ar ,.= fi
we fi nd
~ (4.23)
~ l I
Equation 4.23 is known as the Grllneisen relation . Table 4.3 shows value of
some of the quantities in equation 4.23 with r~sultant calculations of y. It
will be observed that y normally has a value between about one and two.
The Gruneisen reLations hip is very useful for estimating the magnitude of a J
given thermod ynamic quality in equation 4.23 if values of the other th ree are 1
I
known or can be estimated. Typicall y we know the molar volume for · j
•
Table 4.3 Calculat ions o f the G runeisen Constan t fo r Some S ubsta nces [
The comp ressibi lity term that has been di scussed up to now is known as
the isothermal compressibility since it measures the cha nge of volume with
pressure under iso thcrmnl co nditions. T hu s
f3 =
T--
.!.v (av)
op '1 ' (4.24)
dV= (av)
op
dp+ (a~~)dT
a1 , T
Divide through by dp
dV
-
dp
- (opav)r + (av) dT
ar ,.dp
and hold S co ns tant
(4.26)
c, -
The bulk modulus B is defined as the reciprocal of the compressibility.
Thus the relation between adiabatic bulk modulus Bs and isothermal bulk
modulus BT is
B'l' = Cv
Us C,,
(4.27)
where Y0 is the modulus at T = 0°K and band T 0 arc constants charac teristic
of a particular material.
From elasticity theory it may be shown that Y is proportional to the bulk
moduli through the following equation
Y = 3(L- 2u)BT
where u is Poisson's ratio. Since u varies only slowly with temperature, one
may assume that the bulk modulus BT or Bs varies with temperature
according to an expression si milar to 4.27. Thus
Bs = 8 so - b s T ex p ( - ~0) ( 4.28)
Examination of this equation shows that as T-- 0°K, B.c:;-- B80 , and
further that (oB8 joT),, -- 0 in accordance with the third law. At high
temperatures exp (- T 0 /T)-- I and Y decreases linearly with temperature.
There has been co nsiderable altcntion given to justilication of the empiri-
cally based equation 4.28 by use of atomic force models. Changt has shown
-
N
E
~ 1.60 1------J...A~------1-------1
c
>.
"0
-£ 1.551- -- - - - 1 - -- -·...
~
Now the total entrop y of a substa nce in the absence of a magnetic field
increases wi th temperature in a monot onic fashion as shown by equation
3. 14.
dS = C,d ln T (3. 14)
This is illustra ted schematically in Fig. 4. 5. From this figu re it can be seen
that the temper ature can be reduced if the entropy ca n be reduced. This may
J
I
I
I
1 Path 1 r
'
--~~~--~
I
I
t
>-
a.
I
,I
-0
~
c:
LLI
• C. Kittel, Introduction to Solid State Physics, 4th ed ., Wiley, New York, 1970.
4.5 T he Magnetocaloric Effect 69
dS = 0). Conseq uentl y pa th 2 is fo llowed HnLI the temperature is thereby
reduced to T 1 • This may be described by the following eq uations. Our state
variables a re S, H , and T . S may therefore be expressed as a function of ll
and T. Thus
dS = (oS)
oH
dH + (oS)
or dTT 11
(4.3 1)
dS = (aS)
all
dH (4.32)
From cyuation 3.HJ
and
dS = (oM) dH
ar r
Upon integration
6.S
1
=J:II (o/Vf)
0 U
~ ·/ · II
d ll
6.S = _ C ll!!
1 2T2
Thus the entropy decrease in step l is proportional to H2 and inversely
proportional to T 2 • The equation for the line shown in Fig. 4.5 is
S= JCp d In T
and therefore the temperature change which results from s tep 2 is calculaled
to be
-CH2 2 = 1:1'!C II
dinT
T2 '1' 1
The relation between (T2/TSl and H 2 is shown in Fig. 4.6 for gadolin ium 'I
sulfate.
30
~0
25 v
/
t 20
/
(~~r 15
/"
.
~ --
I
f
10
,V Gadolinium sulfate
(Giauque and McDougall)
·I
I
v
'5 I
II
I
10 20 30 40 50 60 70
H 2 (k0e2) - +
Fig. 4.6 Adiabatic demagnetization of gadoli nium sulfate. From M. W. Zcmansky,
lieu/ and Thermot~}'tlllmlcs, 4th cu., McG raw-llill , New York 1 ~57. Used with permissio n
of McGraw-Hill Book Company.
The Born-H aber cycle may be employed to illustrat e how the stability of
an ionic compou nd is related to a variety of disparat e factors such as the
heat of sublima tion of the pure metal M which forms compound M X, the
dissociation energy of X 2 , the ionization energy of M , etc. To illustrat e
this pr ocedure consider the following reaction :
Na(s, 298) + ! Cl2 (g, Latm, 298) = NaCI(s, 298) IJ. II/
Lel us put the metallic component into the gas phase, dissocia te the Cl 2
molecule, tra nsfer an electron from a sodium atom to a dista nce of infinity, J
transfer an electron from infinity to a Cl atom, and then combine the
4.6 Hea ts of Formal ion of Ionic ompounds : Born-ll aber C)cle 71
Na 1- + CJ- io ns to fo rm a crystal. Our reactio n of interes t will consist of
the following five steps, a ll al the same temper ature.
(1) Na(s) = Na(g, 1 atm) 6.H 1 = 6.H, = heat of sublim ation
(2) t Cl 2 (g , 1 atm) = Cl(g, 1 atm) 6.H2 = D = dissoci ation energy
{3) Na(g, I atm) = Na I (g, I atm) + e(oo) 6. // 3 = I = ionizat ion energy
(4) Cl(g, 1 atm) + e( oo) = CJ- (g, 1 atm) 6.H4 = electro n affinity
(5) Na+(g, 1 atm) + Cl- (g, 1 atm) = NaCI(s) 6. H5 = lattice energy
r,
Na(s) + ~ C l2(g, 1 atm) = NaCI(s ) tl. J/ / = L, 6. 1/ 1
1
The qua ntity 6/f1 is the enthalpy of sublim ation , tl.H,, and is readi ly
available in the literatu re as determ ined fro m va po r pressur e measuremen ts.
Similarly 6.H 2 , the enthalpy of dissociatio n, is avai lable experim entally for
di atomic gases. The term 6.H 3 is called the ionizat ion energy and can be
determined fro m optical meas uremen ts. The io niza ti o n energies for a large
numbe r of electro ns in an atom are availab le. [fa do ubly charged io n were
needed for th e reactio n, ano ther reaction woulu ha ve lo be consid ered in
which a second electro n is removed . This is called the second ionization
energy. The q uantity tl.F/4 is known as the electro n affinity and is determ ined
by the process of measurin g the io ni za tion energy or a C J- ion. The term 611
6
is kn ow n as the laflirc energy and may be cakula tetl by usc of a t ltcory
proposed by Born. whid1 is described below.
In the case of a n ionic crystal , the fo rces holuing the ions togethe r in the
crystal a re co ul o mbic in na ture. Thus the energy between two univalent
ions separat ed at a distanc e x is
e2
Uo = ±-
X
where e is the electronic c.harge. Accord ing to 1he co nventio n employ ed
here, the nega tive sign refers to unlike io ns (a ttracti o n) a nd the positive
term refers to like io ns (repulsio n). In the case of a crystal , a given io n is
affected no t by only o ne ion hut by many. For examp le, in the NaCI stru cture ,
a sod ium io n ha s G Cl - nea res t neighb ors al a disl:lllCC .r. 12 Na ' seco nd -
nearest neighb ors :tl ,/ 2 .1· , H C l tltirtl-n carcst neighb o rs al J] .c, 6 Na I
fourth-nearest neighbors at 2.t, etc. Thus the net co ulombi c energy of this
Na 1- ion tn the crysta l is the s um of these repulsive and aLtracti ve in ter-
actions:
u = - :· 6 -
4
') [ ~~ + 53 - + .. i J
or 2
U
(l
=_ .rfe
X
72 Some Relatio ns Between Thermo dynami c Quantit ies
where B and 11 arc constants for a given system. The total laUicc energy for
N 0 positive ions and N 0 negative ions is
V, = No[Ua + Ur] = No ( - .Jde
- -
2
+ -x" ( 4.33) B)
x
The quantity Ul, as a function of X as well as the ua and u, terms individually
are shown schematically in Fig. 4 .7. The equilibrium atom spacing will be
x0 , whereupon dUzfdx = 0. In order to obtai~ values for the constants B
and n in the repulsive term, appeal must be made to experiment. One of
these parameters can be eliminated by use of the fact that the equilibrium
spacing occurs when dU2fdx = 0. Differentiating equation 4.33 with respect
'
I
'I
+
',u, \
\
\
'
\
\ )
\
' '' zo Distance of separation - x -
Or-~----~-.----------------~---------
)
---~ I
I
I
I
1 U0
I
I
I
I
e
Fig. 4.7 Lattice energy of a crystal as a function o f ion separation . Ur is the repulsiv
contribu tion and U0 is the attractiv e contribu tion.
! 4.6 Heats of Formation of Ionic Compounds: Born-Habcr Cycle 73
to x, setting equal to zero, and solving ror /J, we find
l and thus
l.
I
(4.34)
( U)
l :~:-xo
= _ N0 .9fe"-( 1 _ ~) (4.35)
x0 n
Strictly speaking, this calculation is valid only at T = 0°K, since the
equilibrium spacing x 0 is governed not by the point where the energy is a
minimum but where the free energy is a minimum. In order to make a
calculation at T > 0°K, the entropy term TS, would have to be considered.
This contribution is fa r more difficult to C\'al ualc than the energy contri-
bution and will be neglected here.
The only coefficient now remai ning to be evaluated is n, and it remains
to find a relation between this and some experimental function. It would
seem reasonable to expect the repulsive contribution to U, to be related to
the compressibility of the crystal since the main factors entering into the
compressibility result from the repulsive interaction between ions. Therefore,
let us examine thjs point further by considering the compressibility at
T = 0°K. By definition
V' - 1~,
(4.36)
J1 ~ - /IV.,
The work performed by the solid during the compression from V0 to V' is
v'
w= J,
Vo
ndV
'
1
I
}
74 Some Uclat ions Uctwccn Therm odyna mic Quan tities
{3 Jl'o Vo
Reca lling that V 0 is a cons tant we find upon integra tion that
( V' - Vo)2
w= - .!.----- -=:..:.. .. ( 4.37)
2{JV0 •
on :
Consider now the internal energy change !l.U, upon compressi
fl. u, = u,' - (u,)x- :ro
It will be recalled that U,, a state prop erty, may be
considered to be a
at T = 0°K,
function of any two state variables. The temperature is cons tunt
been
so there fore press ure and volume are the obvious variables. p has
ss
expressed in terms of V by relation 4.36 and thus we may expre
U 1 = f(V)
(4.40)
II
I
I
4.6 Heats of Formation of Ionic Compounds: Uorn-Haber Cycle 75
From equa tion 4.40 it is seen that the compressibili ty o f a crys tal is inversely
proportional to the curvature of the energy ve rsus distunce c urve a t the
min imum. For a crystal, the molar volume is rela ted to the interatomic
distance x by
V = CN 0 x 3 (4.4 1)
c1u = ("u)
dV dx
(d..c_)
dV
we find , using 4.41, that
( 4.42)
9Cx0 4
II = 1+ (4.43)
{Jez.#
m n L
- - - M(s) + X (s) = MmXn
(m + n) ( m + n) (m + n)
• W. M. Latimer, Oxidatiou Potetttials, 2nd ed ., Prentice-Hall, New York, 1952. [
-I
4.7 Empirical Predictions of Entropy 77
The entropy of this reaction at 298°K is given by
Average 6S~118
Reaction Type (J/g-atom ·K)
Ill ll 1
Carbides - - M(s) + C(s) = - 1.05 ± 2.60
(m + n) (m + n) (m + n) MmCn
, II I
Sutridcs - - - M(.,·) + S(.\') = - -4.35 ± 5.15
+-11) M S,.
-
(111 + 11) (m + 11) (111
111
lodjde l " 1
(l t- n) M(s) + (1 + n) I (s) = (l + 11) Min -3.47 ± 3.64
indicates that D.s;fla for the reactions involved is indeed small. A similar
analysis has been performed for reactio ns involving one gaseous species.
The absolute entropy of a gas is very large compared with solid phases and
thus the reaction entropy wo uld be governed by this contribution. Table 4.6
provides data for a variety of gaseous reactions which involve one gaseous
component. The values for D.S~98 are al l negative in sign and are all about
the same value as expected from equation 4.44. Similar tabulation may be
made for other types of reactions, such as reaction between a gas and a solid
that yields a gaseous product, etc. A principal use of these tables is for
predicting the thermodynamic properties of a reaction when one does not
bave complete thermody namic information about the rroducl or reaclcllll
of interest. T his ortcn is the ca~c ro r high-temperature reactions for which
thermodynamic data a rc dilllcu ll to achieve.
Reflection will indicate that one ·would expect a direct rela tion between
thermodynamic properties and the physica l properties of the substances
• A. W. Searcy. in Chemical and Mecluwiccll Behacio~ oj Inorganic Materials, D. Ragone
et al., Eds., Wiley, New York, 1970.
78 Some Relations Between Thermodyna mic QuanCitie.~
-1.85 X I 0 2 ± ll
- 1.80 X 102 ± l8
2 2
- M (s) + F 2(g) =- MFn(s) - 1.64 X 102 ± 13
n "
2 2
- M (s) + C l2(g) = - M Cin(s) -1.53 X 102 ± 10
n n . ..
- 1.48 X I 0 2 ± 10
2 2
- M(s)
n
+ I 2(g) =- Mln(s) - 1.56 X 102 ± 10
n
6.Sv = _b_
T,
= 88 (4.45)
"·ll·
ln this equatio n, L'f) is express ed in Jf mol. Similar ly , the melting temper ature
should reflect the binding forces in a crys tal , since melting introdu ces
d iso rder into the crystal and a high binding energy betwee n atoms would tend
to oppose the creatio n of disorde r. Richar ds' rule is
L
6.51 = ~ = 8.4 (4.46)
T.m.p .
where L 1 has units of Jfg-ato m. The usefuln ess of such empiri cal rules lies
in the ability to predict reason ably well , proper ties of heretof ore unin vesliga ted
materia ls of interes t. Thus correla tions form an import ant aspect of physica l
science. Also when detaile d atomic models o r theorie s of crystals a re pro-
posed, these empiric al correla tions may be used as a test of the validity o f
these detaile d models. Such theo ries must predic t that suc h correla ti ons would
be found. Very often the correla tions themse lves sugges t detaile d atomic
theories.
Richar ds' rul e d oes not hold partic ularly wel l fn r a wid e varicLy o f sun-
stances . Trouto n's rule ho lds surpris ingly well, o n the other hand, as s hown
by the tabulat ion in Table 4 .7. The va lue of flS is within the limits of
84-105 Jfmoi·K for a wide variety of substan ces in good agreem ent with
the Trouto n's rul e value of 88.
In Table 4 .8 are listed so me values o f tlS calcula ted from experim ental
1
values of L 1 and Tm.p.· These should be compa red wi th the Richar ds' rule
0 :! 6 .RI 90. I 76
Cd 10 .00 1038 96
Na 9.92 11 55 86
Mg 12.75 1378 92
Zn 12.05 1180 102
Ag 258.00 2420 107
KCI 163.00 1680 97
NaCJ 170.00 1738 98
AgCI 178.00 1837 97
TiCI4 36.20 410 88
(
l
•'
Som e Rela tion s Hctwcen Ther mod ynam ic
Qua ntiti es '
80
Tab le 4.8 Some Entropies of Fusion
i
I
I
I
Com pou nd 6.S1 (J/g-atom ·K) Com pou nd 6.51 {J/g-atom· K) I
8.4 Vzls 9.8 j
Pb
28 CCI" 2.0
Si
13 CdSb 22
NaCI
13 CuA1 2 15 f
MgO
9.6 A uSn 19 I
FeO I
t.S,
0
= - R [x : y In c: ) +x~ y In c~ )J
AuS n gives 5.7, 5.3, and 5.7
Calc ulat io n of 6S3 for CdS b, CuA I2 , and
listed in Tab le 4.8 and sinc e
1/g- atom ·K , respectively. Val ues of 6S 1 a re
tracti o n. 6.S2° is foun d to be
6.S1° = t::..S 2° + !::..S3°, we find 6S2° by sub
I , a nd AuS n , respectively.
16, 9.3 a nd 13 J/g- ato m· K for CdS b, CuA 2
e value.
The se va lues a re clos er to the Rich a rds' rul
4.8 Estimation of Heat Capacities of C rys tals 81
With regard to the entropy of fusion fo r the elements, there appears to
be a proportio nality between 6.S/ and alo r11ic number. This relation is
shown in Fig. 4.8 for Group IV elements. The fundamen tal paramete r in
this case is probably not atomic number but binding energy since the binding
energy of the crystals a lso shows the same relation to ato mic number as
does 6.S/.
These rules ass ume that the arrange ment of mo lec ules in the gas phase is
more or less the same. Serious implicatio ns may result, however, in the case
29.4
-:.:::
~ ~Ge
I 25.2 -
"~Sn(gray)
E
B
-
n)
I
co
\k
:::!. 21
c:
0
'iii
2
0 16.8 - -
"'Ci
cu
Sn(whlte) \
...0
..... Q \
w
c: 12.6 1·- \ - - ·- -
\
\
\
8.4 Pb
0 20 40 60 80 100
Atomac numbers
Fig. 4.8 Relation between e ntropy of fus ion a nd uto mac num ber. rrom 0. Ku baschcwski
and E. Evans, Metallurgical Thermochemistry , 2nd ed., Pe rgamon, London, 1955.
Cv = 3R or 251/lll <'·I·K
es
82 Some Relations Betw een Ther mod ynam ic Qua ntiti
-2
-3
l------Uo:
------
-4
~
(
-5
- 6
----
·······..... ··}
Total
·· .... ········ U02 uo2
-7
~O0 a
-.s -a
-nl
Q,
tlO
~
.......
v
~
Pu02
PuOz
1
.Q ~
-9
-10
'\
'~ \
\
-11
""~ "----- -- ~
- 12
1\ t--
-
-13
- 14
'~
'\
\
"-- ----~ 2.10
1.95 2.00 2.05
0/M Ratio
v at 2000° K. From M. H . Rand and
Fig. 4.9 Parti al pressure over (U 0 •85 Pu 0 • 16) 0 2 l:
rials, l.A.E .A., Vienna, 1961.
T . L. Mark in, in Thermodynamics of Nuc lear Mate
betwee n C 11 a nd Cv.
As we fo und earl ier the follo wing relat ion exis ts
C = C + cx2 VT ..
p v f3
·K for crys tals, and thus
The term ct.2 VT/f:J is gene rally abo ut 2.0 Jf mol
ld expe ct Cv ~ 27 Jf mol· K .
acco rdin g to the Dulo ng- Peti t relation one wou
have lowe r va lues of heat
This rule is very appl'Oximate since some crys tals
ond , for exam ple, with
capa cities and ma ny have large r va lues. Diam
4.8 Estimation of Heat Capacities of Crystals 83
C - C = (/.2VTC/
, v cp '!.fJ
The term («2 V/{3 C112 ) is found to be relatively independent of temperature
and the above equation is written as
C 1, - Cr = AC,,2 T
which is called the Nernst-Lindemann equation . For copper, for example,
A va ries from 3.85 x lQ- 6 mol/1 at 50°K to 3. 7 1 x 1o- e mol/J at 1200°K.
Thus A may be evaluated for a particular substance if (I. , V and {3, Cfl, and
Cp are known at one temperature and employed to calculate Cv at other
temperatures if cfl is known.
Very oflen an approach known as the Neumann-Kopp rule may be applied
with reasonable success for the estimation of heat capacities of co mpounds
formed from clements in the solid or liquid slates. Tli1s approximation
considers the value tlC 11 for a reaction in which a compound is formed .
Thus for the reaction
xA (s) + y B(s) = A:r B.,(s)
According to the Ncumann-Kopp rule
(C,JA n
z "
= x(Co)A + y(C")n
Tbis, of course, says that the heat capacity of a compo und is the sum of
those of the clements forming the compound . A lest of this rule is shown
in Table 4.9 in which predictions of the Neumann-Ko pp rule are compared
with actual values for some substances at 300°K. It can be seen from this
table that agreemen t ls ge nerally excellent.
At first gla nce, it might appear that the co mpounds have high heal
capacities compared with lhe elements from which they were formed . It
Ni2Si 53 20 73 70
PbS 26 23 49 50
Ni 3Sn 79 26 103 100
Sb 2S3 51 69 120 I 18
ies
Th erm od yn am ic Qu an tit
So me RclatiDns Dctwecn
84
case. Fo r
ile at thi s po in t to ind ica te th at thi s is no t th e
mi gh t be wo rth wh s th at 1 mo le of co mp ou nd
ac tua lly
ati on of Sb S sh ow
ex am pl e, co ns id er 2 3
mo les of sulfur. Th er e ar e th
us 5N0
of an tim on y an d 3
co ns ist s of 2 mo les co ur se , the re ar e on ly N 0 ato
ms in a
Sb S wh ere as , of
ato ms in a mo le of 2 3 at ca pa cit y Cf) fo r N 0 ato ms or
a gr am -
le of S. Th e he
mo le of Sb or a mo x ( 1/5) or 24 Jfg -a to m· K.
In lat er
eq ua l to o nly 12 0
at om of Sb 2 S 3 is er ne d wi th qu an tit ies de fin
ed in ter ms
be pr inc ipa lly co nc
ch ap ter s we sh all y will rep res en t fra cti on s
an d th e
. In thi s ca se x an d
of the gr am -a to m
y be res tated as follows:
Ne um a nn -Kop p rul e ma a so lid phase may he cons idered to
be
a gr am -a tom of
The he at capacity of the ele ments for mi ng th e phase.
he at ca pa cit ies of
the weigh ted su m of the
N OF CO M PO UN DS
~ .9 HE AT S OF FO RM AT IO
ic Nu mb er
Re lat ion to Ca tio n At om
, ;,.H/ , of
s to be a rel ati o n be tw ee n th e he at of fo rm ati on
Th er e ap pe ar t, sim ila r to
d the ato mi c nu mb er of the me tal lic co mp on en
co mp ou nd s an me values of
py of fu sio n, D. S/ . Ln Fig. 4.1 0 a re sh ow n so
th at of th e en tro
s as a fu nc tio n of ato mi c nu mb er . Lo ok in g a t
ide
D.H/ fo r ch lor ide s an d ox
I
80
l
I
60
~
RbCl CsCl
KCI X
? LiCI /x
X
I
£ lS- x
10
t L'l:zO NaCl
E
~ 40
~
jij
u
.X
_,
K2 0 ltl.>:zO Cs 20
::z:
<1 I
I
20 · - CuCl - - -Ag-CI - - - - - -
x-
-x~ I
Cu:z~
N g2 o ~, I
80
20 40 60 I
Atom1c number
ic number. 0 {
we en he at of for ma tio n of co mp ou nd s an d ion
Fig. 4.10 RelatiQn bet al Therm
m 0 . Ku ba sch ew ski an d E. Ev an s, Metallurgic
ox ides; X = chlorides. Fro
n, Lo nd on , 1955.
chemistry, 2n d ed ., Pergamo
I
4.9 Heats of For mat ion of Com pou nds
85
the series Li, K, Rb , Cs, it will be see
n tha t the dependence upon atomic
number has the opposi te sig n for chlorid
es as for oxides. Th e value of 6.11,0
tends to increase wi th ato mic num ber
for the chl orid es and to decrease for
the oxides.
70 I I I I I I I I
%
- -
M~c.o
60
~
Sn>
- -
~
0
50 s
s
- C. I -
~
SrS..lo MaS I
c.o ~t!C"" ""' u.s.
0 u u;-----j
- C.11•
CoO o
~
ouN o MnO -
~ o
Ul -
oCaN
VN !.AN
CrNo /"'
~
.
1..&,
ALCo
J>bSO •
,. AJNI
-
20 ~Br
_gUC
:A aCt
,_
----
PbSe
o M4Se -
~ PbTe
10
X.·
.". • I\1Cd
AuCcl
" Mc'fe
"SnTe
-
/ AaZn
Bin I I I I I l l
10 20 30 · 40 50 60 70 80
- tJ./1 (kcal/gm-atom ) -~
Fig. 4.11 Heat evaluation and vo lume con traction upon formation of comp~1untl s or
s imple structure. 0 = NaCitype ; x = CsCI type. From 0. Kubaschewsk i and E. Evans,
Metallurgical Thermochemistry , 2nd eel., Pergamon, London, 1955.
PROBLEMS
•
5.1 PHASE T RANSIT IONS CLASSIF I ED ACCORD ING TO O RDER
o(G/T)J = H
[ o(l/T) p
,/Gs
/
/
/
t
G
/
/
/
/
r,,
r- -
Fig. 5.1 Illustration of a first-order transition.
which is continuous in the Gibbs' function and its first derivatives, for
example, but which is discontinuous in the seco nd derivatives. Thus there
would be no discontinuity in S, V, or II but th ere would be discontinuities
in the heat capacity C1, the compressibility fJr, and thermal expansion
coefficient a, for example. This is readily seen si nce
(~;.).=-(~a =-~
(oopG) _ (aopv) _ fJ v
2
2 '1' - '1' - -
~[o(G/T)J _ (oH) _ C
.ar o(J /T) ,- ar , - 'J)
..
tG
t •
cJG\
( iJT )p
T~
t
(a2o),
aT p
Ttr
T~
0.40
0.36
t
G
- --
--
•• 0.32
tlO
~
~
0.28
y ........
~
0.24
473
/ 673
(T.K)~
873 1073
Fig. 5.3 Specific heat of quartz near the second-order transition temperature between
ex-quartz anc.J fJ-cristoba lite.
becomes infinite at the transition temperature. This is true perhaps for most
of the second-order transitions with the exception of the superconductio g
transition, which is second order when II -:;!: 0 and for which flC 11 docs
appear finite. There is no thermodynamic principle which requires that the
difference in second derivati ves of the Gibbs function must be finite. In order
to predict whether or not the second derivatives are finite or infinite for a
second-order transition one must resort to specific models of seco nd-order
processes. For example, Landau and Lifshitz assumed that the Gibbs free
energy niay be expressed as an ana lytic function of some orper parameter Ni
at least to the fourth power.
G = A0 +AN +A
1 1 2 Nz2 + AaN4:t +A 4 N4 1 + ···
If this assumption is valid the seco nd derivatives are finite for seco nd-order
process for example.
A general theory has been developed by Tiszu whic h yields inlinitc va lues
of the second derivatives at the transition temperature. A s pointed ou t,
however, it is difficult experimentally to determine whether or not the heat
capacity. for example, goes to infinity at the transition temperature. This
problem is illustrated in Fig. 5.4 for US. Does C 7, go to co at I80° K ?
92 Thermodynamics of Reactions
20
us
)
)
52'
.
•
-~ 10
0
E
/
I --~
~ ........ .,
_,..
cJ ~// /
/
r;F
0
0
/ 100
T (• K)
200 300
Fig. 5.4 Heat capacity of US invo lving a magnetic transition. Fro m E. F. Westrum and
W. G. Lyon. in Thermodynamics of Nuclear Matedals, I.A .E .A., Vienna, 1967.
Therefore
dG« = V« dp - Sa dT
dGp = V 11 dp- SpdT
In view of equation 5.1 we find upon rearranging that
dp = Sp- s«
dT Vp- Va
or
dp = D.S (5.2)
dT 6V
5.2 First-Orde r Transition s 93
tl.S =l~
«
DQ
T
=l' a.
dH
T
= L
T
where L is the enthalpy change of the trans itio n . S u bsti tu ti ng in equation
5.2, we find
dp _ L
(5.3)
dT T~V
This relation is known as the Clapeyron equat ion . From t his rela ti on we sec
that a change o f tra nsition tempera ture dT equa l to (T 6. Vj L) dp results
upon a pressure cha nge dp. If the c hange in the phase transiti on temperatu re
is small compared with T. ~ V, L, and T m ay be considere d constant a nd
Illustration
Problem. Calcula te the change in the transition temperatu re of the
reaction
Sn(gray) = S n(whitc )
7 2
when the gray tin phase is under a hydros tatic pressure of 10 N/ m •
Solution . From the literature we find that L1 = 2090 Jj mol. The equilib-
rium transform ation temperatu re is 286°K, the ato mic weigh t , !vf, is 11 8.7,
and the densities o f gray tin and white tin are 5.75 x 10 and 7.28 x 10
3 3
~V = M(
1
- -
1
- ) = -4.35 x 10- o m!\f mol
Pwll ILc Pgray
dT ~v
dp ~s
..
aD
c
Qi
2073 v /
::E
~ --
v
__.. ~ ~ ~
1873
v
v
v ./
7
1673
0 20 40 60 80 100 120
Pressure - lOS N/m2
623
/
573
/
/ ~ r--
VI
Liquid
--
523
' ~
II(~[ (Bundy)
" )
~
•
~ 473
-
::1
E
"i- J'\.
"'""Y
,f.
-
~ I III ill
a. I
II
E 423 I
~ \
\
I
\
I
I
373 \
\ I -- ·
\ I
\ I
\ I
323
\
~¢
: (Kennedy and La Mori)
273 ' l ·1 I I
0 10 20 30 40 50 60
Pressure <kbar)
Fig. 5.6 Phase diagram for bismuth. From G. C. Kennedy a nd R . C. Newton, in S olids
Under Pressure, W. Paul and D . M . Warscl1auer, Eds. , McG raw-Hill, New York, 1963.
Used with permission of McGraw-Hill Book Company.
96 Thermodynamics of Reactions
1 300~-------r--------~-------.--------,
Claussen-range between a~ 1' on
1200
I cooling and heatinll by differential
thermal conductivity
• Kaufman. Leyenaar. and Harvey-,a -1'
• Hrlhard. a -+1' metallography
1000
o Kennedy and Newton. a -1' differential
thermal analysis
-.
-• 800
~
~
....
Q)
P.
~ 700
Q)
a.
E
Q)
t- 600
500 -----
400
t
300
200
100
0 50 100 150 200
Pressure (kbar)
Fig. 5.7 EITect of hydrostatic pressure on the cx-y transformation in iron. From L.
Kaufman, in Solids Under Pressure, W. Paul and 0. M. Warschauer, Eds. , McG raw-H ill,
New York, 1963. Used with permission of McG raw-Hill Book Company.
V6 » v«
Therefore ~V may be approxi ma ted by Vp. Further , the pressu res of t he
vapors of interest he re a re generall y very low. This mea ns t hat th e gas
mo lecules are sufficiently fa r a pa rt fo r little interacti o n to occur be tween
them. As a result the perfect gas law wi ll apply a nd the mo lar volume o f fJ
is given by
_ RT
Vp- (5.6) ·'
p
5.2 First-Order Transitions 97
where p represents the partial pressure of {J. Substitution into 5.3 yields
dp L
- = - -2 ciT
p RT
or
d In p L
= -- (5.7)
d(1 / T) R
Upon integration we find therefore that
In p = - ___f.__ + In A (5.8)
A- ~T .__,\,.. ..
• . • rz.,- • ~
? -- ~,cr ~.h) .
where In A IS a n 1ntegrat1on constant. hus 1t 1s seen that the vapor pressure
of a substance increases exponentially with tempera ture. In Fig. 5.8 the
equilibrium pressure or vapo r pressure of a substance is shown, schematically,
as a function of I f T. The slope at any temperat ure is equal to - I~/ R accordi ng
to cq uution 5.H. D. L. for u solitl is the heal of s ubl imatio n, and is somewha t
dependent upon temperctture because of the heat capacity dilrerence of o:
and p.
..
I/T~
we see that there is an exponential dependence o f the vapor press ure upo n
temperature . Jn Table 5.2 values of the heat of s ublimation a re listed for
a variety of substances. These were measured at melting points of the sub-
sta nces.
If L , was independen t o f tempera ture, only two co ns tan ts would need to
be kn o wn in order to determine p at any temperature : A ami L ,. 13ccause of
Substance L, Substance L,
Ag 2.74 Li 1.60
AI 3. 15 M o0 3 2.55
Al 2 18 1.17 BeO 6.08
Au 3.71 Zn 1.27
Fe 3. 17 v 5.01
Ge 3.76 Si 4.42
Mo 5.63 Ni 4.17
the heat capacity difference between a s ubstance in the conden sed fo rm and in
the vapor form , the temperature dependence of L~ must be taken into
acco unt for p to be evaluated accura tely. This is pa rticula rly impo rtan t
since a small erro r in L, will res ult in a large erro r in p because of the occur-
rence of L, in the expo ne nt. A s a res ult of this temperature depe ndence of
L,, In p is generally expressed in the fo llowing form for convemence 10
evaluation . j
log p = -a + b log T + cT + d -·
T
Some values of the constants are tab ulated in Table 5.3 fo r a variety of
substances.
Temperature Range
Substance a b c X IO:J d (K)
thut the temperature is held constant but we au mit an inert gas at pressure P.
The question then arises: how does the vapor pressure p of a substance
depend upon lhc ex ternal pressure P upplicc.l lo the system '! Since U in the
vapor phase is in equilibrium with B in the condensed phase
dG ('(JII d = dG IC II.'<
Let us now change the external press ure by dP. Since this is <.lone reversibly
we may use the equation
dG = VdP- SdT
and since Tis constant
dG co u d = Vco nu d P
The pressure change dP of the inert gas will effect a pressure change dp in
the vapor pressure of B. This will result in a free energy change of the gas
8 in gas phase p 8
Fig. 5.9
.
- - - - -.. .F--=·---
.~
given by
Since
dG cond = dG gas
we find
dp Voood
- - (5.10) \
dP V~ens
dp pVcond
(5.11)
dP RT
From equation 5.10, il is seen that dp/dP is small, si nce V('nnd << Vga8· A
l
typical ratio of Voond/ Vg(UJ is 10-4. Thus a change in P of an o rder of l I
newton/m2 will resu lt in a change in vapor press ure of the order of I Q-4 i~
this case. Very large external pressures could, of co urse, result in noticeable u
changes in vapor pressure. Therefore we are safe in co nsidering the vapor
pressure of a phase to be dependent only on temperature at ordinary pressures.
·I i
dT
- - TV tla.
dp llC,,
dT 6.{3
- --
dp 6.a.
This effect of press ure on the Curie temperature for a va riety of magnetic
material is shown in Fig. 5. 10.
In Fig. 5. 1 L is illustrated a low-temperature specific heat change for a Nb. -V
alloy which undergoes a superconducting transition . The superco nducting
transition is an interestjng o ne to consider si nce it may be considered quan-
titatively in some detail. For a type 1 superconductor at low temperalure
under isothermal conditions, the material is superconducting below a
101
5.3 Second-Order Transi tions
--
::;:::
•
......
c:
·aa.
Q)
·c
8 - 10 1 -- --\-l -..l,----
.s
'1
l 2 4 6 8 10
10-:l x Pressure (atm)
Reu., 93, 384
Fig. S.lO Shift in Curie temper ature with pressure. h om L. Patrick, Phys.
( 1954). ..
-
critical field H 0 • Above this field , th e material is in the norma l state. Experi
ments indica te that below ll r• U = 0 un<.J sinc;c
I 4TTM
I
B = H +-
1\ V
'
HV
M= for H < H e
47T
This is called the Meiss ner effect. Above lie
B = 11 .
j I
102 Thermodynamics of Reactions
25
Nbn.2tlVo.71i
1
-.
N
20
I
~
.·
-----
~
•
0 15 ....--
..
E
. ~
-
- .,
CIO
E 10 ~
- I:
....... ,~
e-.. . )
c.J 5 I
-~
I
I
.1
50 100 150 200
T2 (•K2)
Fig. 5.11 Low-temperature specifi c heats of a Nb- V alloy which undergoes a super-
conducting lransition. From M. Ishikawa and L . E. Toth, Phys. Reo., 83, 1856 (1971) ../.')
\/~
and therefore I ,/ \ ..~
M =0 fo r H > 11 0 ~ \)\'
Recalling that the enthalpy Hi s equal to U p V and recalling the relati on- +
ship of H and M top and V, we may write for a Gibbs functi on
G = U- TS- H M
Differentiati ng,
dG = dU- TdS- SdT- H dM - MdH
T dS = dU + DW = dU- H dM )
dG = -M dH
.
'
Since M = 0 fo r the normal material the Gibbs free energy is not changed
upon application of the field . The free energy change of the superconducting
.material upon application of a field H is therefore equal to
5.3 Second-Order Tran itions 103
Upon substi tuti on of M =- H V/41T we obtain
I
I
I
I
I
I
Normal
t
G
Superconducting
Fig. 5.12 Free energy- magnetic field relation between s uperconducting and normal
material.
O r----=--------.------------~------------~
-0.1 -
-0.2~------------~~-----------4----------
--~
..... -0.3
0
~ -0.4 ~=========t==-~....-----1------'--~
-,
-E - 0.5
~ - 0.6 1--------1-------..:::!~...-~------'--
..... -l
~ - 0.7
cu
:! -
..... 0.8 1------ ------ --1--- ------ --4--..3111. - - - - ---1
u.. -0.9 -
-1.01---------------1-------------+----~~----~
-1.1
-1.2L-------------~------------~--------------J
0 0.5 1.0 1.5
Temperature (°K)
Fig. 5.13 Experime ntal values of the free energy as a fu nction of tempera ture for A I.
From C. Kittel, httroduct ion to Solid Stole Physics, 4Lh ed ., Wiley, New York, 1971. /}Y
permissio n of Jo hn Wiley & Sons, fnc. (Acknowledgment made to N. E . Phillips in
original source.) ·
(S um)
The free energy cha nges associated with reactions 2 throug h 5 are zero
because PJ..0 , Pu 0 , p0 °, and Pn° are chosen so as to be the equilibrium va lues
for pure components. A s a result, a reactio n between gaseous components
in equili brium with their solids gives the standa rd free energy c ha nge /:iG1°.
If one of the components were sta ble in the gaseo us state at the tempe..ature
T, however, then in o rder for l:iG 8 to be equal to AG 0 , it wo uld have to be at
1 atm pressure. ·
Let us now change the val ues of P1.. , p 11°, Pc , a nd Pu0 to new values
0 0
(7) llG 7 =0
In o rd er to co nvert reactio n (6) to reacti on (7), the partial pressure of •f
each com po nent must be changed fro m p,0 top/ . To evaluate the free energy
change due to s uch a pressure change we may use
dG = Vdp- SdT
.,
Thus, starting with reaction (6), we obtain
-,
5.4 Chemical Reactions 107
and convertin g each compone nt top/
(8)
0
Pu
(9) 6.G 9 = bRT In -
Pa'
(11)
6.G1 =0
The free energy change fo r th is reacti on is of co urse zero si nce it is at
equilibriu m.
Upon summatio n of the free energy changes,
( 5. 12)
Under these conditi ons the quantit y p,/p,O is defined as the activity , at, of
compo nent i. Thus
(a 0~) 0 • (an•)d IT (a,'tt (for produc ts)
K = = (5.14)
(aA•t · (aa•)b IT (a,')"' (for reactan ts)
where aA•, a 8 •, ac•, and au' represe nt the activiti es when the reactan ts and
produc ts are in equilib rium.
From the definiti on of ai,
(5.15)
dG = RT dIn a, (5.l6)
and
G1 - (a')
G,o = R1, 1n -
a,o
(5. 17)
Equati on 5.17 must not be confus ed with equatio n 5. 13. Equatio11 5.1 7
might be envisio ned as a basic thermo dvn -:a rnir '";~t:ttinn . ... :... ,cas 5. 13 might
be thoul!h t nf -: ~ ... .unema t ical "uc..:cidcnl."
·' equatio n 5.13 shows tha t from knowlcc.lgc of the standa rd free energy
change of a reactio n, which has nothing to d o with the reactio n at equilib -
rium, the relation betwee n the quantit ies themse lves at equilib rium is
0
obtaine d. The va lue of the activities depend s, of course , on p, , which in
turn depend s on our choice of standar d states. Thus far we have used the
pure conden sed phase as standa rd state, if this is slable at the temper ature
of interest . If the stable form is a gas, then it is co nsidere d that the stand ard
state is l atm pressur e. From the definiti on o f activity , it is see n that the
activity o f the pure stable substance in the consid ered form is equal to one
by definiti on and for a stable ideal gas is eq ual to the pressur e itself measur ed
in atmosp heres. In dealing with solutio ns it is so metimes more0 co nve nient
to change the standa rd state. Thus the equatio n to obtain /1G is changed
and a lso p 1° will be change d.
Consid er now the free energy change of our reacti on (not the standar d
free energy) in which the compo nents are at some arbitra ry activity . This
could occur, for exampl e, if its compo nents were in solutio n.
(1) aA(a..J + bB(a 0 ) = cC(ac) + dD(a 0 )
To evaluat e let us begin with the reactio n in which all compo nents are in
standa rd states; thus a 1 = 1' for all compo nents. The activities will then be
5.4 Chemical Reactions 109
reversibly changed from a1 = I to a1 and the free energy associated with
each step wilJ be calculated by usc of equation 5. 17.
Upon summation of reactions (2) through (6), reaction (I) is obtained an5i
~G 1 = RT ln
·.
(a cca
a
a.A.a
t/) +~Go
b
(5. 18)
11
~ Illustr.1tion
Problem. Consider the equilibrium reaction of pure solid CaSi at l000°K
with Ca and Si dissolved in a solvent. Suppose that Ca initially has an
activity of 0.5 in solution and CaSi is pure. What this means is that the
vapor pressure of dissolved calcium is 0.5 times the vapor pressure of pure
calcium at this temperatu re. Let us now find
(a) the activity of Si in equilibrium with Cn(a = 0.5) and CaSi(s)
(b) the partial pressure of Ca(g) in equilibrium with the dissolved Ca
(c) the free energy of the reaction
~G = R{lOOO) In °· 8
(0.5)(0.4)
- 1.72 x 10 5 = -160 kJf mol
(d) Since /1G is negative, the reactio n as written is thermodyna mica lly
possi ble.
Illustration
t
Problem. Calculate the standa rd free energy change llG 0 of the followin g
reaction at 1000°K .
Ca(a = 0.9) = 'Ca(a = 0.5)
Solution. D.G0 is calculated by measuring the free energy change of both
reactants and products in their standard states. Since caJcium is solid at
l000°K, the standard state for both reactants and products is pure solid
Ca as indicated and thus
K=l
Illustration
Problem. Calculate the free energy change D.G of the following reaction
at l000°K.
Ca(a = 0.9) = Ca(a = 0.5)
Solution.
llG = RT In a<produot)
a(rcaotao t.)
= RT In °·0.59
D.G = -4.88 kJj mol
Let us now consider the variation of K with temperature . The equilibrium
constant for a reaction may be markedly dependent upon temperature .
We determined earlier that
o(~GJT) = D.H
ac 1/ T)
5.4 Chemica l React ions 111
Substitution of the relation llG 0 = - RT In K into the equation above yields
a InK = - - -
(5.19)
a( t/ T) R
From equation 5. 19, it ca n be seen that the value of K varies markedly
with temperature. Whether or no t K increases or decreases as the temperature
increases depend s upon the sign of 1:1H 0 for the reactio n. This quantity , of
course, may be either nega tive o r positive. A s a conseq uence o f 5. 19, small
errors in 6.G 0 may result in large errors in K. To illustrate we write
/::,.G o
InK=- -
RT
Differentiati ng at constant temperature , we obtai n
dK
- - d flG
0
-
K HT
or
/::,.K 1:1(6G 0 )
-~
K RT
Suppose that 6G0 is eq ua l to 50 kJfm o l and t hat the ex perime ntal erro r is
±5 %. At I 000°K, thi s would lead to an erro r in K given by
IlK ~ 30 %
K -
Standard free energy c han ges have been d etermined for a large n umber of
reacti o ns a nd are available in sta ndard references. For those reacti o ns fo r
which 6G 0 is no t tabulated, o ne may often calculate 1:1G0 from the relatio n
6H 0 and 6S0 arc of course the enthalpy and entropy difference between
prod ucts and reactants. The heat of fo rmation of ma ny substances is avai lable
and 6.S0 may be computed in many cases from appl ica tio n of the thjrd law
if heat capacity data are available. I f heat capacity data d o not exis t , a pproxi-
mations may be employed as discussed in C hapter 4. Thus from the th ird
Jaw S 0° is constant fo r a ll materials in interna l equi librium and fo r convenience
is assu med to equal zero. Thus
s T=iTctl
0
d In T
Table 5.4 Standard Free Energies of Reactions0
~co =a + bTlog T + cT(J)
Temper ature R ange
Reacti on (a in 104 J)
- b c ±kJ COK)
2 Al (s) + f 0 2(g, 1 atm) = Al 20 3(s) - 167 -16.7 367 13 298-923
2 AI(/) +! 0 2(g, 1 atm) = Al 20 3(s) -170 - 15.7 386 17 923- 1800
2 Be(s) + O.l g) = 2 BeO - 120 - 13 .9 235 42 298-1557
Ca(s) + Si(s) = CaSi(s) -15.1 - -2 17 298- 1123
2 CaO(s) + Si0 2 (s) = Ca 2Si0 4
2 Co(s) + C = Co 2 C(s)
-12.6 - -5.0 10 298-1700
1.65 - -8.70 21 298- 1200
Fe(s) + ! Oz(g) = FeO(s) -26.0 - 62.5
--
13 298- 1642
i- Ge(s) + t GeO(g) = GeO(g, 1 a tm) 22.8 28.9 -260 17 298- 860
N Graphit e = diamon d 0.13 - 4.73 1 298- 1500
La(s) + t N2(g) = LaN (s) -30.2 - 105 38 298- 1000
2 MgO(s) + Si0 2(s) = Mg2 Si0 1(s) -6.33 - 0 10 298- 1700
MnO(s) + SiOls) = Mn$i0 3(s) -2.48 - 13 17 298- 1600
Mo(s) + 0 2(g) = Mo0 2 (s) -58.6 -19.3 234 25 298- 1300
Na 20 (s) + Si0 2(s) = Na 2Si0 3 -23.3 - -5.86 33 298- 1361
Ti(s) + 2 Cl 2 (g, 1 atm) = T iCiig, 1 atm) -75.7 - 7.5 145 13 298- 1700
Si(s) + 0 2(g, 1 atm) = Si0 2(s) -90.2 - 174 13 700- 1700
CJ Based on Kubasch ewsk i et al., M etallurgical Thermochemistry, 4th ed., Pergamon, London
, 1967.
,.
5.4 Chemical Reactions ll 3
Convenient tabulations of a large number of thermodynamic data for
inorganic substances are provided in
Two convenient forms are generally employed for tabulation of free energy
data. For most accurate calculation 6.G 7 .o is generally expressed as an
analytic function of temperature. lf 6.H 0 and oS 0 were independent of tem-
perature, 6.G0 would of course vary linea rly with T. 6./f 0 and D.S 0 arc found
to vary with temperature and a convenient empirical form to express this
relation is
6.G0 = a + b T log T + c T
The constants a, b, and c are listed in Table 5.4 for a variety of reac t io n ~.
A second convenient form of presentation of 6.GT o values as a function of
temperature is by use of what is known as an Elling ham plot. This is a graphical
representatjon of the standard free energies of formation of compounds from
the elements in which 6.GT0 is plotted versus temperature. The most useful
form of representation for reactions which involve oxide formation, for
example, is to express the quantities in terms of 1 mole of oxygen gas. This
allows one to easily compare the relative reducing or oxidizing rclutions of
various solid phases. An Ellingham plot for the formati on of 3d oxides is
shown in Fig. 5.14. From such a plot one ma y readily obtain the partial
pressure of oxygen in equilibrium with the solid and metal. Co nsider, for
example, the formation of CuO. Since the tabulation is in terms of I mole of
oxygen we write
2 Cu(s) + 0 2 (g) = 2 CuO(s) 6.G1°
where the subscript f stands for free energy of formation . We have
Since the CuO and Cu phases are considered to be in their pure stable form
': at all temperatures avu = I and a<.:uo = I . Thus
6.G/ = RT In Po,
or
lo - 6.G/ (5.20)
g Poa- (2.303)RT
I .
114 Thcrmodyuamics of Reactions
·.
( -150 kcal)-209 - o,-;.
""'
(); ....
~0
CJP''"
~0
-!-~n
'lo 10-1
( -100 kcal)-418
,....
0""
0
--
E
......
10-3
-
...6
-eo..o
~ ......
C>
~ ''
<1 ( -lSO kcal) - 628 ' 10 -A
IQ- 7
Melting Boiling
(-250kcal)1-1045 - point point 10- ll
Element 0
•
Compound a •
0 1000 lOOO
Temperature (°K)
3000
10-13
'•
Fig. 5.14 Free energy of formation of 3d oxides per mole of oxygen as a function of tem-
perature. From T. B. Reed, in Chemistry ofEx temled Defects in Non-Metallic Solids, L. R.
Eyring aod M. O'Keefe, Eds., North-Holland, Amsterdam, 1970.
is shown in Fig. 5. 14. lt is seen that the line passes through the poinl!:::..G,O = 0
at T = 0°K. Wherever this line intersec ts the 6.G,0 curve for a particul ar
oxide, the equilibrium pressure of oxygen is I 0 - N/mt. Thus we see that the
5
reduced to V. One migh t duplicate this process for any oxygen pa rtial
pressure. The scale on the right-ha nd ordinate side of Fig. 5. 14 is given in
uni ts of Po, (N/m2).
A graph of this type is useful in evaluating relative red ucing or oxidizing
tendencies of materials. For example, a t all lempera turcs Ti will reduce
Fe0~, 5 (Fe 2 0 3) to Fe. This may be readily obtained from consider ation
of
~G/ for the two compou nds. At 1500°K
which has a negative value of tlG • Since all compon ents in this illustration
0
are in their pure standard state the activities of all phases are equal to unity,
and therefore ~G in this case is the same as 6.G for the reaction. As a
0
J, ~·
It
0
-l't
j,.
1
I
""It •••
1o'
-· ' I
~ ..-J
-·
"
- 60
~·
..
II
-· ~~ !9-,-
'
..-·
-ICII I .. "
-IJf f ,..
-· 10 -
l>aiC ,.. I
~
~·
10 10
~.
_.. ~·
,. I
s
I
It '
-u
10... . .
IJI' tq.•
- NO I "
I
-m to•
... ......
-110
It'
1 ...
-ItO
""I
JJ.'" _,.
--~
- 110 I .., 10" II
1
CO/CO, u t•
Jtll
.. , , . , , t4o
llll 141J
10-JIIO ..- · · 10- 100 10-to 10- 'G .. -10 ••-11) ..-)Oo
'o, 10-u ..-... 10_,.
'
Fig. 5.15 Free energy of formati on of several oxides as a functio n of temper
ature. From
L. S. Darken and R. W. Gurry, Physica l Chemistry of Metuls , McGra w-Hill,
New York,
1953.
116
:
I
According to what is known as the Hertz- Langm uir expression, the maximum
l rate of vaporiza tion of a substance is given by
t j _ (p~•I) MgO
(5.21)
MgO - (21TM RT)'A
I where Peq is the equilibrium pa rtia l pressure of MgO in this case and M is
the molecular weight. The equilibrium constant fo r our reaction is
tiG 0 = - RT In K = - R T ln [(Pctt)~rg(peq)o4 ]
Upon substitution
J (max.) = [
2'A cxp ( - tiG 0 / I{ T)]H- - - (5.22)
lttK O . M ~~g. M ~: (21TRT) ~
PROBLEMS
Similar equations could be written for the free energy G', enthalpy H ', etc.
Comparing equation"$.! wi th the verbal deijnilion of a partial molal volume,
119
120 . Partial Molal and E xcess Quantities
X 1 dfil + X 2 dH 2 ;- • • • = 0 (6.24)
X1 dS 1 + X 2 dS2 + ··· = 0 (6.25)
where
n,
X~=----
nl + ,2 + ...
Equation 6.23 or 6.11 is called the Gibbs-Dufzem equation.
t
v.·
Va
I
0 a
Xa-+
1.0
.I
Fig. 6.1 Molar and partial molal volumes of a binary system.
o - V- PuXo
.f
J' A -
l - X0
and substituting into equatiqn 6.26 we find
Applying equations 6.27 and 6.28 to Fig. 6.1, we see that i1A and Vn are
given by the intercepts of the tangent to the curve at X A = 1 and X a = I,
respectively, for the composition of interest. The molar volumes for pu re
components are designated VA. and V a ··
Identical equations for the free energy, enthalpy, energy, and entropy
may be obtained.
I
J
6.3 Relations Between Partial Molal Quantities 123
a 10
Xa -
fig. 6.2 Partial molar volume of one component of a binary system as a function of
composi 1ion.
but not that of the other component. Consjder, for example, that VA is
known as u function of composition in the binary system A - 13 as shown
in Fig. 6.2. The problem now is to obtain P0 as a runc tion of composition .
To do this consider equation 6.22.
Thus
(6.30)
t
v~
I ,
I
I ~
I II
I><
I
0
Fig. 6.3 Graphical method of ob-
taining one partial molar quantity from
another.
!.
quantity is obtained. This is shown in Fig. 6.3. The quantity (V.a- Vn") is
represented by the shaded area in Fig. 6.3 . _..
The quan tity V also may be obtained, since now both VA and Vu are
known from
.•
where G', H ', and S' refer to the appropriate thermodynamic values for
an arbitrary amount of solution. Keeping temperature and pressure co nstant, J
Dividing both sides by dn., keepin g the other components the same, and
tlte temperature and pressure constant, we find
or
O,=R1 -TS1
From this example it can be seen that the relation between partial molal
thermodynamic quantities is exactly the same as the relations for pure
components already derived. Thus
-')
(ac. = -.,)f' .
oT P.nl·"•···· I
In future use the subscripts will be deleted in connecti on with partial deri va-
tives. Their presence will be understood. Subtracting the appropriate eq ua-
tions for the relations for pure substa nces gives
dG = RTdlna
where G and a represent the free energy and activity for a particular substance.
For component i in solution
dGi = RTd In a,.
and since a1 = 1 for the pure component o f free energy G,· , we find upon
integration that
The free energy change associated with th is is called the free energy of
formatio n or more commonly the free enerJU' of mixing. Fro m th e a hove
reacti o n we sec that
(6.35)
Substitution of equation 6. 15 in to 6.35 yields
.
11Gm = x~.. (G~..- G~..·) + X n(Cu - Gu·) (6.36)
I
The equations derived thus far are ge neral. .It is convenient at th is point
to consider some applications to specific types of solutio ns.
Most real solutions do no t fall into this category, but it is a conve nient
base from which to start, since the properties of real solutio ns may he
co nve niently compared with ideal solutio ns. To illustrate an ideal solution,
consider the vapo r pressure of component i in a binary so lution. When Xi
is e4ual to l , Pi obvio usly is equal to pi·, the value for pure component i.
When X 1 is eq ual to 0, Pt is equa l to 0, since now no component i is prcscnl.
The question now arises as to how p, varies with X i between these two
limits. An ideal solution is defined as a solution in which the vapor press ure
of a com.Ponent_i is a linea r function of compositi on:
.. ,
(6.40) •
6.6 Ideal Solutions 127
~ - - -------- ---------
t
p,
1.0
x,-
Fig. 6.4 Vapor pressure of a component in an ideal solution as a lunctton of composition .
This is known as RaouiCs law and is illustrated in Fig. 6.4. Since ai = p1/pi·
by definitio n, we find for an ideal solution that
·. a1 = X 1 (6.4 1)
Substituting equation 6.41 into equation 6.34, we find that
C1 - G1• = R T 1n X 1 (6.42)
Substituting 6.42 into 6.32 we find
aIn X 1)
(
R o(JfT)
(6.43)
we find
(6.44)
P~•rtial Molal autl l~ xc c~s Quantities
S lllCC
As a result
11 H 111 = 0
nv, = o
/1S"' = - R ( XA In XA + X 11 In Xu)
Th us the enthal py and vo lume of an ideal solutio n are the sa me as .,those
qu an tities for a mechanical mixture of va ri o us amo unts of pure components.
The cut rnpy of mixiug . ho wever, is dif h:rc nl. The eq uat io n shows th at /\ ,\',.
is positi ve and is symmetric abou t X A = Xu = 0.5, where 6.S,. is cq uul to
5.73 J/moi·K.
a0 =(~) Xu
flu
or au = J1 11 °X 11 (6.45)
X A dG A + X 11 dC n = 0
From eq uation 6.34 we see that
dG1 = RT d In a;
Subslitu 1io11 uf equation (,)4 inln (,.2J yields
(6.46)
.
Stnce a 11 = Yn ox u w here Yn 0.
ts a constant,
d ln an _ d ln Xu
and thus
dX11
dIn aA = - _ _.:..;,_
I -Xu
fij.!. 6.5 Activity or Ni ami PI in the Ni Pt alloy sy., lcuL I 10111 IC A . \Vall-.cr and J . B.
Darby, Acta Met., 18, 1261 (1970).
we find that
s. . - sA·= -R In X ,,
R~. - H A. = 0
v."-- v,..· = o
For the solute U, (R 11 - Hu· ) and (V 11 - V 11 . ) will not be equal to zero
but will be constants independent of composition.
fi = H
D
+ (1 - X ) d /1
0 dX
(6.49)
ll
From equation 6. 16 we ha ve
1l = ·X.~fi A + Xu l7 11
and also
f:..H 111 = H - XAH A. - XnHn'
Thus upon substitution in equation 6.49
_ . d(X .•JI A' + Xu H u' + D. Hm)
Hn = XA H.A + XuHn. + D. Hm + ( l - X 11 )---=.......;;.;.-----"'----~
dXn
(6.50)
Substitution of equation 6.48 into 6.50 yields
+ X 11 H 11' + a'X11 + bXu2 + eX u3 + · · ·
H11 = X AH A'
+ (1- X 11 )(- 11,: + H 11' +a'+ 2bX11 + 3cX112 + · · ·)
or
fia- Hu' =a' + bX1J + (3c- b)Xu2 + ···
Similarly for Ra,
HA - Ha' = -.bXu z + ...
132 Partial Molal ~md Excess Quautitics
if the emf is measured between componen t i in so lution a nd in the pure sta te, ,
the activi ty of component i may be obtained since
C, - G 1' = RT In a,
and
a[( G.- - G;.)/T] - . a(C/ T)
ar
a(l /T) = ( H1 - Ht ) = - n.':/' a( 1/ T )
' I
.,
The logical lower Jimit of integration to use is a A at X 13 = 0 and au at
. /. X11 = 0 si nce in this case aA = I and On = 0. (Obviously On = 0 since
\
20~----~~----~~----~
I
II
~
15 ------~ -~-------------
~
(3
)<
><I 10 1- - - - - --+--------+------1
·. ....
fig . 6.6 Method of finding the activity
of one component of a binary system if
5 -- - - - - - - -1--- - the <lthcr is known as a function o f
<.;~Hupm;it ion . Cu rv~,; ~,;annot be into-
grated accura tely because log acd _.
- oo as X('tl 0. From L. S. Darken
and R . W. Gurry, Phy.rica/ Chemistry
0
o 0.2 0.4 0.6 of Metals, M cGraw- H ill, New York,
1
- log a cd 1953.
1\
XA d ln YA + Xn d In Yn + XA d In X A +Xu d In X 13 = 0
Jf Considering only the last two lerms we see upon expansion that these equal
l
Since
XA +Xu = I
dXA + dXu = 0
134 Partial Molal and l ~ xccss Quanlilic~
In YA = J:
YA
dIn YA =-
j'ro Xn
dIn Yu (6.52)
YA- lni.Xu 0 >'n• (l - X11)
At the lower limit of in tegratio n corresponding to X 11 = 0. J' '' is the llcnry's
law activity coenicient y 11 °, and as Xu -~>- 0, the solven t A follows R:wul t's
law and hence YA = I . In Fig. 6.7 arc shown the activity da ta for the Cd- Pb
system plotted in this fashion.
20
15
- ----
~
5 1------
I
t 6.9 Excess T hermodynamic Quant ities 135
~
I of A and Bin the same proportion as in the solution with a resultant tempera-
ture change 6.. T 2 •
XAA +X8 8 = A and Bin liquid Sn
By subtracting the former reaction, if the weights are kept in proportion
I
we have
I
(
I available for only a small fraction of the possible systems. One source of
thermodynamic data is available from the phase diagrams of the systems
themselves. In certain specia l cases much information may be gleaned from
these diagrams. This topic forms the subject matler of Chapter 8.
I Mi,X' = RT In I y, (6.53)
T he re fo re
6. // Ill l{'4 = 6. // til
ixing
F or the volume of m
an d
an d (6.SR)
D. vx s = D..V
I
I
im po rt an t, si nc e, an id ea l solution
excess qu an tit y is The excess quantities
T he co ncept of an ee n at om s oc cu rs .
t interaction betw equation 6. i3 , for
is one in which no ne th at oc cu rs . Fr om
the interaction partic ular component
renect the nature of ity co cf lic ic nt of a
example, it can be se
en th at the activ
ra ct io n. If y is I , !J .C, :c!! is zero. If Y; > I,
re of this inte 1
n from Rao ul t's law
. If
in so lu tio n is a mea su po si tiv e de vi at io
assified as enerally,
D..G/s > 0. This is cl a negative deviation from Raoult's law. G than it
}', < I . D..G,x .. < 0 anwdhiisch a given compo ne nt has a hi gher :tclivity s itself" in
th e former case, in tio n of th e sa m e composition, rellcct
eal solu ractio n
would have in an id l. T hi s in dicates repulsive inte
positive values of 6. v,x.and ~ Fi/· R as w
w
el
he re as th e latter situation re nc
cts an
nts in so lu tio n,
between the compone
n.
at tr ac tiv e in teractio
L FI E LU 0
vn·A Tl O N A L O R C E TR fF U G A
F GRA
f 6.10 E FF E C T O
E E l T \'
A LL O Y H O MO G men.
l fie ld w ill ad d a force <P to the speci
centrifuga give n by me/>. The to
tal
A gravitational or m e po te nt ia l is
ergy by ut = u + m,
speci men is th P.
l f the mass of th e to th e in te rn al en
energy of the system
ut is relate d
d to or su bt racted from the
system~
ld no he at is ad de
By imposing the fie
y is unchanged.
therefore the en tr op
ry
kn es s, ~I I , th e pr essure p will not va
very small thic n by
If the system has a bs free en er gy will therefore be give
d the G ib
within th e sample an
G, = G +me/>
6.10 Gr.tvitational and Centrifugal Fields 137
where lit is the number of moles of component i and the mass m is given by
m = 2 11 1N(i
where Mi is the molecular weight of component i. By combination of tile
above three equations we find
(6.59)
Suppose now we consider a system of macroscopic length in wltich 4> is a
function of length, z. If the concentration of component i remained the same
at all val ues of z, the partial molar free energy at z would be
G, 10 (z) = Ct + M 1</>(z)
Since </>(z) is not constant. GtC 0 (z) varies along the specimen. This results in
a n ow of component ; along the speci men in nruc r to equalize C,w(z) at
each point along the specimen. Thus the value or [Ci + Mi</>(z)] is a constant:
Gi + tWA>(z) = constant (6.60)
Because of the presence of the field, the pressure will dilfcr along the specimen
and therefore at conslant temper-ature G, = f(X1, p)
{ IG; = aci)
(-
axi /). ·r
{ Jx.' i + (aca .)
- 1
tp
JJ }.:1 • 7'
which becomes
dp = p(r)w 2r dr (6.63)
where pis the density at poi nt r. If the specimen is hasically inco mpressible
p is eonstanl. Consiucr now ClJU<tt io n 6.(> I . L)iviuc thr<Jugh by dr a mi ~u h
stitute 6.63. This gives
(-oXac.)•
1 u. T
dx .
- '+
dr
Y
,..,
,p(r)w-r -
.. ..
M, w~r = 0
or
CJG)dX
-
1
= 2
w r[M 1 -
V,p(r)]
( ax,
' -
dr
-
Now
oCj) = RT(o In
( aX, 7'.,.
y,) + RT
aX ·r... I X{
Therefo re
(6.64)
dIn X 2 (M 2 - V2 p)w 2
-
d(r 2 ) 2RT
p=
X 1A/ 1 + X 2 Af 2
X1 V1 + X 2
and since X 2 << X 1
pr-Jr-
M,
J
Therefore
d ln X 2 (M 2 - M 1 V ')w 2
- (6.65)
d(r 2) 2RT
1:
'
Problems 139
impuri ty forms a pai r with a vacant lattice site, V' ~ 2. Figure 6.8 shows
experimental results for Au in solid K. A restriction o n experiments of this
type is that the solu te must be sufficiently mobi le at the temperature of the
experiment in order for redistribution to occur in a reasonable time.
3.2
/0
,..~v·-
-
o
.-::"o
/~;'()
.."() "" _.. = 1
...... ,.."''v·
.~ 6"\J , ...
,..o ~
,.......
,.. .... ,.. .... ,..-- v· = 2
0
,.. ....
0
, o,...0/__
,"
.... , -
~
__
n,o..,..,.,,.,.
....
·~
a.
.e 2.6
....
~,
P!:~,. .. - I
>~-
110
..2
65 70 75 80 85
(Otslance from axis of rot alton) (em) 2
The results indicate that V' = 0 and thus that Au dissolves interstitially
inK.
For a gravi tational fi eld , <P = gz where g is the gravitational consta nt and
z is height. The reader may show that redistribution is negligible in the small
gravitational fi eld for solid systems.
PROBLEMS
l. In a Ti- ll solution .J. i1 11 and 6C 11 are given in the rollowing table as a function
of X H at 9 l0°K (t:. ll values in calories per gram-atom).
(a) Find 6C'l' l at Xu = 0.4. (b) Find D.C 111- at Xu = 0.4 (c) Find uS 11 at
Xg = 0.4 (d) Find D.Gmxa, 6Guxs, and D.Saxa at XH = 0.4.
Part ial Mohal and Exce ss Qu:w lilics
140
Calculate CI H at XII = 0.2
2. In Prob lem 8.1: (a) Find }' H at x,( = 0.2. (b)
or Ti cont a in ing :w at " ~ I I
(c) Find the equi li brium II ~ pressu re for a n alloy
(mon ato m ic).
odyn a mic beha vio r. 6 /( 111 a t
3. Solid Au- Cu alloy s are regula r in their therm
the follo wing table.
773° K is liste d as a func tion o f com posi tion in
ll H ,, -u.o - IH10
- 1240 - 11 30
(e« l · mo l) - 355 - 655 - 9 10 - 11 20 - 1230
7. 1 I NTROD UCTlON
Very few liquid or sol id binary systems behave in an ideal fashion . One
generally observes that the heat of mixing 11H 111 #- 0 and often the entropy
of mixing /1S ~ 0. In addition, the curve of D. lfm versus mole fraction is
often not symmetric about the val ue X A.= X 11 = 0.5. Some thermodynamic
results for alloy systems are shown in Figs. 7. 1, 7. 2, and 7.3, which illustrate
Atom•c fraclton Ni
Fig. 7.1 Experimental values of the heat of mixing a nd free energy o f 1mixing in the Au- Ni
system. From B. L. Averbach et a l., Acta Met., 2, 92 (1954).
J42
1000
'E
~ 0
•
DO
::::-
IU
u
1
~-1000
f..,
~
<] -2000
c5 .· I -~
<] I
x~j
Fig. 7.2 Free energy or mixing, hea t or mixing, a nd entropy or mixing in the Ni Pl
system at 1625° K. Broken curve represents ideal entropy or formation . From R. /\.
Walker and J . 0. Darby, A cla Mel ., 18, 1261 (1970).
0 0
-
-0.50
-t
0
--e
0 EI
E
::.::
-10oo -1.00 :::.
........
~
-gcv -1500
-
10
v
~
~
"'0
c
~ 10
- 2000
~
-2500
0 100
Cu Pd
Atomic% Pd
Fig. 7.3 Thermodynamic fun ctions in the Cu- Pd system al J000° K. Based on Hultgren
et al., Selected Values of Thermodynamic Properties of Metals and Alloys, Wiley, New
York, 1963.
11.~~. 11 • and /1 1111 • res pectively. The mean pot e ntial re fers tn the pntc-ntial
between pairs in the dosc-pac"cJ array in ~ol ut ic.lll. ·1 his potenltal i" dilkr~nt
from that for two atoms, say, in a diatomic molecule. There is in f<:t ct no
unique potential between a given A and B atom, but rather the val ue depends
upon the environment. Parentheses will be employed ( B A ) when the total
of A - B and B- A pairs is im plied . In a solution which con tai ns N ions.
there will be p A ,\ pairs of type A- A P (.\lt) pairs or type A - l3 anti Pill\ pair
of type B- B. Thus the enthalpy of the sol ution will be given by
( 7.I)
The next step is to evaluate P.._ 1, , PL, 111 , and P 1111 • 13cf'orc attemp ting this,
the treatment may be si mplified by elimination of P" ·' a nd P 1111 as fo llows .
The crysta l contains N., atoms of type A a nd each one of these has Z
neighbors where Z is the coordinnli on number. Each A B pair con tains one
ion of type A . whereas each A - A bond contains two ions of type A . Furtha.
each ion is shared among Z bonds : thus the number of ions or type A
involved in A - B pairs is P1 \lll/Z and the number in l ) pe A~A pairs is
2P AI./Z. Since Lherc arc N ,, atoms or Lypc A.
Thus P,u + /' 1,11 can he exp ressed in terms of / 1 1 " 11 • N .\· N 11 • and%. and
substituting into equation 7. 1
11 = ~ZNaii,, J, + ~ZNn llu 11 + PcAu>[//" 11 - Hll ., , + 11 1111 )j (7.4)
We arc interested in knowing the heat of tnixing. ~ /1 111 • Thi ~ is given hy
the reaction
N A ions of type A (s) + N 11 ions of type B(s)
= ( N" + 11 ) i<Hl ~ in solut ion !l/1 ,,,
and
11H,. = If - H A(N A ions of type A. pure) - //( t\
ions of t) pc B, pure)
11
The enthalpies of pure element A and pure element B arc given hy !ZA!l_, ,,'
a nd -~Z 11 lfu 11 ', respecti vely. ZA a nd 2 11 arc the coordinatio n num ber of the
pure elements, respectively , and /1 6 A' and 11 1111 ' are the appropriate mean
potentials. For the sake of illustration consider Z _, = 7. 11 = Z <tnd let us
7.2 Application to Idea l and Regular Solutious J45
make the assumption that HAA• H 111 " and H"'' are independent of con-
centration. Thus H 1111 in this crude approximation is the same in pure B
as when B is a dilute sol ute in A. This would have only approximate vaJidity
when A and B are closely rel ated chemically. If these assumptions are made
we find that
~H"' = P IA II ,[HA B - HHAA + HuuH (7.6)
A quantity n is defined as
n =ZNo[HAII - HH At\+ lfuu)] (7.7)
\
rellecting a balance between ilHm and 6.S,. in order to minimize 6.G,.. The
system can achieve a maximum D.S 111 and hence a maximum T !:iSm con-
tribution to D.Gm by the destruction of o rder, hut at the expense of the ti ll ,,
\ term. which would be minimum for an ordered :,ystcm. Because in the
expressiOn I I I
D.G m = 6.H"' - T !:iSm
f
the f:lS,, term is multipl ied by T. the T ~S,, term will he more impo rt a nt
at elevated temperatu res. As a result the degree of o rdering or clustering in
a system will decrease as the temperature is elevated.
From this discussio n it it evident that a regular solution fo r wh ich I
tl.S,/9 = 0 will be found only at elevated temperatures in systems where ·, f·
n is a small quantity.
We may find 6.R A and !J.fi 111 the relative partial molal enthalpies fo r a
)
l
regu lar solution , fro m equation 7.9 by use of relations derived in Chapter 6.
we find that
6.CA = (1 - XA) 2!l + RTin x.A = RTfn aA
6.C 0 = (1 - X 0 ) 2!l + RTin Xu= RTln au
We see that
(L-X A) 2fl
I nyA = (7. 12)
RT
2
I (I - Xn) fl
n Yo= RT (7. 13)
Thus for a regular solution, the acli vtty coefficient is strongly related to
the interaction parameter, fl. As will be shown later, Y t for a nonregular
solution is also a function of 6.S/•.
When tbe interaction between unlike atoms is attractive, n is negative,
and hence In Y£ is negative and y 1 < 1, giving negative deviation from
Raoult's law. Conversely, when !1 is positive, Yt > 1, givi ng posi tive
deviation from Raoult's law. In Fig. 7.4 are shown values of tlGm at l000° K,
as a function of composition for va rious values of .n. It is observed that the
function is symmetric about X A = X 11 = 0.5. In Fig. 7.5 are shown.valucs of
aA as a function of composition, and n at l000°K as calculated from Fig.
7.4. From the equations derived, it may seen that Henry's law is only an
Or---~---.--------~--,
0
---r
= =
4000
--
n = sooo
2RT
./
- 500 I
--~ -1000
e
c:>
<J
- 1500
6Ga
- 2000
lOOO"K
- 2500 .____...__ _.__ _.__ _ _ . L_ __,
y's law. In
•
')', v =co nstant when com pone nt
appr oxim ation . Acco rding to llcnr
In )', a ppro ac hcs ~~ co n-
i is dilute , wh ereas fro m CtJua lio n 7. 12 we sec I ha t
ore the: va lidity of
sla nt value , D.j RT, asym pto tically as X i-+ 0. Furtherm
io n where Henr y's
Rao ulfs law being a pplic a ble fo r the solve nt in a solut
since In Yt approaches
la w is obey ed fo r the solute is also a n Jppr oximatio n,
tio n 7. 12.
zero asympto ticall y as Xi appr oaches un ity, fro m eyua
ng term s of highe r
Ex panding the ex po nenti a l in eq ua tio n 7. 14 and eliminati
o rder th a n th e seco nd , il is fo und that
\• :! \ ' " I\ ,
,, , - "'...:..Il'-~-1.
-"'.....:.A.:-
u:::>
A • X"
,. Z J< T :!
(7. 17)
, 1952.
1 E. A . G uggenheim, Mtxtu res, Oxford Press, Lond on
7.3 Nonregula r Solutions 149
0.20
0.16
0.12
- -1--
/.
v >--- -
/
0.08
v
l ·- - -
0.04
I
I Fig. 7.6 Short-range order in the AI- Zn
1/ system as u function of composition at
10 20 30 40 50 673°K . From P. S. Rudman and B. L .
Zn, at% A verbach, Acta Met ., 2, 576 ( 1954).
150 A Model Approach to Alloys
~ ~~--~---~--~----~---.
.
-i
~ GQOI-- - +
~
~
<l 400 1---11-~--+---l---t --- 1
where
and
N = ex p (_Q_)
ZRT
From ex perimenta l data for y. n mny he de termined directly and / 'A l l • for
example. ma y be ca kulul cd . In Fig. 7.H arc shown cxpc rilllcnlal adivit y
data for the liquid ln- Sb system which ha ve been fit to a particular value or
)
n.
The interaction parameter i2 has been examined in some detail by
Averbach.2 The value of U is, in a general case, dependent upon both
1.0
0.8
I~
L7
I
....a 0.6
~
-
.~
<
u
0.4
v
7
v v
0.2
0 ~
0 0.2 0.4 0.6 0.8 1.0
Xtn
l'' lg. 7.8 Expcrimcntul uutn fur uctivity of In in the I n Sb system li t to cqun tion 7. 19.
!l ca lculated to be -3980 cal/mol. G . B. Stringfellow and 1'. E. Greene, J . Phys. Chem . Sol. ,
30, 1779 (1969).
co mposition a nd tem perature; let it be assumed tha t these may be sepa ra ted.
T hus for n we may wri te --
,.1 - p!
'// - p AA·I p BU I· p AU·I jJ
UA·
I
This term actua lly co nta ins ma ny una llowable co nfigurations. To illustrate
consider a B atom. All pai rs involving this ato m must be ei ther B- 8 or 13- A
pa irs. No A- B or A- A pai rs a re a llowed . T !1e exp ressio n fo r 'W' is modified,
152 A Model Approach to AIJoys
therefore, to take into account the factlhat whenP(AIIl is that for a random
solution, t:,.S,, must also equal that for a random solution. The final equation
employed is
p! N A ! N ll ')7.• ( N )
if/'= (
PaA.! Pun! PAu l P 11 ,..! N N,..l N 11 !
Upon substitution we find that
P (AH> = ZNXAX 11 (l -a.)
and recalling lltal t:,.S 111 = - (a t::,.G,JaT),, one may derive that
we obtai n
a. ~
2X},)( u[u + j(X) + g(T)]
- kT
Upon examination of the above equation for uS,/\ one sees that the sign
cannot easily be predicted. The fi rst term on the right-ha nd side is always
slightly negati ve but the tempera ture dependence of g(T) may he very
large in principle and may be either positive or negati ve in sign. Also one
sees that n may not be obtained from thermodynamic measurement ..
~
of /!:,.H"' since only the terms [u + j(X)] are involved in the expression for
/!:,.Hnu whereas O.fZN0 = [u + j(X) + g(T)].
1\s a simple case, assume that K is linea rly dependen t upon l cmpcra lu rc
[g(T) = gTJ anu let liS examine SO illC alloys. Fro m thcrmodyuami<.; dala
D..Hm and D..S"'xs are often available. The terms [u + j(X)]g and g may be
obtained as a first approximation from /!:,.//"' and 6.Sx , respectively, by
8
Atomic Order
a '
a
a
/a
{3 13
a a
/ / a /
a
and the fraction of {J sites occupied by wrong atoms (A atoms) , ll'p, is given
by
ll'p = l - r p
For complete order, r(J = r p = I, and for complete ra nuo mness, the prob-
ability that an A site is occupied by a n A atom is X A; hence the fractio n of ex
sites occupied by A atoms for complete disorder is X.,... It is convenient to
define a long-range order parameter ,97 in terms of disorder on the ex sites as
13 atom s
The fraction of B atoms on a. sites is (I - r 0J and the number of
on a. sites is (1 - r.)N/ 2. Upon subst itution in equation 7.2 1, we find
Pun = ( l - Y' 2 )N
or
if/"= (N/2) !
{[( I + .9')/4] N}!{[ ( L -.YJ)/4JN}!
(N /2) !
X ------------~------------
{ (( I - .9')/4JN}! {l( I + .9')/4 JN}!
Upon applic ation of Sti rling's approx imatio n
m ''
Jn the limit of !/' = 0, S0t"'c = R In 2, which is th e entrop y for a rand o
ent
solution for X A = X 11 = !. ln th e limit of .!/'= I , S cunr = 0 in agreem
with wha t is expected fo r complete o rder.
The free energy o f solutio n is
G = II - TS
and upon substitutio n
l
where S0 represents the excess entrop y pe r atom (exclu sive of co nfigurationa
or
contri bution s). The entropy, of co urse, is a maxi mum when .(/' = 0,
when there is co mplete rand omness. (f ~ (/zAA + hn 11 ) > hll ,h the enthal
py
term wi ll be reduce d and an optim um va lue of .9' will be altaine d in order
to make G a minim um.
As T increases, S <'lnlt becomes mo re impor tant relati ve lo the enthal py
term, and hence !/' dimini shes. At a cri tica l tempe ratu re, Tc, .'/' in fact
be
beco mes zero. Fro m equati o n 7.24, the cc.1uilihrium value o f .V' may
calculated us a function o f tempe rature . This is shown below in Fig. 7. 10
.
The critica l tempe rature 7~ is govern cu by the relatio n betwee n 11 .\ll and
!(hAA + 11 1111 ). The lower the energy o f the A- 13 pair in relatio n to the
average of th e A- A anti B B mea n potentia ls, the lughcr 7~ will be.
Soluti on of equali on 7.24 y idus
~ J.O
.:
Ql
....
"'U
0
Ql
00
I cIQ
....
00
c
~ .3 0.5
""'\l\\\
...
tV
....
"0
0
~
c
\\
...
~·
Ill
I
00
c
0
....J
'
0 r
0 1
FiJt. 7. 11 I un g- ranl~C nrdl'f i~ar: lll lC i cr a-; :1 runl"l i u n , ,,. ICI IIJ'I.·r:rturc ,., , .. So":. C u.
50 /~ :ln. Compa rison l>ct wccll theory anJ cxpc rilllClll.
J
7.
1
0
Zeroth
~ ~ Experiment \__
0 1
1'/1~
Fig. 7.12 C omparison between cxrcrimc ntal and c.tlcukttcd values o f ( , for 50 ~{. Cu.
1
50 % Zn . Experimenta l tlata fro lll F. C. Nix anJ W. Schoc klcy, R.c11. M ad . J•hys. , 10, 1
(1938).
158
-
159
7.4 Order-Disorder Transitions in Solids
Tr
Absolute tempe rature
1.0
l
-
,-
)(- )(- )(
0.8 i"'--x j(
X
0.6
,!Jl
0.4 - \- )<
~
0.2 ~\
'
100 200 300 400
Temperature (•C)
Magnetic Order
For a pure component in which the atoms have magnetic moments, or for
an alloy in which at least one component has a magnetic moment, order-
disorder theory may be applied to the ordering of spi ns. 1 A paramagnetic
material corresponds to a disordered array of spins whereas the ferromagnetic,
anti ferromagnetic, or ferrimagnetic states correspond to an ordered assembly.
The transformation from an ordered state to a disordered state is usually
found to be second-order, as discussed earlier, and has a magnetization-
temperature curve a s illustrated in Fig. 7. 15. One therefore observes a dis-
continuity in the heat capacity versus temperature curve.
t
/II
ferromagnetic
l.O
'l'/7~ -~
For an alloy A- B in which A has a magnetic moment ~~~11 " }' and B a
moment /l'::J uy , the entropy of mixing associated with the mixing of moments
alone is calculated to be2
~S m(mag) = R[ln (J.L~Io> + I ) + In (J.'~11ln r + I)
-X" In (p. _, +I)- X 11 1n (tt 11 +I)] (7.27 )
where !1-.t.. and JJ.u are the moments in pure A and 1:3 , respectively.
eratures, the
Assuming v to be independent of temperature at high temp
vibrational entropy per oscillator is found by substitution to be:
S.., = k(tn k T +
lz v
t)
gram -atom
Since a gram-atom of crys tal has 3N oscill ators, the entro py per
is
Sv = 3R In - kT+ L) (7.28)
(
hv
162 A Model Approach to Alloys
Suppose now that the oscillators are changed from frequency v to v'. The
entropy change associated with this process is
:.
6.Sv = 3R In (:,)
Thus if the frequency is lowered, 6.Sv will be positive.
Consider equation 7.28 in the case of alloy formation
Xr.. (pure A)+ XH (pure U) = Alloy (X", X 11 )
The Ochyc frcqu~nt;y of pure 1\ is J' ,,, of pure B is l 'rtt <llld of the alloy is 1• 11 • •
Therefore
6.S v = 3R In V
A
XA. 11
n
Xu)
(
1' I)
9.0
8.0
I-
o Th1s expenment
I
• Hoare and Yates
7.0 1- o Quenched from 950" C
(f;J pha se)
..... 6.0
('0
~
•.
I
-
-
0
E
.,
5.0 i-
I
v
E
~ 4.0
3.0 - -
2.0
l
/'
_ ,.... "' "'
...
-
1.0 - ~
1'1.. )
l l I I
70 80
I
90 100
10 20 30 40 50 60
Atom ic% Pd Pd
Cu
o, J. M.
n com posi tion in the C u·P d sys tem. Fro m Y. Sat
Fig. 7.16 The dependence of yo
. Ul , 140 2 ( 1970).
Sivertsen, and L. E. Tot h, Phys. Rev
0.2
0.1
-
0
-0. 1
E -0. 2
~
•
~
.,v - O.l
-
= - 0.4
~
- 0.5
-0. 6
- 0.7
- 0.8 0.6 0.8 Pd
Cu 0.2 0.4
Xpd
fro m 0 and y
ess vib rati ona l and e lect ron ent rop ies at IOOO ' K as calc ula ted
Fig. 7. 17 Exc
E: Tot h, Plty s. Rev., Bl, 140 2 ( 197
0).
values. From Y. Sat o, J . M. Sivertsen, and L.
164 A Model Approach to Allo)'S
PROBLEMS
)
r
I'
~~
8
Phase Phase
a {3
Component i .. Component i
-f-
Activ1ty n i a Achv1ty a, 0
Fig. 8.1
If a/ < a/x. the reaction above will proceed spontaneously since in this
case 6.G < 0. Conversely if a/1 < a/ the reverse reaction will occur since
similarly l:l.G- 0 by such a reaction. When the co mposi ti o n has linally
changed so that equilibrium is attained, 6.G = 0 aml therefore a,« = a." or
Gt = C/. Therefore we ca n generalize that, at equilibrium, the pa rtial
molal free energy or chemical potential of component i will be the same in
all phases. lf we haver components and c/> phases, then
.,-;a _ Gp_.,-;y_,,_G~
U1 - 1 - Vt - - 1
G2
«- -
GP-C
2-2
1 -··· - G~
--2 (8.2)
Ga=CP=C r =· .. = C~
1
r r r
We presumably have several variables under our control. We may consider
that we can vary the composition of all r components. In addition T and p
may be varied, in principle. Since the composition of a given phase is given
. by
X1" + X2« + x 3Q + · · · +X/= J
there are only (r - l) component va riables. Since there are 4> phases, the
number of independent variables is c/>(r- 1). If we add temperature and
pressure, the number of variables is 2 + cp(r - J). These ca nno t all be at
our disposal, however, since at equilibrium 8.2 must hold. For each com-
ponent we see that there arc(</> - J) equations of equality for G. There are
r components. Therefore the total number of equations is r( 4> - I). The
167
8.1 Gibbs Phase Rule
is the total numb er
numb er of varia blesfactu ally unde r our contr ol there fore
een them
of indep ende nt variables minu s the numb er of relat ions betw
f = 2 + cP(r - 1) - r(cP - 1)
or
(8.3)
!
i
ibriu m is there fore
The numb er of degrees of freed om for phas es in equil
of phas es plus 2.
equal to the num ber of comp onen ts minu s th e num ber
n in Fig. 8.2. Since
Cons ider for illustrati on a simp le binar y syste m as show
r:
(!) liquid
T
a+P
®
A B
X a~
Fig. 8.2
Uquld
B +liquid
t
1'
a+B
Tt
A x:cwu B
Xa-
Fig. 8.3 Phase diagram for case where B is solu ble in A but A is insoluble in B.
and consequently
0 1 (8.5)
Yu =
X71 Ct:~aL)
We may gain information abo ut the shape of the solvus line of ~ as a
function of temperature for this type of phase diagram. Unfortunately
equation 8.4 for the solution reaction is not too useful from this point of
view, since flG is zero. As a result let us consider a different equation. Let
coJnponent B be transferred from the pure state to some arbitrary composition
in ex., say, X 8 = 0.01, instead of to X.U(aat)· Thus
B(s) = B(Xn = 0.01) flG 1
Let us now evaluate flG 1 •
an .
llG 1 = #n -
RT In - Pn = (8.6)
a a·
an· = l as before, and a 11 = y 11° (0.0 I). Substitution into equation 8.5
yields
0.01
au =
Xfi (IHll.)
Thus from equation 8.6
(fLn - fLo")= RT In (0.0 1) - RT In x;<sat)
We know that
o(/;ldT)
--'--'---- = H.
o(l f T) - '
, , I
Therefore
o(t-t 11 /'f) a(flu·rr > - 11
(a In X7,<,.,
o(J/T)
11 1)
o( I/ T) - o(l / T) = ll u - ". = -R
f:lff 11
---
R
or
( 6. H n) (&. 7) •
a
X Uleo.L) = A exp - RT
Slope= -tl.H8 / R
1
I
# •
)
1
r
Fi.g . 8.4 Solvus line from Fig. 8_3 plo tted
a ccording to equation 8.7.
from the sol yus line 617 11 , as for most cnthalpics of solid state reactions. is
virtually independent of tempera ture. Experim enta ll y, when In xr~(ll:iL) is
p lotted versus 1/ T, a straight line is obtai ned, with a slope equal to -6.17 u/ R,
as shown by eq uation 8.7. This is shown schematical ly in Fig. 8.4. Generally
!J.Hn is positive for solid solution s, so X» c~~<ll) increases with T. This treatme nt
is not valid for temperatures above the eulectic tempera lurc since the <Y.
t
8.2 Thermody namic Quantities and S imple Phase Diagrams 17l
phase is in equilibrium with a concentrated liq uid . lf one knows the thermo-
dynamic properties of the liquid, the problem is again tn.ctable. In some
systems regular solution theory is a reasonabl e a pproximation.
The problem just examined may be approach ed from a statistical point of
view, which will yield informati on about the nature of the term A. Let us
consider a gram-atom of solution consisting of N A atoms of compone nt A
and N 0 atoms of compone nt B. Thus XA = NA/N0 and Xn = Nn/ N0 • An
atom of B has a vibrational entropy when in the pure state of Sf). When the
B atom is put into solu tion it will undergo a vibrational entropy change to
S"', resulting in a change per atom of 6.S11 • Further, there will be a con-
figurational entropy change given by tl.S"' = k In (if/"' /if/"). In the pure
state if/' = 1 aod in the alloy
i f/' = No!
Nul NA!
It has been shown that the ideal entropy of mixing for a gram-ato m of solution
is given by
8.S111 = -N 0 k [XI\ In X" + X 11 In X 11 ]
The partial molal mixing entropy 6.S0 per gram-ato m of B is given by
l\Su(w) = - Nof<. In X 11
and hence the mixing change per atom of 13 is
!1Sc =-k In Xu
The initial entropy change per ato m of B is
Comparing equation H.9 with 8.7, we see tL1at the integration constant A is
Phas es of \'arial>le Composition
172
th sides or eq ua ti o n H.9,
equa l to ex p (6S 1,x /k). Taki ng the loga ri thm o f bo
8
A C. X ll A J-j
« L.l0 H 0 II
In XlH tull. l = _....;;.;.__- - - (8.10 )
k kT
t 6Sux 11 is inde pe nden t of
This , o f co urse , is base d on the assu mptio n tha
idere d here , the approxi-
conc entra tio n . At the low conc entra tions bein g cons
mati on is good .
We see that ifln Xfsc,.at) is plott ed vers us 1/ Tas in f
ig. 8.4, and ex trupo laled
beco mes zero and t he
to l/T = 0, the seco nd term o n the ri ght- hant l ~ide
-.: /A. .
11
inter cept o f In Xu<sat.> at this poin t is eq ual to 6S11
prov ides a meth od of
Thu s appl icati on of simp le statistica l mech anics
n rela tive to t he valu e
e valu ati ng the exce ss e nt ropy of a solu te in a so lulio
<.lata fo r vari o us solu tes
of the p ure solu te. ln F ig . 8.5 are show n solu bi lity
0.2 -
0.4 - f xce<><>
I"OIIOJlY
~Oiutf' IIICior
0.6
N• (j()
0.8 Mn 20
Cr 25
Si 17
l.O IS
Cu
1000 1.2 Zr 10
1' Cll
1.4 - .2 400
"'Q:;a.
E
~
200
• 0
0.1
Atom•c concentration ( % )
consequently Henry's law coulu JlOL be applicu. For these cases a mouilicu
form of equation 8.9 was employed in order to obtain 6Snxs and .1Ru. It
should be noted that all values of 6Rn are positive, which indicates that the
solubility of B in A increases with tempera ture.
At Jow solute concent rations the degree of short-ra nge order will normally
be small as may be calculated from equatio ns developed in Chapter 7. As a
consequence, con figurational contribu tions to the excess entropy will be
small.
LIQUid
I
I
1
T
I I
a+IJ
XB
~G =0
Hence
p 12
,u n (Hal) = ,u H (!tnl)
The difference between this case and the former case is that
p •
.Utt{M Lt 1 ~ ,Un
Since oc and {3 are both dilute solutions, Henry's law is obeyed by the sol utes
and Raoult's law is obeyed by the solvents. In the case of the fJ phase, U is
the solvent and hence
• p
= P-n + RT In a 11 = !lu + RT In
{J • {I
P-u Xu ( 8. 1r)
f I i
for the solven t, si nce Yu = I. At the composition XfscllliL)
I l
P
fJ.II(snt.) = ,Uu • + RT I n X PII(Hnl.) { l
ln saturated phase oc, compo nent B is the solute and f'ollows Henry"s luw.
Th us ~ . I
P.ua =!-ln. + RT In X~ ctlat.> + RT In Yu 0
(8. 12)
Equating 8.1 l to 8. 12, we sec that
or
(8. 13)
8.2 Thermodynamic Quantities and Simple Phase Diagrams 175
t
0
0 1.0
Xa -
to the phase
Fig. 8.7 Activities of compo nents A and Bat temper ature T1 . Corres ponds
diagram in Fig. 8.6.
ra ture
The activit ies of A a nd B arc shown schem atica lly in Fig. 8.7 at tempe
T as a functi on of compo sition .
Illustration
Problem. N ickel and cleme nt A are related by a phase diagra m of t he
type show n in Fig. 8.6. At 1000°K , eleme nt A will disso lve 4 at % nickel
and
nickel will dissolve 6 at % A.
Calcu late the oxyge n pressu re at which nickel dissol ved in A to the extent
than
of L at % wi ll just begin to oxidi7.c to NiO. Eleme nt A is more stable
nickel and will oxidiz e only at higher oxyge n pressu res.
Solution. From therm odyna mic data we ftnd the sta nda rd free energy
fo r the reacti o n
NiO(s) = ~ 0 2 (g, 1 atm) + Ni(s)
to be
~Go= 146,000 J = -RT1 n K
Since the nickel is assumed to follow Henry's l <~w. the uclivity coellicicnl ·
YNio is constant and, since a~ 1 =-J'NiuXI'n, we knowa~i at x~i = 0.04. I I
0 94
Yr-;t = · = 23.5
0.04
Thus the activity o f nickel in a I at % solution is
ar>H = 0.01 (2J.5) = 0.2J5
Upo n substitution into the equilibrium constant above, we find that the
equilibrium pressure nf oxygen is
Pot= 9.6 X tO- tO N/ m2
Let us now turn our attention to the solvus lines of lhe «a nd fJ solutions
in order to see what thermodynamic information mny be obtai neu. Our
basic reactio n is,
As before, however, th is is not useful for this problem since b.G = 0 anti ' no
meaningful operations may be perrormcu .
To eliminate this problem let us start with the above reactio n and transfer
o ne gram-atom of U in fJ from concentration Xf! ~:.. au to, say, X/ = 0.99.
Similarly let us transfer one gram-atom of B from X~c~•tt.> to, say, X11 ~ = 0.01.
( L) D.Ci, = 0
(2) B(X~IC~t\t.l) = 11
lJ(X 11 = 0.01) nG 2 = I<T In O.O I
..r 7, c..,l, 1
'\·II
p p ~G.l = RT In ; lll~<nt.l
(3) B(X 13 = 0.99) = B(X u(ant))
. 0.99
1-
p
Xn (r;nt.)
= B exp ( - - - u.HA)
A - fJ
(8.1 5)
1- xrHIInt.) RT
where A a nd B are integration constants. As a result we see that, by plotting
experimental values of the ratios of XiJc~nu and Xllc1111u in the manner of the
above equations, both 6. /7 11"' and 6. 1--7/ may be obtained. Furthermore, if
the logarithms of these ratios are plotled as reciprocals of absolute tem-
perature , tWO Straight lineS ShOUld be Obtained. It iS ObServed that Xll(Riltl
and X~(lmtl should vary exponentially with temperature. If this is not found
for very dilute solutions , the validity of the experimental data are open to
question.
diatomic form rather than monatomic, the exponent will be equal to one.
The temperature dependen ce of the solubility nwy he readily calcul:1 led by
foJJ owi ng the proced ure o ullined in eq uati ons 8.4 th roug h 8.7. Thi s yields
6.17,,)
Xo lsRt.l = A exp (- -2UT- (H. I H)
·.
We sec, therefore, from eq uation 8. 19 that the change upon solubili ty with
pressure is related to tempcmturc a nd the partial molal volume of component
i in solution. Upon integratio n fro m p = I atm to p we obtain
X,hmt.l Vi( P - I )
In - (8.20)
xi(•mL.11"" 1 1\t.rn) RT
if pis give n in atmospheres. At large values of p the term (f' - I) ,....., p.
The solubility of hydrogen in a Pd- Ag alloy has been studied as a function
of tensile and compressive stress by Wriedt a nd Oriani . For an i so tropi~;
1
33.05
1 - - -1- -
--d 33.10
- ---f--- -1 33.15
1- ---1 33.20
33.25
Elfecl of jaw
backlash w1th ~C.LJJ ~·'""'"'! 33.25
-~ - - flexible enclosure-
J.-- 1 - - 1 - - + - - - + - - + --+- - f............,: - - 1 - - l
-- l 33.30
. 33.35
- - l - - - - 1 - - - - 'lo<.l 33.40
in slope at 0' = 0 is an artifac t and is due to slippage in the appar atus at the
point of conversion from tensio n to compression. From these measu rements,
the value of vi in the alloy was calculated to be 1.90 X Io - R m
3 /mol H.
For a more genera l case such as the phase diagra m illustrated in Fig. 8.6
it may be shown that at consta nt temperature
(8.2 1)
dp {I
{X U(t<ul,) -
a ';)
cJf.lu
X U (lmt.)) ( ':l Jl
(1 )-1
. uX Ul,.o.Ll
v
where ~ V11 = V« - ( 1 - xll(Rnt .l) A.f.l - x~(flr\U v,/). Equation 8.2 1 may be
readily deri ved by using the relation that al equili brium , P·n« = p,l. express-
ing P.n = f{p, Xu), and elimin ating term ~ by use of the Gibbs- Duhem
8.4 Solubility of Small Particles 181
Fig. 8.9 Pressure of B in the vapor phase and gas phase of spherica l particle and particle
with an infinite radius of curvature.
under the constraint of total constant volume, the Helmholtz free energy F
will be a minimum, and hence at constant ~emperature
dF=-d W=O (8.23.)
After the process is complete the vapor phase will have undergone a volume
change dVg and the particle at pressure p.. will have undergone a volume
change dVn . Jn audition the clement of area dA has changed by d(dA). The
volume change of vapor and particle results in work, dW, of p,' dVg and
p, dVB, respectively. The area change of the particle results in work, dJV,
equal to -u d(dA) . The total work wi ll be the sum of these terms. Suhstitution
in equation 8.23 gives
- p/ dV 11 - Pr c/VJI + CT d(dA) = 0 (8.24)
T he rela tion between the area cha nge a nd dn is
d(dA ) = -2 dA · d 11
r
However, dA · d11 = dVu; hence
1 2a
Pr - Pr = - (8.25)
r
F rom eq ua tion 8.25 we see that when r = oo,
I
Poo = Pc.o
and hence
I
Pr = P<n
I nsert ion into equation 8.25 yields
. II
2a
Pr - Poo = - ,. I
dp. = vu· dp
We find
(8.26)
aoo = l = Y n ox«IH!<nU
RT In a = 2 avo· .J
r
r
.I
8.4 Solubility of Small Particles 18J
and thus
ln (X~<a"u),. = 2uVn.
X Blllntl T Rr
The quantity Va· = M / p, and
12.0
10.0
8.0
4.0 \ \
I
2.0 ~ - .... -
1.0 1 - - -- - - - -1- ·- - - ..
00 10 20 30 40 50 60
Particle rad1us, r (angstroms)
Fig. 8.11 Solubility of small particles of Bin ex solid solut ion compared to t he solubiliLy
of very large particles.
184 Phas('S o f Vnrial>lc 'umpus il iuu
In Section 8.2 the solubi li ty of' a solu te terminal solid solution was l,;( lll -
sidered for constitu ents which form a simple eutectic diagram. Since the
relative partial molar enth alpy of a solute is general ly positive, the solubility
was shown to increase experimentally with tempera ture. In this section , let .'
us consider th at part of the phase above the eutectic tempera ture. Conside r
th e equili brium between rx phase and liquid for a system such as illustrated
in Fig. 8.6. Just belo w the melting poi.nt of pure A , dilute rx is in equftibrium
with liquid alloy. Therefo re
t
,u II CRt~L) = 1-" ll (fii\L )
Gr
Since
or
RT ln X~tsnt> = -(~fiu~a- 6.fi0 ') + T 6Snxs + L1 (l- _I_)
Tm.p.
(8.29)
X B(icnl )
The term X~(sllt) / X[1<w> is referred to as the ,\'('Kregation constant. For a
eutectic diagram x~(sat) increases strongly as the temperature is lowered
from the meJting point of A. As a consequence of equation 8.29, X~<snt)
will also increase slrongly as Tis lowered, until the eutectic temperature is
reached. Below the eutectic point, the equation developed previously for
sol id phase equilibria holds. A s a consequence, the maximum solubility
most often occurs at the eutectic temperature. In certain cases, however, a
pronounced maximum occurs at a temperature near the melting point of the
solvent. An example is shown in Fig. 8.12 for the Si- Cu system. This phenom-
enon is called retrograde solubility and is quite common in semiconductor
base systems. In the Si- Cu system, for example, the maximum solubility of
Cu in solid silicon is about 30 limes higher than the solubility at the eutectic
temperature. The key to the existence of th is type of solubil ity is due to the
magnitude of /18 8 4 which can be very large in semiconductors such as Ge
and Si. Figure 8. 13 shows solvus lines calculated for various values of
(6. fl 11« - l1fl 8 ') with the simplifyin g assump tion that llSuxa is zero.
It is observed that the tendency toward retrograd e soluhility is directly
related to the difference relati ve partial molar enthalpics of solute in solid,
1
solvent and liquid . Curve (d) for example, for which (llfiu«- 8.11" ) is
relatively low, shows no tendency toward retrograde solubility, but, as
(6fln«- 6fi 11 ') is increased, the tendency toward retrograde solu bility is
also increased. If the solute has a low melting point, L 10 will not appear in
equation 8.29, and thus retrograde solubility will occur for mucll lower
values of 6H1 ,~~.. The reason why retrograde solubility is not observed in
most metallic systems is that 6R11« is too low. From our earlier discussions,
it may be seen that a large value of 6Fi Btr is associated with a low solubility
186 Phases of Variable 'omposition
1800
eul i
1700
1600
liq.
I
v I
V"
r--
_L
~
Uq. I 0
52 1500 _,_ -- --
t_.
tU
:;
~ 1400
Cll
c.
E
\\ t-
a
Cll
.... 1300 - t-- - - 1- ... 1- -
1200 --
11 00 .
\.
1000
' '...,
1.0 w-• w- 2 10-:1 10 -" 10-r. 10- 6 10- 7
Cu. atom1c l racllon
Fig. 8. 12 Phase diagram for the Si- Cu system shov.ing rctmgrauc so lubility. From C. 0 .
Thurmond and J . D. Strut hcrc;, J. Phys. Clll'm., 57, 83 1 (1953).
( I
8.6 SOLUOlLITY Of A METASTAULE PI-lASE
1250
v - v -v v --- v --
B-Ge
~
1200
Liquid
1150 I I I
1100
juq.+a( I I I
- I
-
=-::
•
2
~
~
1050 J Ie d c b
~
-a\
~ 1000
....
Ql
950 1-
,\
900
\
850
\
800
1.0 10 - 1 10 - 2 10 - 3
i\ \
10 - .c 10 - 6 10 - s 10 - 1
B. atomic fracllon
Fig. 8.13 Solvus lines calculated fro m equa tion 8.29 for various values of (a l711"'-
6.8 8 '). Curve a, +92 kJf mol; b, +69.5 kJ/ mol; c, +46 kJ / mol; d, +23 kJ/ mol;e,liquidus.
From C. D. Thurmond and J. D . Struthers, J. Pltys. Chem., 57, 83 1 (1953).
A
Xa-
or phase boun darie s imo metas table regi on~.
Fig. 8. 14 Phase diagr am showing exten sions
PRO ULE MS
at % A and cornp onl.!nl A
1. At a given lempr..!rature, component B llisso l v~.:s 0. 7
ts o f U in A and A in B.
disso lves 1.2 at % B. Calculate the activ ity coefficien
No inter media te phases exi t in the binar y system.
com pone nt B ~ till
2. The temperatu re in Problem 10. 1 ic; 5001) K. /\L 700° K .
ll (a) Cc.tlt:ulal.; Lhc n.:l;al ivc
disso lves only 0.7 at % A but A disso lve-; 2.4 :tl "~
B. (b) Cuku lale the cxces"
parti al mola l entha lpy of B in A and also of A in
o f A in 13.
relat ive parti al mola r entropies of B in A and also
of vacuum tubes is the
3 An impo rtant reaction involved in lhe oper ation I ,
follo wi ng
Ba (g)
y BaO {.~) + x M ( XM, s) = M:x:0 11 (solid or gas) +!I
in the base nickel cathode.
where M is an oxide -form ing solut e disso lved
0.0 1% and M.,..0 11 i COt(,f).
Calculate P 11 " in equil ibdu m at I 175° K if M is Cat
C is soluble to the extent of 0.1 % in M .
,......... .__..__ ......... , _ --- - ·-
189
Problems
the «
4. The phase diagra m for the A- B system shows retrog rade solubil ity in
r solutio ns
solutio n po rtion of the diagram . Both « and liquid behave as regula
is 6000
with 6B8 equal to 3250 Jfmo l in the liquid. The heat of fusi o n of B
ively.
J/mol, a nd the meltin g points of A and Bare l000° K and l200° K, respect
ate the
(a) Calcu late the minim um possib le value of 6R 0 a in «. (b) Calcul
temper ature where the solubility of B in ex is a maxim um.
9
i I
Free Ener gy of I
i
( I
I I
In the las t chn plcr some s pccia I cases were co nsidcrcu for which qua nli tali vc
thermody namic data could be obtai ned strictly from phase uiagrams. It is
the purpose of this chapter to examine the relation between thermody na mic
quantities and phase diagrams from a more general point of view. Generally
speaking, we shall not be able to ohlain q uantitative results bul i~t~porta n l
semiquantitative ded uclions may o ften result
First, Jet us examine lhe general shape of a free energy versus composit ion
curve for a general solution, in the vicinity of ei ther end of a bi nary system.
The free energy of mixing at some particular composi tion will be given by
the equation f I
\
WHE RE
9.2 FREE ENERGY VERSUS COM POSI TION FOR CASE
A AND B HAVE THE SAME CRYSTAL STRUCTU RE
nuous
In this situat ion it is theore tically possible for A and B to form a conti
ure. A
solid soluti on since both comp onents have the same crystal struct
ures a con-
little renec tion will show that if A and 13 have differ ent struct
tinuo us soluti on is impossible. We know that
!:::..G, = !:::..Hm- T !:::..Sm
1
X will he
at a given tempe rature . If 6.H 111 is negative, 6G,11 as a funct ion of 11
These terms
negative at all comp ositio ns, since - T 6.S111 is alway s negative.
situat ion
are show n in Fig. 9. 1. If, on the other hand, 6.Hm is positi ve , the
ositio n
becomes more complicated . The shape of the free energ y versus comp
ratures, the
curve may. chang e stron gly with tempe rature . At high tempe
Xa -
e.
Fig. 9.1 Free energy versus composition for a solutio n when tlHm is negativ
192 Free l ~ IICI'J.!Y uf Uiuary Sys ll'lllS
c
AL-~a~--------L_~~--~----~----~__J s
Xa - -
9.2 Free energy versus compositiC.Hl for a solution when ~H 111 is a large posili\'C 'aluc.
Fi~.
From L. S. Darken and R. W. Gurry, Physical Chemistry of /llern/s, M cGraw- H ill, New
York, 1953.
(e - x ) (x - cl)
D.G m =
(e - d)
B + (e - d)
C = D
9.2 Free Energy Versus Composition 193
The value of Dis lower than A, the in itial va lue of tl.G, before dissociation,
but llG 111 will be lowered still further by making the solutio n of composi tio n
d richer in compo nent A and the solution of compo sition e richer in com-
ponent B. The lowest stable value of tlG rn which can be attained by the
decomposition is G at compositio ns y and z, respectively. These solutio ns
a re in equilib rium with one anothe r si nce compo nent B wo uld have the
same chemical potential in both. It is import ant to note that compositions
y and z are not necessa rily associated with the minima of the tlG ,.1 versus
X 11 curve. The free energie s at £ and F may he considerahly different from
the minimum values, since the importunt cri terion l'o r ClJ Uilib ri um is that the
chemical potential of a given component is the same in both phases, not
that the free energy of each phase be a minimum. This criterion obvio usly
cannot be met by drawin g tangents at the minim um va lues of the 6.Gm
I versus X 11 curve unless they happen to coincide at the same 6.G,. val ues.
Th us solutions to the left and the ri ght of y and z, respectively, a re stable,
whereas solutio ns of composition y and z are unstable and will dissociate
·t
I
iQto two coexisting phases . Such a free energy curve is associated wi th a
miscibility gap oo a phase diagram . At higher tcmpe ratu rcs the minima move
closer together in composition and finally disappea r completely at a critical
temper ature, Tc. The type of phase diagram associated with Fig. 9.2 is shown
in Fig. 9.3. At temper ature T2 , the free energy ve rsus compositio n diagram
would be similar to that shown in Pig. 9.2. In connect ion with Fig. 9.2 it will
be observed that two inflecti on points exist betwee n y a nd z. Such an
inflectio n poi nt is called a spinode and plays a n impo rtant role in the kinetics
of phnse decomposition, as shall he tliscussctllal cr. The spi nodal compol)ilions
l' are illustrated in Fig. 9.3.
Let us now conside r the activity of compo nents A and B associated with
.I
..
the free energy ~ ur ve shown in Fig. 9.2. Considering compo nent B as an
example we may find (Jtn - p. 11 ") at any composition by extrapolating the
slope of the curve at that composition to X 11 = I. The value of aH may
readily be obtained since
/tu - #u· = R!. In On
As deri ved from Fig. 9.2, the curve of a 11 vers us X 11 is shown in Fig. 9.4. At
.f the compo sitions y and z, component B will have the same activity acco rding
to the require ment for equilibrium. The maximum and minimum in au
correspond to the spinodal points of the ~G,. versus Xu diagram. It may be
shown that the areas of the shaded portions are cq ual.
Let us now consider the phase diagram shown in Fig. 9.3 at temperature
T 1• The situation is somewhat more complicated, since T 1 is above the
melting point of compo nent B, and therefo re the standa rd state of com-
ponent B has changed from solid B to Liq uid B. It is impossible to have a
f ree Energy of Binary y~ l c ms
a
t
'1'
A B
Fig. 9.J Phase diagram showmg a miscibility gap. At T2 free energy d iagram is ghcn by
Fig. 9.2. Dashed line shows spinodal cornposition'i. ..
continuous free energy curve bel ween solid and liquid solutio ns and tltcrcro 1c
two curves will be needed; o ne for the soltd solution and one for th e liqu id
solution, as shown sch~m a tica lly in Fig. 9.5. At pure component B, the solid
curve intersects the free energy axis at a poi nt equal to the negative of the
free energy of fusio n for compo nent U. This point represents the free cucrgy
of formati o n of solid B from liquid B. D.G ,,, fo r liquid B is equal lo ze ro since
this is the standard state. Similarly , the liquid curve intersects the free energy
axis at a point higher th an zero fo r pure A since !lG,, for solid A is tcro at
T 1• It is appuren l rrom free energy consideratio ns that when X 11 < X11" on
.,/
t Stable configuratron
Two solutions
I
I'
I
""' I'
'-t- Raoult's law lrne I
I
I Iz
.Y
Fig. 9.4 Ac tivity of componen t B a t tempera t ure T2 for solution o f Fig. 9 .3. Fro m L. S.
Darken and R. W. Gurry, Physical ChemiJ·try of Metals, McGraw-Hill, New Yo rk, 1953.
9.2 Free Energy Versus Composition 195
---
Fig. 9.5 Free energy of solid and liquid solutions corresponding to temperature T1 on the
phase diagram of Fig. 9.3.
Fig. 9.5, the solid solution is stable and when Xn' <Xu <Xu', two phases
will coexist, ex solid phase of composition X 11', and liquid phase of Xu'·
When Xn >Xu', liquid sol uti on is stable.
The value of (}tn'- p. 0") and (p.A'- p,11 ·) may be readily estimated at
any temperature . For compo nent B at the melting point
B(l) = B(s) D.G = - 6.G1 = - (t.t 11 " - !'H.)= - D.L, ( I - T ..,.,•.,,7 '1)
r·
At a temperature above the melting point of componen t A, bqth liquid A
and B are stable and the !::..G"' versus Xu diagrams for liquid and solid
solutions are shown in Fig. 9.6.
- - - -,----
........ .......
Fig. 9.6 Free energy of solid and liquid solutions corresponding to a temperature abO\'C
Tm.p. of component A of Fig. 9.3.
The crilicnl tem perature , '/ ~. :assm: i:11cd with tl1 c 111 iscih ili ty gap <lr 1l1c
phase diagram of Fig. 9.3, is largely determined by the magnitude of Lhc
heal of mixing. For purpose of illustration, let us conc;ider a miscibility gap
for a regular sol ution , because of ease of calculatio n fo r this type of system.
For such a system
and (9.5)
6.G,. = nxAxlJ + RT(X,, In X .\ + Xu In XII) J
'
~
,. _ ()6.1~ ~ ILL - z.n.:I. )l,l• ,. 111_ ,"""
. ""
2!L.
Let us calculate t e maximum critical tempcra t~fe. Tr, where decomposit ion
1
J
will occur, and the composition of the sol ution X 11 r al this Lc111pcraturc .
These points are shown on Fig. 9.J. Above the tempera tu re T,.• the curve of J
!1G,, ve rsus X 11 is everywhere c onca ve d ow nward . Below ll lis lclllj)cralurc.
two minima will occur, as already discussed , and there will be two infleclion
points where
2
a
( ax1:1.c ,.) = 0
u:.!
As the temperature is raised toward Tc• the minima will move closer together
in composition and as a result so will the inncclion points. 1\t 7~. both
9.2 Free Energy Versu s Composition J97
minima and the inflection points will coincide at the same temperature.
'l equal
Thus T, is the temperature where both CJ 6.G ,,/CJX 11 and 0 tl.G,J oX 11
2
find
zero at the critical composition X uc· Performing these operations we
~ to he
From equation 9.6 we see that U must be positive in on.Jcr fo r '/
position
positive. Further, Xu~" is such that Tr is the maximum decom
that
temperature associated with the miscibility gap. The value of Xn'
make s T, a maximum in equation 9.6 is X ue = 0.5. Thus
T
c
=~
2R
(9.7)
ive
Accordin g to quasichemical theory, a positive va lue of !1 indica tes a repuls
larger
interaction between unlike components. Thus from equation 9.7, the
decom -
this repulsive interaction, the higher the tempe rature will be where
systems
position begins. As a generalization , we might say that virtually aJI
found
with a positive tl./1, should show a miscibility gap. This is not
is
experimentally. The rcHso n for this lack of agreement with expectation
be so
often related to the fact that unless l:lH,n is sulliciently large, T, will
tesimal,
low that the kinetics of the decomposition in the solid state will be infini
table.
and at low temperatures a solid solution will usuall y exist which is metas
phase
Because of the slow rate of diiTusion at low tcmperatur~s, most
diagrams are not accu rate in the low-tempe rature region .
From an experimental point of view, the curve of 1:1G m versus X
may
I
tem-
usually be determ ined onlY. for those phases that are stable at a given
in the
perature. As a consequence the exact shape and posi tion of spinodes
cases,
metas table regio n can be evaluated only by conjecture . Jn some
been
however, measurements may be made on metas table alloys which have
on are
quenched to some lower temperature where kineti cs of decompositi
interest.
sluggish. These results are then extrapolated to the temperature of
I.
,.
9.3 FREE ENER GY vgRS US CO MPO S IT ION FOR CASE
WH ERE COM P ONEN TS A AN O 8 H AVE OI FFER ENT
CRYS TAL STRU CTUR ES
this
A typical D.G,, versus composition diagram is shown in Fig. 9.7. On
terminal
diagram the b.G..,, versus composition cu~ve s are show n for the two
198 Free 1-:ucr~;y or Ulnary SystcmJ
·'
to~~~~~~~~
J<l
Fig. 9.7 Free energy or solid phnscs having c.J ilfcrcnt crystul sll uctu rcs.
of the diagram , it is clear that when a < Xu < h, the situation yielding the !
most nega ti ve val ue of /:lG"' is a coexistence o f a. and J' phases. For fJ to be
present in this range, the /:lGm curve for the intermediate phase m'ust be
lower than the dashed line representing the equilibrium composition of a. in
equilibrium with the equilibrium composition o f y. Such a situation is shown 1 I
in Fig. 9.8. From examination of the diagram it can be seen that when
I
Fig. 9.8 Free energy versus cOmposition diagram showing intermed iate phase.
~
I I I
I I I
0 I I I
0 1.0
Xa -
Fia. 9.9 Ac1ivi1y of componenls A and Bversus composil ion for F/
200 Free Energy of Uinary Systems
Liquid
•
·i
0 1.0
Xa - l
Fig. 9.10 Phase diagram corresponding to free energy versus composition diagram of
Fig. 9.8. "
or
_ J [(1 - X~(Hat)) flG/ J (9.10)
YB 0 - exp
XiHIIn t) (b - x~\(H&t)}RT
e and the inter-
Thus by knowi ng the comp ositio n of the satur ated ex phas
e, the activity
medi ate phas e, as well as flG/ for form ation of this phas
the free energy
coefficient Yn° in ex may be evalu ated. Very often , howe ver,
heat of form ation ,
of form ation of inter medi ate phase s is not avai lable . The
to obta in . Thus we
however, may have been evalu ated si nce it is oflen easier
may estim ate that 6.0/ ~ flH1°. Supp ose now that the fJ
phas e exists in a
of this struc ture
meta stabl e crystal struc ture. The free energ y of form ati on
stabl e struc ture.
will be more positive than the co rresp ondin g value for the
it woul d he more
This is true, of cours e, since if flG/ were more negat ive
s will become
stable. As a result the comm o n tange nt to the ex and {3 phase
large r, indicating ,
more horiz ontal and the comp osilio n Xjj(,.at.l wi ll beco me
e phase is always
as discussed in Chap ter 8, that the solubility of a meta stabl
higher than the solub ility of a stabl e phase.
da ta exist.
For some inter medi ate phases consi derab le therm odyn amic
react ion of meta l
Ther mody nami c data in the case of comp ound s fo und by
from equi li brati on
and gas may be readi ly obtai ned from emf meas urem ents or
6;~,
(f OIS UeHC _l ~\
202 Free Energy ur Uinury Systems
1 1
with a gas phase. For an oxide, for example, the compound may be eq uili- '
bra ted directly with p.,,. or if the ClJ Uili hrium ~;due of f'u 2 is too low ..ratios of 1
p 11 , o/p 11 2 or /'cn,//'c ·t,, may be employed. l·or a ny of these rcact1 nns the
value o f p(11 in equilibrium with the crys tal ma y be readil y c.lctcrm incJ a nd f
consequently the value of the chemical potentia l of 0 in the crystal relati ve
to l-'o,0 in the gas phase may be determined by the relation 1 t
(U 0 •7 Pu 0 .3)0 2+x, as determ ined from emf measure men ts. T his phase JS
1 I I
---
170
0
160
150
0
r--
~~~~ - -- -- - -It>
~
;---
~~~
"'1:
K~
(
140 ~ ·--- -- --
_...
«!
~ 130
~'
_...
('0
Q 120
Cl.
..= o 8oo· K
~ 110 c. 950•K
u ~
~ o t too·K
~ 100 -- -- -- -- - - - - --- - -- - -
II I )
.......
-
('0
0 90
C!>
<] I '
I 80
70
~
60
50
\: t-- ,1....
~ ~1-6..
ru'"
40 1-o-
1.86 1.88 1.90 1.92 1.94 1.96 1.98 2.00 2.02 2.04 2.06
Oxygen/metal ratio
Fig. 9. 11 Rela tive pa rtial mola r free energy of oxygen as a func lion of compo ition for the
phase ( U 0 . 7 Pu0 . 3 )02+x· 0 / M = R a tio of concentra tion of oxygen to sum of concentration
of U and Pu. From M . H . Ra nd a nd L. F. J. Roberts, in Thermodynamics, Vol. I, I.A.E.A .,
Vienna , 1966.
9.3 Free Energy Versus Comsx>sition 203
Or---------~--------~----------~---------r--------~
Uranium
valency
l'o,- lo - 3
co -
Fig. 9.12 Relative partial molar free energy of oxygen as a function of temperature and
compositio n for (U0 . 86 Pu0 _16)02+ x · FromM . H . Rand and T . L. Markin, in Thermodynam-
ics of Nuclea r Materials, l.A .E.A., Vienna, 1967.
the curve, no oxidation will occ ur. 1n a reacto r, for exa mple, in which the
(U, Pu)02 +x fuel is enclosed in stainless steel materia l, a phase with a high
0 / M (large value of X) ratio must be employed . As an interestin g aside,
this compound is in equilibrium with several gaseous species at elevated
temperatures. The value of 6C 0 , in the solid phase will alrcct the cquilibriulll
concentration of the various gaseous species. The calculated va lues of the
partial pressures of some of these gaseous species as a function of the 0 / M
ratio were shown in Fig. 4 .9.
In so me binary systems a large number of intermediate phases may exist
at vuriuus COIIlJH>sitions. I :ig urc <). I J shows u plot of'L\.(7 111 vcssus collt:C IIIrulioll
for the Ti- 0 and V- 0 systems. The horizontal lines represent the two phase
fields and tbc seeming discontinuities represent the rapid chan ge in chemi cal
p o tential across very narrow single-phase fields. A simila r plot is shown in
Fig. 9.14 for manganese oxides. The oxygen pa rtia l pressure in the range
-"
" - - Two- phase region
--,tv-Ti203 - - - Single-phase region 150
II J'- 'l'iaOu
-30 _ I _ _ ,1 - ~l'i,O,
I TisO!I
I L.....; TiGOu
I ~Ti7013 -
_ I [::' -;rillYHi
I I
I
I TIO
I - 100
1
I V203 2
- 20 - II I ..-.
N
I 0
J/ I t 0
Ill)
I E
.Q I _y1--V305 ::::::-
RI
~v.o7 ..¥
u
~V6011
0
...
~V;013 (.:>
Vs016 <1
- 10
- 50
I
I
1
vo2
I
-
V20s
v GJ13? V3l7?
0 0
1.5 2.0 2.5
OxyEen to metal ratio (X)
Fig. 9.13 Variation of 6G0 , and log p 0 , with composition for titanium oxides and vana-
dium Q)Udes. From T. B. Reed, in The Chemistry of £:<tended Defects ;, Non-Metallic
Materials, L. R. Eyring and M. O'Keefe, Eds., North ~Ho lland, Amsterdam , 1970.
I
.I
'( 9.4 Calculation of Phase Diagrams 205
l -40
- [ - Two-phase region
--;- - Single- phase reg ton
- 150
I -30
; .: -
I
1 I
I
.I ...-20
-Iu,m,a
CO/C02
IMnO
I
- 100 ';I
0
-
I 0
I ~ E
/ ~
. --
1:
- - 50
I ii
~
;~MnJO•I
I -~-
-1 0 0'
:: ~
I {)
<l
IMn203
>-Io;rect 0
''·I
0 control
I
I
.:
,,
I
I
I Mn02
••' "
! -1 0
:; '• "~ .~ - 50
0 0.5 1.0 1.5 2.0 2.5
'~ Oxygen to metal ratio ( X)
I for manga nese oxides. From
·\ Fig. 9.14 Variat io n of 6 G 0 , and log p 0 2 with composition
etallic Ma terials, L. H. . Eyring
T . H. Reed in The Chemistry of £xtemletl V cfects in Non-M
.f and M. 0' Keefe, Eds., Norlh- Holland, Amsterdam, 1970.
Fig. 9.15 Free energy for solid and liqu id solutions below the melting point of component
A but above the melting point of component B.
(9.l3)
(9. 14)
T
t l
I
I
t
\
A B
Xa-
Fig. 9.16 Phase diagram for case where A and B form ideal solutions in both liquid and
solid states.
calcu lated the Ji4ui<.lus and so lidus cu rves for the ge rman ium- s ili co n bina ry
~ystcm and finds ,·cry d <,sc agr<.'Cilll'lll with experimental curves. A s a result.
'''"''I(
1\.11\ \ '"'' ~'" '' ~'· '" ''~" :11\\ d ·\\ :1. ,,t,l,· "' ,.,,,"."'"'' ch,\1 •: ' t lll:ll 1i um anJ
1\11111 "~''") ttknt M 1 h111 1 1 1\~. 11 11'> d tag iHIIl is sit''"'" i 11• l 'ig. 9. 17.
;,Ill\ 1111
One may extend this approach in order to treat a wide variety of systems.
For ex~mpJe, suppose two elements A and B have c rystal s tructures <l and {3,
respecttvely. In order to calculate the phase diagram, the free energy o f
1
C. D. Thurmond, J. £/ectrochem . Soc., 51, 821 (1953). tt
I
I
9.4 Culculalion of Phase Oiat;rnms 209
1750
1700
Ge-Si
A d
1650
/
'j"'
v
-- -- -
7
/
1600
0 1-
~
l-/
1550
v: ~/
---
7
.-1500
~
::.:::-
<U
~..... 1450
v:
v, 1/
I
~
~
I
I
<U
0. j
E
~ 1400 ~
I
I
1350
I
I
L
I/ /~
I I
f Lv
1300
1250
1200
v /
1100
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Si, atomic fraction
Fig. 9.17 Phase diagram fo r the nearly ideal Ge-Si system . Solid line, experimental;
dashed line, calculated . From C. D. Thurmond, J . Electrochem. S oc., 51 , 827 (1 953).
r
210 Free Energy of Binary Systems
Group number
4 5 6 7 8 9 10 11 12
+ 2000 1.00
(\ ... - 1\ JI
...1
v . ,·'
,'
'1'
E'
+ 1500
I I
I \
\
0.75
-•
:::.::
•'
2IU
r--lI I \
- \ E
~ + 1000 ~ a s fJ+E ~ 0.50 2ro •
],
~
cu
u
.... + 500
--
-\ ' /
(right scale)
1\
\
0.25
-~
cu
u
I
bO
n;
l
,.
I
I
~
-o A c:
....
(II
(II
:::: 1
>-
a.
IU 0 /\ l 0
-o
>-
.'
-:
..c
c:
cu t-
I
\ \
\
a.
E
c
I (II
""'
fQ.
::t: -500 - f- /
~--(left
AH8+• -
\ - 0.25 .;{- •
I I scale) \
- - 1- - -- ----- V- (I)
II
•
- 1000
I
1
I
\ /
L ~~
\
- 0.50
...I
(I)
'il
J 0
-/- '
-1500
_... / 1
I
- - - "'-v - 0.75
I
.!
Zr Nb Mo Tc nu lUt Pd Ag Cd j'
Hf Ta W Re Os lr Pt. Au
Fig. 9.18 Calculated enthalpy a nd entropy differences between h .c.p. (E) and b.c.c. ({J)
forms of the transition metals. From L. Kaufma n and H. Bernstein, Compwer Calculations
ofPirase Diagrams, Academic Press, New York, 1970.
mation for many elements has been calculated. In Fig. 9.18 is shown, for }
transition metals, the calculated enthalpy a nd entropy dirference betwee n
the hcp and bee forms.
9.5
l
R ELATION S BETWEEN PHAS I~ OIAG I( AMS
OF DIFFEIU~ NT TYPES I )
Superficially there does not seem to be much simila rity between , say, a
phase diagram for which both elements are miscible in a ll proportions and
1 1.• Kaurmun nml II . llcrustcin, Camputu ralcult~timi of 1'/m.\£' Diagrams, Academic
.·•'
l'rcl>S, N ew Yurk, Lo11don, 1970.
9.5 Relation lktwccn Phase Diagrums 211
x, -
Fig. 9.19 Free energy diagrams of liquid and solid solutions at temperature T 1 below
melting points of A and B ; llHm' more negative than l::lHm'·
1+ Xu- c
£ 0 !..--J..----.:;:..___ ___:;:..___ _____;r -- --Fr---.1
0
~ -
Fig. 9.20 Free energy diagrams of liquid and solid solutions at tempera ture T2 above the
melting points of both components.
.. ...~
••
t
T
I f
r, -- - - - - - - .. - - - - - - -
A
x,- 8
Fig. 9.21 Phase diagram corresponding to free energy curves of Figs. 9 .l9 and 9.20.
1
Let us now consider the case of a positive value of the heat of mixing 1
with 6.H"' for the solid solution being more positive than that for the liquid.
Above the melting point of either component the 6.G"' versus Xu diagram
may appear as shown in Fig. 9.22. Al some temperature T 2 below the
~ I
( ,
x,, - ( I
~ ..
Fig. 9.22 Free energy diagrams of liquid and solid solutions at temperature T 1 above the
melting points of both components; 6.Hm 4 > H ,,. l > 0.
213
9.5 Relat ion Between Phas e Diag rams
t
J<l
ar as shown tn
melting poin t of the compone nts, the curves would appe
Fig. 9.23.
The mos t stable si tuati on at vario us com posi tions is
(a) X n < a, solid solution is sta ble
(b) a < Xn < b, solid and liquj d coexist
(c) b < X 11 < c, liquid solution is stable
(d) c < Xu < d , solid and liquid coex ist
(e) Xn > d, solid solution is stab le
This gives rise to a melting poin~ minimum . At a lowe
r temperature, T3 , the
situation may be as shown in Fig. 9.24.
phase diagra m
I I At th is temperature a miscibility gap will result. The
where Figs. 9.22,
associated with this type of system is shown in Fig. 9.25,
ctively. If a case is
9.23, and 9.24 are associated with T 1, T2 , and T 3 , respe
than in the former
considered for which the heat of mixing is more positive
re and the cri tical
case, the melting poin t minimum is reduced in temperatu
they overlap. When
temperatu re for the miscibiJity gap is raised until finally
this occurs a simple eutec tic will result.
is shown in Fig.
This grada tion between va rious types of phase uiagrams
solu£ion. If the heat
9.26. Figu re 9.26a shows a phase diagram for a n ideal
but tllim' > llH'"t'
of mixing in the solid and liquid solut ions is positive
the melti ng poin t
the critical temperature for the miscibility gap is raised and
\'.) )
te +
0
Xa~
~ I)
<2-
Fig. 9.24 Free energy diagrams of liquid and solid solutions at temperature T 8 below T2 •
T, ____ ___ _ l'9_U~- -------
1
T a
Ta - - - - -
A B
Xa-
Fig. 9.25 Phase djagram corresponding to Figs. 9.22, 9.23, and 9.24.
Liquid Liquid
• I )
t
T
• I
a ' + a" I
• I
8 A 8
Xa~ Xa ~
() )
Xa~
214
9.6 Nonuniform System s
215
ant eutec tic
minim um is lower ed until finally they overl ap, with the result
will result in
phase diagr am show n in Fig. 9.26c . A furthe r increa se in 6.Hm
a larger two-p hase regio n (oc + oc') and thus more narro w termi
nal soluti on
region s.
is show n
The oppos ite situat ion, for which the heat of mixin g is negat ive,
is negative
in Fig. 9.27. [f the heat of mixin g for liquid and solid soluti ons
um will
but 6.J/m' is more nega tive than 6.H.,.,.', a melti ng point maxim
to order so
result. Furth er, at low tempe rature s, the solid solu ti on will tend
Liquid LiQUid
T
t
A B A B A B
Xa~ Xa~ Xa -
(a} (b) (c)
a nt phase
as to maxim ize the numb er of unlik e pairs in soluti on. The result
negative, the
diagra m is show n in Fig. 9.276. As 6.H,' becom es more
the numb er
tendency for order ing in the solid soluti on i 11 order to maxim ize
phase would
of unlike pairs will be increa sed. Ultim ately an interm ediate
t phases.
result which would have a crysta l struct ure differ ent from the paren
unlike pairs
This struct ure wou ld be such as to maxim ize the numb er of
tend to be
and minim ize their distan ce of separ ation . Such a phase wou ld
would be
stable and hence would have a high meltin g point . In a sense , this
similar to the critica l tempe rature for order ing being increased.
U this phase
maxim um
were suffic iently stable , its meltin g point would be highe r than the
type show n
of the liquid us and solidu s result ing in a phase diagr am of the
in Fig. 9.27c.
where
(9.16)
In 9.15 and 9.16 y represents distance and the subscript i,j refers to x, y,
and z components. For an isotropic structure
K tul
J -
- K 1--
.·
2!7
9.6 Nonunifor m Systems
where
dK1
K= - - + K 2
dXn
9.19 Jet us assu me that
In orde r to exam ine som e prop ertie s of equa tion
that
sinu soid al ftuctu!ltions in com posi tion occu r so
X- X 0 =A cos {Jy (9.20)
conv enie nce. For
whe re A << X 0 and the subs crip t B has been drop ped for
small amp litud es / 0 may be expa nded
.Xo 1 Xo
and
AF = AzV ( o:fo 2 + 2K{J2) (9.21)
4 oX 8
is nega tive in sign , the free
From 9.21 , we see that if the term in pare ntheses
is lowe r than that for the
energy of the syste m cont aini ng the fluc tuati on
on wi th wav elen gth ..t =
unif orm system. Und er this cond ition a fluct uati
n (o2fo foX8 2) > 0,
21r/P is stab le. Upo n subs titut ion one may obse rve that whe
the unifo rm sol utio n is stab le, whe reas whe n (o2f0
/oX0 2) < 0, the system is
..tc whe re
stab le for all fluct uatio n of wav elen gth larg er than
(9.22)
'
1"" - - --r
-- I
'I
I
A B
(b)
(c)
Fig. 9.28 (a) Free energy versus compositio n diagram for case where l:i Hm > 0. (b) First
derivative of (a) as a funct ion of composition. (c) Second derivative of (a) as a function of
compositio n.
(9.23)
where Y and p are Young's modulus and Poisson's ratio, respectively. The
term N is given by
V = V0 [1 + 3N(X- X 0 )]
and is the linear expansion per unit composition change.
Problems 2 19
PROBLE MS
1. Componen ts A and B form a regular solu tion in the solid state for which
ll.Hm is 20,000X,..Xu 1/mo l. At a temperatu re of 1000° K, calculate the com-
position of r:~.' and r:~." in equilibrium and the compositi on of the inflection
points.
2. For the problem above calculate the temperatu re for immiscibility for a solution
in which Xu = 0.3.
3. Draw schematic ally free energy versus compositi on diagrams for the Ag- Pt
peritectic diagram at T = 1300°C, I 100°C, and 900°C.
4. Componen ts A and B have melting temperatu res of l000° K and 900° K,
respectively. Regula r solutions fo rm with ll.Hrn equal to (20,000/ T)XaXu and
(200,000/T)XAXn J/mol in the liquid and solid states, respectively. The
enthalpies of fusion are 6000 Jfmol and 5200 1/ mol for A and B. respect ively.
(a) Will a minimum occur in the solidus and liquidus 1 (b) lf so, calculate the
temperatu re of the minimum.
5. The distributio n constant which is equal to X t..'IX8 ' is of considerab le impor-
tance in the zone-refining operation. Consider that the liquid solution fo rms a
<<
regular solu tion and that X 11 11 X 11 1 ncar Lhc mclling point of componcn l A.
Near the melting point of A k -+ k , a constant. Deten:nine the dependenc e
0
of k 0 on 6.Hm • and 6.Hn'· ~hat thermodyn amic properties should the solute
have in order to make the zone-refining operation easy 7
6. Draw a phase diagram for which 11H,.' < 6.H m' < 0 but where tl /1 m' is less
than that shown in Fig. 9.27b but more than that shown in Fig. 9.27c.
...
10
Thermodynami cs of Surfaces
and Interfaces
I
Consider a planar interface between pure phases ex and {J. This interface
is characterized by a surface tension a expressed in te rms of force per unit
length. The interface is a site of disturbance on an atomic scale , since the
)
environment of atoms at the interface is not regular as it is in the interior
of the phase. As a result, to increase the a rea of an interface, wo rk musl be
expended by the system. In C hapter 2 this work was fo und to be given by
dW = -qdA ( I 0.1)
Consequently
dW
a=-
dA
The surface tension o r surface work a is the reversible work needed to
create a unit area of surface under co nditi ons of co nstant temperature and
220
221
10.1 Surf ace Tension and Surf ace E nerg y
hat con fusi ng whe n one is con-
volu me. The term surf ace tens ion is so mew
the exis tenc e of a stre ss. The term
cern ed abo ut solid bodies sinc e it implies
scie ntis ts who wor k wit h liqu ids.
tension arises principally from usa ge by
of stre tching the surf ace , whe reas
For liqu ids the app lica ble pro cess is one
ing the surf ace . The read er may
for solids u is related to wor k spe nt in f orm
fo r exa mpl e, the spre adin g of a
readily visua lize the difference. Con side r,
ord er to incr ease its surf ace area .
dro plet of liquid necessar y und er stre ss in
readily mov e from the interior
Because of their rapi d mob ility , atom s may
inal atomic densi ty at the surface .
to the surface in ord er to pres erve the orig
lent to surface wor k. Sup pos e
In this case then use of surf ace tension is equ iva
at low tem pera ture . Jn this case ,
now that a solid is subjected to a stre ss
surf ace in ord er to preserve tbe
atom s can not move from the inte rior to the
inte ra tom ic sepa ration to increase ,
pac king densi ty. The stress will cau se the
proc ess of stre tching the su rfac e
and consequ ently at low tem per atures the
ing sur face for solids.
will be differen t from the pro cess of form
phe nom eno logi cal aspe cts of
Fol low ing Gib bs, let us exa min e some
een pha ses cr. and {J. At con stan t
su rfaces. Con sider a plan ar surf ace betw
excess qua ntit ies a t the surf ace
tem pera ture one read ily obt ains that the
are given by
(10.2)
d Ux s- T dSx a- L I-lt dn 1x" = u dA
I
p o ut and sinc e F = U - TS we
At co nsta nt volu me the p dV term s dro
find that
dFxs = -sx a dT + Jl.i d11 1 + C1 dA 2 ( 10.5 )
and
'
C1 = (OFx8) ( 10.6)
oA "t·7' .V
222 T hermodynamics of S urfaces and Interfaces
If one integrates equation 10.5 and then subtracts equation 10.5 from the
total differential one finds tha t
sxe dT + A dcr + L n,x• dp.l =0 ( 10.7)
t
Defining the surface concent ratio n r1 as n/'/A, surface energy Us as
.1 l
i
I d" = - s8 dT - f r, dfL, I ( I0.8) I.I
Equation 10.8 represents the Gibbs adsorptio11 equation. Suppose now that
we have a two-component system. At consta nt temperature
(10.9)
Since /ln = p. 0 ° + RT In au
dp.n = RT dIn au
For a dilute solution of B in A, Henry's law may be applied and
r _ _1 ( au )
n - - RT () In X n T
Equatio n I0.9 indicates that if the interfacial energy is lowered upon addition
of solute B, the excess concent ration B, r 0 will be positive. The reverse will
occur if a is increased by the additio n of B. Eq uatio n 10.9 provides a means
by which the excess concentration at the surface may be measured. On the
other hand, this equation indicates tha t the value of cr for pure material s
might be difficult to obtain experim entally since accidental adso rption of
impurities may markedly reduce u and thus yield incorrec t values. In the
case of mica, for example, the value of a in high vacuum is about 4.5 Jf m2 ,
whereas in ai r the val ue drops to about 0.4 Jfm2 because of adsorpti on of
oxygen. For adsorp tion of a gas such as 0 2 equation 10.9 becomes
RTr o = - ( oa ) I . ·'
t oIn Pot
I {
i!MM I a-. e f"W"• "
223
10.2 Anisotropy of Surface Energies
I
/ y•Ag = 1140
1200
-- --- --- --- It-- - --- -- v-y
1000
,_ _(9 3Y .
"'Eu c.
-OD
Iii
.....,
800
600
7
b~
400
200
v
1-
-JZ
/
c. 1- --
o 932• c
x 923· c _
t:. 912•c
0
0 10 2 10 -4 /
Po~ (atm)
'
..
versu s In f'n, yield s: th7.refore, a val ue for r 0 , from
th~ slope.
A plot of r1
A grnp h uf' this type is shown tn hg. I0. 1. The
slope of the ex pen mental
tcu, tt 111t t' " • ,.. . tO'" utoms/ tll~ or abou t one. com plete •monolayer.
.11\0 ·l lll1·. • • . . . •
I Ill 1
of h4ut d tron ts show n tn
The ctl'cct or uddition s on the surface lellston
Fig. 10.2.
1200
-~
c::
0
'iii Fe - 0 ' ~
....,c:: 1000
Ql
u
"' 800
~
~
't: Fe - S
:::1
(/)
600
400
0.0005 O.<XH 0.01 0.1 1
Weigh t % addition
n of liquid iron. From F. H .
Fig. 10.2 Effect of variou s additions on the surfac e tensio
Halden and W. D. Kingery, J. Phys. Chem., 59, 551 (1955) .
I
tl )
I
I
that have appea red . From
Fig. 10.3 Etched spher e of germa nium. Note crysta l faces
B. W . Batte rman, J. Appl. Phys., 28, 1236 (1957).
224
225
10.2 Anis otro py of Surf ace Ener gies
,., lei
·. '
'
'
10101
J
226
227
10.2 Anisotropy of Surface Energies
Suppo se now that three phases meet as shown in Fig. 10.7a. The angles ex,
n
{J, and y will tend to adjust thems elves into the lowest energy config uratio
possible. The question then arises as to what are the factors govern ing the
of
magni tude of these respective angles. Consi der the proble m in terms
interfacial tension. There is a bound ary between the ex and fJ phases with
a
surface tensio n u«P· This tension is acting in such a way as to reduce the
length of the bound ary between the ex and fJ phases. This force may theref ore
be represented as a vector acting along the oc- {3 bound ary, in such a djrect ion
as to shorte n the bound ary (from the origin of the three bound aries outwa rd).
Similarly there are cx- y and {J- y bound aries wilh. tensions u«Y and CTpy,
respectively, acting in such a way as to shorte n' the respective bound aries.
fray
(a)
l ~~~------------0+
1
t
(b) Force
Fig. 10.7 (a) Forces along boundaries which govern the bounda ry angles.
diagram for angular displacement of boundaries between phases.
228 T hermodynamics of Surfaces and Interfaces
T hese forces a re shown in Fig. 10.7a . The angles <X , {J , and y will correspo nd
to the equilibrium between these forces. At eq uilibrium we have from
trigonometry
a, 6 = cr,., = cr,., ( 10. 10)
S ID ')I sin P Sin <X
or
a, 6 - cr,., cos c/> - u 6 ., cos() = 0 (10. Ll)
For the special case w here a, 11 = u,1 = apy'
0: = {I =y = 120°
These eq uatio ns a re well known a nd are valid for liquid phases. For interfaces
in solid bodies they a re not complete, however, si nce there is an addit io nal
factor pointed out by Herring1 which has not been included in the above
treatmenl This consideration co mes from the fact that a is a function of
crystallographic o rientation o f the bo undary in the case of solids. As a
result there will exist the forces previously discussed trying to shorten the
boundaries; in addition there may be angu lar forces attemptin g to ca"use the
boundary to turn into a crystallographic o ri entatio n having lower energy.
Herring treated this problem along the foll owing general lines. Consider a
balance of forces similar to that shown in Fig. l0.7a; let us now displace the
boundaries as shown in Fig. 10.7b. The displacements AP, BP, and OP are
chosen to be infinitesimal and we shall place the further condition that
OP << AP and OP < <BP. Let us consider tha t the free energy change is
related to a by equation I 0.6 and that the speci men has dimension L perpen-
dicular to the plane of th e page. The boundary o:- (1 the refore increased by
an a rea OP x L. The force opposing this is
dF2 = (oa0 ; 1 )-
0</J AP XL ( t0.13)
t''
and f
oa(l y -
cl F..I =- sin 0 · 0 P X L ( I 0.17)
(}{)
A significant amount of su rface energy data exists for metals and nonmetals.
....
For seve ral solids the temperature dependence of a has al so been measured.
Since a is actually a free energy term,
a= Us- TS8
where Us and Ss a rc the energy and entropy change associated with th e
formati on of the surface. To a first approx imation if Us and Ss are temper- )
ature independent a in a pure material will va ry linearly wi th temperature.
Tbe surface entropy has been determined for several materials and some of
these are shown in Table 10.1. Listed in Table I 0.2 are some values of a for
solid- vapor interfaces. The method generally employed in determination of
surface energies is the zero-creep technique. In this technique applicable
only at high temperature, an adjustable weight is suspended fro m a wil'C.
Creep of the wire will occur unless the weight exactly balances the surface
forces tending to contract the wire. The a values obtained refer to the surface
of the wire and are therefore generally average values of a and do not
normally refer to values associated with particular crystallographic planes.
Values of Us may be readily calculated from the data in Tables I 0.1 and I0.2.
Some experiments have been performed which yield, instead of average
va lues of a, the rati o of a values for two types of planes. If the data are I l
sufficiently accurate ratios of U;/ u,
and S../ U1 may be obtained from the
relation I ~·
- I 1
a1 U 1 - TS 1 I
I ) )'
''
Cu 0.5 ± 0.4 0.09-0.3 l ! '
Ag 0.4 ± 1.5 0.13, 0.16
Au 0.5 ± 0.1 0.10,0.52 I ')
I )
10.3 Surface Energy Values for Metals and Compounds 231
Metal e1 (Jfm'l)
Ag 1.12 ± 0.065
AI 1.08 ± 0.20
Au l.39 ± 0.07
Be 0.90
Co 1.95 ± 0.19
Cr 2.30 ± 0.35
Cu 1.72 ± 0.1
Fe(o) 2.08 ± 0.11
Mo 1.96 :±: 0.20
Nb 2.26 ± 0.30
Ni 1.81 ± 0. 18
Pt 2.28 ± 0.80
Sn 0.68
Ta 2.50 ± 0.5
Ti 1.69
w 2.65 ± 0.34
Zn 0.83
• t
; where subscrip ts i and j refer to particular types of crystallog ruphic planes.
~ Comparis o n of q;fq1 at three temperatu res y ield the results for Cd and Zn
shown in Table 10.3. Extensive data do not exist with regard to the actual
values of surface energies for particular planes and the data for a as a function
of fJ are practicall y nonexiste nt. In the last section so me discussio n of cusps
t was presented. One might expect that cusps would exist fo r low index planes.
I
I
~
If this is true dafdc/> is disco ntinuous at the low index su rface and is large as
the orientatio n of the surface charges an amount de/> from coinciden ce with
the low index plane. This situatio n is illustrated in Fig. 10.5. The torque
term (1 /a)(dafdcp) has been measured for orientations near ( Ill ) for Cu and
the results are illustrated in Fig. I0.8.
Some useful semiempirical relation s exist for estimating average values of
a for solid- liquid, liquid- vapor, and solid- vapor interfaces. Based on
quasichemic al theory, one would expect a propor tionality between the
interfacial free energy of the interface listed above and the heat of fusion of
solid, heat of vaporization, and heat of sublimation , respectively.
0.12 I I I
• o.f.h.c. copper in
graph1te boat
0.10 o High-pur ity copper in -
i', graphite boat
'' x o.f.h.c. copper with no
graphite in system -
0.08 ' ••
'
'~ •••
1 2cr
~ 2tj) 006
~
-
..
~•
•
• •
0.04 xx •
~ .. ••
• t
~
•
0.02
(111) Plane
Dry hydrogen annealed
.' -~·
• li • -~
I I I ~
0.1 0.2 0.3 0.4 0.5 0.6
fj) (radians)
n
Fig. 10.8 T orq ue terms for surfaces near ( Il l), annealed in dry H2 . From P. G . Shewmo
and W . M . Robertso n, in M etal Surf aces, ASM, Clevelan d, 1963. f I
f I
The term a is expressed in terms of energy per unit area , wherea s the bulk
thermodynamic terms are genera lly expressed as energy / unit mass o r energy/g- f I
atom. One therefore converts a to units of energy/g-atom of surface atoms
(Fs) by use of the relation
Fs = N 'A V~ a
( I
where N is Avogadro's number and Vis the molar volu me. Then
l J
Fs = KLt
where K is a consta nt and Li is the heat of vaporization, fusion, or sub-
limatio n. Values of K are found experim entally to be 0.15 in terms of the
heat of vapori zation for liquid- vapo r interfaces , and 0.15 in terms of the
heat of sublim ation Ls for solid- vapor interfaces. A plot of Fs versus Ls
10.3 Surface Energy Values for Metals and Compounds 233
L, (kJ/g atom)
0 200 400 600 800 1000
30 -
I I I I I I I
r I I
- 120
- ~ w -
- . VNb - 100
vfMo
25
- Pt -
.......
E
0
--
;Q
bO
I I)
u
.:c
20
15
-
-
-
Cu~ ~
Cr
Fe~ v -
-
-
-
80
60
-E
.8
--
~
II)
bO
..)C
J ~ - Ag~ Al ~
10 - - 40
_Zno/ / Sn -
Be 0
5 20
0
0
/ , so
I
100
I
150
I
L, (kcal/ g atom)
I I I
200
I I
-
0
250
Fig. 10.9 Graph or molar surface energy Fs at melting point versus heut or sublimation
Ls for metals. From H . J ones, Metal Science J., S, J5 (197 J).
which illustrates the correlatio n is shown in Fig. 10.9. For solid- liquid
interfaces K is found to be 0.46 in terms of the hea t of fusion .
It is interesting to compare these results with prediction s of simple nea rest
) neighbor theory. •
1 let us consider a crystal with a coordinat io n num ber
Following· Herring,
Z . The number of pairs in a crystal containin g N 0 atoms is tZN0 • ln a very
simplified picture the pair energy E is equal to the heat of sublimati on L 8
divided by the total number of pairs or
Ls
E= - -
~ZNo
therefore , 3 bonds are broken per atom. By the process, however, two
surfaces are formed, so the number of bonds broken per atom on one surface
is t. Thus the enthalpy of surface forma tion per atom is
3 Ls
h per atom =-E=-
2 4N 0
If there are N atoms per square centimeter in the (1 11 ) plane, the surface •'
enthalpy per unit area
N L~ r,
H = -'
' 4N 0
and 2.40 J/m 2 , respectively. In view of the gross nat ure of the approximations
in the q uasichemicaJ theory, the qua ntita tive predictions are in reasonable
{ .
accord with experiment. . M ore importa ntly, the quasichemical approach I .
predicts a relation between the energy of the surface and bul k thermodynamic
properties such as heat of sublimation . I I
Some results have been obtai ned for a variety of materials fr.o m cleavage
experiments at low temperafures. Since T is low the TS term is relatively
small and a is approxima tely equal to U8 . These results are shown in
Table 10.4. ( I
10.:3 Surfac.e Energy Values for Metals and Compounds 235
·; n the case of ionic crystals, the forces holding the atoms together are
coalombic in nature. As a result it is useful to take a general view which,
however, may also be applied to metallic and covalent crystals. Consider a
plane in a crystal which is cleaved in order to form two su rfaces. Prior to
cleavage, the energy between atoms across the plane as a function of inter-
at~mic distance will be represented as shown jn Fig. 1O.lOa. At equilibrium
t.,.
c:
.2
c:
Cll
0
~I
Cll
~ 'A/2
Cll
.J:l
Cll
u
.....
0
u...
(b)
Fig. 10.10 (a) Potential energy between atoms in a crysta l as a function of separation.
(b) Force between atoms in crysta l as fun ction of separation.
the spacing will be x 0 • The su rface energy may be thought of, in terms of
Fig. 10.1Ob, as the work needed to separate the a toms across the plane to a
distance of infinity. In Fig. l 0. JOb the force is plotted as derived from Fig.
l0.10a by taking the derivation dU/dx. The work (and hence surface energy)
needed to separate the atoms fr?m thei r equilibrium distance x 0 to x ~ oo
236 Thermodynamics of Surface s and Interfaces
and we obtai n
df [21T(X - x0)] --....
- =/0 COS j
d.c A
Upon substitution
1·
Under the conditi ons of the derivat ion of J0 , namely, that the strains are
small, (x - x 0) << 1, and thus
1
27T(X - X11) ]
cos [ A ~ I ,j
10.4 Internal Boundaries-Chemical Discontinuity 237
Therefo re
l
YA.
,.....;-
J0= 2 7TXo
and
y,t2
Us = - -
47T2Xo
Young's modulus data are availabl e for most substa nces a nd hence, if ). can
be obtained , U5 may be calc ulated; if the tempera t ure is relatively low ,
Us~ a. Because of the short-ra nge exponen tial nature of atom ic attractiv
e
forces , A. will be a smaU quantity and for the sake of calculat ion we wi ll
approxi mate). by x 0 • The forces are small when the ions are sepa rated by this
distance. The values of surface energies obtained in this manner are com-
pared with experim ental va lues of u in Table I 0.4.
In some ways it is rather surprisi ng tha t these simple models yield good
agreeme nt with experim ental results. Recent work employi ng low energy
electron diffracti on (LEED) of very clean surfaces shows, for exa mple, that
the surface structur e may be quite dirferen t from the idcaliLed structure lhat
one might envision . Palmber g and Peria, for example , have studied clean
1
l
~
1
-
CD
0
c:
0
+:.
a (J
10
!:1
c:
Q)
u
c:
8
cD
u rBoundary ~
direction normal to the interface the free energy across the interface will be
given by equation 9.19. For interfacial area A if high-order terms arc
i
l
J
l
)
I
I
I
I
I
I I
I I
I I
I I I
~AXa 'J:..: L1Xa4
0 1
X 8 mol. fraction of B
I
10.4 Internal Boundaries- Chemica l Discontinuity 239
( 10.20}
where
Equation l 0.20 suggests that u may be reduced in val ue if the term (dX 11 /dy)
is sm a ll, which implies a diffuse interface. l f t his occurs the volume of material
of composition differen t from the equil ibrium inc reases and f~co 6.f(Xu)
will therefore increase. This may be readily seen since
and
and
( 10.22)
Compa ring Fig. 10. 12 wi t h equa tion 10.21 ind ica tes that the concentratio n
of B across the interface will vary as shown in Fig. I 0. 13. If the thermo-
dynamic p roperties o f the a lloy are available o r can be estimated so that
6.f(X 0 ) may be calculated, the su rface energy and effective width of the
boundary may be calcula ted. When ex a nd fJ have different crysta l structures
o r are misoriented with respec t to each other, add itio nal complexi ties must
be considered .
240 Thermodynamics of Surfaces and Interfaces
1~------------------------~
cfJ
f
- I
0
c
0
~
-...
f'O
I
I
I
I
I .
I
I t'
I
I I Fig. 10. 13 C0111position or a and {I in
_"__/_ _ _ _ _ __j_ - - -
1< l ,. I the vicinity of the interfacial boundary.
From J. W. Cahn and J. E. Hilliard,
0~--------------- ---------~ I . Chem. Phys., 28, 258 ( 1958).
x, distance
,..- l ~
r-
rbl
r-
7
-j .-
\
t-
-
f-
\ ..L
r-
1-
r-
....-
r-
,-
\ \
1- \ ..L
r- - r-
- r-
-
-
~
\
.- ..L I
1-" - r- --- -
I
1-
~...--'
l
(a I (b J
Fig. 10.14 Low a ngle tilt boundary. From W. T . Read, Dislocations ill Crystals, McG raw-
HiiJ, New York, 1953.
consist o f pure edge and screw dislocations, respecti vely. Examina tio n of the
figures shows that the dislocation count should be simply rela ted to the
misorientation angle 0. Since the only disturbance in the boundaries is due
to the presence of dislocatio n, the energy of th ose boundaries sho uld therefore
be simply related to 0. Geometrically it may be seen fro m these figures th at
the dislocati o n spaci ng D is given by
b b ( l0.23)
D = -·-~- fo r sma ll Q
sin 0 - 0
for tilt bo und a ries, and
D= b C::! !. for small 0 ( 10.24)
2 sin o - 20
for twist bo undari es, where b is the Burge(s vecto r. The energy per uni L
242 Thermodynamics of S urfaces and Interfaces
..... 1'.
- >-lr'
~
t
)-
1}, J.. b.-~ -~ t l t
llh l 1l I ll ~ 1 1 I
) .)
....... 'f 1I
I
1
~ 1
I
JJ l
l I
'J
1>--' -
)
·- ... -~
~-
.~
.. -· -
-- .. - -
~ :::.· ~
-- ~ ~ -' 1•..;.' I
......... ... - ·- • ·- I• ' I
~
..-
~
~-
~ .. -~""
....
I
I
~-
)
I 1 I I
lA 6-
r lJ
"1
J
l ~},H
c..(
.... . "
'f'~T
I I
--1>-
... t
.J ....
~
l I
· ~- '-~-. t-
ll
1>-
,.._,
- - - --. - - - .. { .
I - ( I•
1'-- •
--: I ~~
~ - -
-~
~
....... .. I"' "
.
I
I l
~ 1 1 ., T l ' f ' f -~
I)-·
Fig. 10.15 Low angle twist boundary. From W. T. Read, Dislocations in Crystals,
McGraw-Hill, New York, 1953.
as the energy per uni t length of dislocation. The number of dislocations per
unit length of boundary is 1/ D and hence the energy U per unit area of
boundary is Ul.f D or
U = GbO
477(1 - v)
In
0
(!) + BOb ( t 0.27)
U = E00[A - In 8] ( 10.28 )
w~ere V 0 a nd A are constants given by
_ Gb
Uo -
477(1 - v)
477(1 _
A =_..,:.__ - v)B
_
2
Gb
1 J. H . van dcr Mcrwe, Proc. Phys. Soc. (Londol/), Scr. A. 63, 613 (1950).
-
144
'I'herroodyna
mics o [ Surf
aces and inte
\
rfaces
.. ....... .......•.·.........................·..•..•... f..••....' ..........··...··...··...=...·=....·:...·:.·:..·:..·:.·:..
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•
.•..•••.••...••....••..•..•'\••t'·... ..__ .••.••..••..••..••..••. ..••.••..••..••.. .••. .••..••..••.. .••. .••..••..
...•.•.•....•••.• •••••••
•• ••
• • •• •• ••
••
~ .-•-.•~.•·.•······
. .
••••••••••••••:·••:·:·:·:·:
•••••••••
....................................··....··..··..··..··..··..··..················..··..··..··.
• ••
•
·~··~··~·:~ •• • • • • • • • • •··•···· • • ·· ·· • ··
• • • ••• ••·· • ··
• ··
.·..••~..•.......·•...·'·. ••.··..·•.. .. .......... .··..
~~·:·:·:·:·: • • • • •
.··.. .. ................
·: •• ·:·:···:·:·: •
'•
·~··
·:·:·:·:• •••
·:·:·:·:
·~··········
. .
·• ·•.·•.··. . . .··.··.··..··..··.... . . \
~
·······
•
·~··:·.~··
.....
•• •• •• •• •• ••
•• •• ••·•
••··
••·•••·• ·· ·· ·· ·· ·· ·· . . . . . . . . . . ... . .
fi g . 10.16 ~· ~·
Uubble cafl m
~·~·:·:·····
odel o f a loW
·
•• •• •••• • ··•·•
•
·· ··
• ·· ·· ·· ·· · ...
J. F . Nye, Pro an g le gcnin b
oundacy. Fco
c. Roy. Soc. (L on W. M . Lom
ondon), Ser. A e< a n d
, 1 1 1 , 576 (195
sim 2).
ple tilt o r twis
'\
t boundary in
boundary dis!l a cubic crysta
p p l a n d in fact
e
Gjostein a n d ars since th e registr a t 0 = 90° , th
Rhines' have y is again perf e
energies fo r si
m
m a d e a n exp ect.
erimental stu .
T h e results a ple tilt a n d twist boundari dy o f bound
ary
re shown in e s in
observed th a Figs. 10.20 a c opper as a fu
n d 10.21. F ro n c tion \
shown in Fig
t the experill
lental points m these ligure o f 0.
s. 10.18 and folloW curves s, it is
o f l:l.G' for hig 10.19 as deriv o f the genera
ha ed by van de l type
a n d 0.5 J /m '. ngle tilt and twist boundari r Merwe. T h e
values
respectively. C es (0 z,< 45° ) a
th e surface en omparison be rc a b o u t 0.6 J
ergy o f copp<;r tween these v
alues and <1N
fm'
o f 1.65 J /m ' le o' for
ad to tbc gene
high angle bo ralization th a t
undary 11 for a
-r-..~
a -
l
CJsv 3 =
1 N . A. Gjostei
n and F. N. R
hines, Acto M
et .. 1 , 319 (195
9) .
\
[
~
.... - .. --.
qf'lg. 10.17 Uu~ble-raft model of a high angle grain boundary. From W. M. Lomcr and
J . F. Nye, Proc. Roy. Soc. (London), Ser. A, 212, 576 (1952).
~0.4
"'
~ 0.3
01
0o 10 20 30 40 50 60 70 80 90 100
T1lt (degrees)
Fig. 10.18 Calculated values of grain boundary energy versus misorientation for lilt
boundary. (a) van der Merwe's calculation; (b) Rc:-~d and Shockley's ca lcu lation . From
D. McLean, Grain Buundanes irt Metals, Oxford, London, 1957.
245
246 Thermodynamics of Surfaces and Interfaces
1.0
0.9
0.8 ~
.....
a
-.....
0.7
0.6 J
/
v
"' ' 1\
~f f\b -
~
~
] 0.5 - - -- - b( 1-- I \
0.4 -- ( I 1
0.3 - - -
0.2
1- ( I
0.1
0
o 10 20 30 40 50 60 70 80 90 100
Twist (degrees) /
Fig. 10.19 Calculated values of gra in boundary energy versus misorientation for tw~t
boundary. (a) van der Merwe's ca lculation ; (b) Read and Shoc kley's calculation. From
D . McLean, Grain Boundaries in Metals, Oxford, london, 1957.
The figures also indica te th at ab does not vary much for misorientations
20° < () < 70°, and so for practical purposes ab may be co nsidered to be
independent of orientation a ngle for a high angle boundary. As a result,
our earlier statement that (Ja f(Jcx is small for most boundaries is verified.
Some typical values o f ab arc listed in Table I 0.5 for representative metals.
There are certain special orientatio n rela tio nships for whic h the aton1_
0.40
:.r ~~
.. ..,...___, - 600 { I
0.32
v
r-........
1'- , - 500 ( ,
/ ' "\ - 400 ;;'
-::. 0.24
~
b
<I 0.16 I
L.4
1\ 300 ~
E
u
--
.....
~ I
I I
J
IU
\ - 200 b
0.08 \ ( .
~ \ 100
0 ,
\
10 20 30 40 50 60 70 80 90
8 (degrees)
Fig. 10.20 Experimental value of the grain bou ndary energy as a func tion of misorienta-
tion for a simple tilt boundary in copper at 1065°C. From N . A. Gjostcin and F. N. Rhines, •
I,
A cta Met., 1, 3 l 9 ( 1959).
I j
10.5 Internal Boundarie s--Structu ral Discontinuity 247
0.32
• - 500
v.-- • .-
•
- 400
024 ./
~
t; 0.16 I
/ - -
300 ('I
E
~
I
CID
<]
- 200 .e
b
0.08
v - 100
0
10 20 30 40 50
8 (degrees)
Fig. 10.21 Experimental value of the grain boundary energy as a function of misorienta-
tion for a simple twist boundary in copper at 1065°C. From N. A. Gjostein and F. N.
Rhines, Acta Met., 7, 3J9 (1959).
Table 10.5 Interfacial Energies for High Angle Grain Boundaries and Relation to
Surface Energy
spacing on one side of the boundary is very similar to the spacing on the
other side. As a result we would expect the bo undary energy correspon ding
to these orientatio ns to be low. These spec ial low energy bo undaries will
lead to the occurrenc e of c usps in the grain boundary energy versus 0 cu rve.
Such a specia l boundary is called a coherent boundary . An example of such
a coherent boundary is a twin boundary when the boundary coincides wilh
the twinning plane. A twin boundary will b_e uoucohere nt if the boundary does
248 Thermodynamics of Surfaces and Interfaces
Crystal Reference
not coincide with the twinning plane. [n Table I0.6 are listed some rep-
resentative values of twin boundary energies of both the coherent and non-
coherent type. From Table 10.6 it is seen that a coherent twin boundary has a
much lower energy than an ordinary boundary, whereas the energy fot a
noncoherent twin boundary is approximately the same as for an ordinary
boundary. The consideration previously discussed co ncerning the torque
on a boundary due to the anisotropic nature of interfacia l energies become
of particular importance in this case. Consider the si tuation shown in Fig.
10.22, where the dashed line represe nts a twinning plane and the solid line
I I
represents the actual pos1t1on of the boundary between the two crystals
situated at an angle of¢ for the twin plane. The boundary energy versus the I J
angle 4> is shown schematically in Fig. 10.23. At</> = 0, the boundary becomes
j
coherent with the low energy shown in Table I0.6. At 4> = 0 the misorientation
I
between atoms on either side of the boundary is small but this increases I I
0 +
Angle c/J
Fig. 10.23 Bounda ry energy versus angle 4> for noncohe rent boundar y of Fig. 10.19.
,•
i:
occurs when a crystal contain ing a grain bounda ry, such as shown in Fig.
10.24a, is heated to an elevated temper ature in an inert atmosp here. After a
period of time, a groove will appear on the surface as shown schematically in
Fig. 10.24b (scale exaggerated). Experimentally this groovin g may be
observed quantit atively by the study o f interference fringes or directly wilh
the aid of a microscope. An interfe rogram for such a bounpa ry is shown in
Crystal Crystal
1 2
Boundary
(o.)
Boundary
'
•
l
\
1
:
t I I I
I ' I
Fig. 10.25 lnterferogram for a grain boundary groove in copper a tlhe surface of a crystal.
From N. A. Gjostein and F. N. Rhines, Acta Met., 1, 319 (1959). I j I
Fig. 10.25. This grooving results from the grain boundary attempting to
minimize its energy by diminishing its area. Equilibrium will be reached
when the force relationships of equation 10. 11 are satisfied. The particular
relationships for this situation are shown in Fig. 10.26. At equilibrium
Crystal Crystal
1 2
r
elements. Thus B will generally be positive. Ln Fig. 10.27 is shown the
segregation of polonium to a grain boundary in lead. The polonium was radio-
active and the image resulted from the blackening of a film placed in contact
with the specimen. We may calculate the value ofru from principles presented
earlier in the chapter. 1 We derived previously that
! ..
L
t
i
\
Fig. 10.27Segregation of polonium at a grain boundary in lead; an autoradiograph. l
From W. R. Thomas and D. Chalmers, Acta Met., 3, 17 (1955). (
1
!t
consequentl y there is no dividing surface for which 1\. = 0. For a sub-
stitutional solution, however.
small the above equation reduces to
rA
= - I"n if the density is constant. If Xu is l
'
r ~ __
1 ( dIn u )
B - RT dlnXa
which is the same as the equation for an external surface. For an interstitial
solution of B in A, r A = 0 and the above equation is valid at all concen-
trations. The temperature dependence of r u is found by differentiati on to be 1
[
I (~)
a(l ' 0 /X 13 )] = _ +_I (aSs)
aT RT 2 aX n RT aX n
r doma in
or abou t 10~ Jfm 3 • This energy can be reduced to zero if the prope
associated
confi gurat ion is created. Offsetting this gain in energy is the energy
with the forma tion of the doma in walls.
in Fig.
A doma in wall (called a Bloch wall) is iUustr aled schematically
and may
10.28. These walls represent regions of stron g local magn etic field
nsion of
be readily revea led experimentally by sprea ding a colloidal suspe
particular
finely divid ed ferromagnetic mater ial on the crystal surface. A
these
confi gurat ion is illustrated in Fig. 10.29 . The energy associated with
N
s
I
I N N
I I
I I
I 1
I N N I
I I
I ,, ,, •Jf}f'j {l
IN N I
I I
I 1
IN N 1
I I
I
York, 1970.
1
C . Kittel, l11troduction to Solid S tate Physics. 4th ed ., Wiley, New
I
254 Thermodynamics of Surfaces and Interfaces l
I
I
I.
I
If
I I
Fig. 10.29 FerromagnetiC domain paltern on the surface of a single crystal platelet of
nickel. From C. Kittel, /ntroductwn to Solid State Phystcs, 4th ed .• Wiley. New York. 1971 .
By permission of John W1lcy & Sons, Inc. In original figure ut:knowlcugmcnt made to
R. W. De Blois.
( 2KJS 2
a::::::2
)~
a
where Sis the spin quantum number, J is the exchange integral, a is the I ]
lattice constant, and K is a constant. The value of a calculated is of the order
of I0- 3 Jfm2 •
semicoh erent boundar y the magnitu de of the structura l term may be esti-
mated. Conside r the configu ration shown in Fig. 10.30.
The disregistry d is defined as
where the a terms refer to the planar spacing normal to the boundar y
between crystals. 1t is observe d from Fig. 10.30 that perfect registry occurs
every seven spacings for ex and every six spaci ngs for {3. As a result there is
Fig. 10.30 Interfacial boundary between two crystals of same Ol"ie ntation but having
different lattice paramete rs. From D. Turnbull , in Impurities and Imperfections, ASM,
Cleveland, 1955.
an extra half plane in IX every six {3 spacings . Co nsequen tly the above interface
may be pictured as a coheren t interfac e with a dislocat ion existing every
six {3 spaci ngs. This may be put in the form of an equation with the dislocat ion
spacing D given by
Op
D=-
IJ
structure of the type shown. The energy associated with a dislocation is large
and the to tal energy of the system may be reduced if, instead of forming
dislocations as shown in Fig. I 0.30 the planar spaci ng is changed in the
I
vicinity of the boundary so as to increase the dislocation spacing. This I•
process, of course, results in the storage of elastic energy in the matrix of 1
the crystal and the actual situation will represent an optimum value of the
two.
I
o
For phases of rad ically d ifferent structures or cases where is large, the
si tuation is not quantitative ly as si mple as that just described. It may still
i
'
1:
be useful in some cases to co nsider the energy as co nsis tin g o f a chemical
contributio n and a structu ral co ntribution, however. The dislocations in
this case are too close together for the l ow angle boundary analogy to be
va lid. Rather, the si tuatio n is simila r to a high angle boundary. As a res ult
w~ ..,_ .. ,,., bV;'."'I the structural co ntrihutirm for this type of interface to be
about equal to the energy of a high angle grai n boundary.
In Table 10.7 a re listed interfacial free energies for various metallic systems
•
12
Table 10.7 Relative Interface Free E nergics
Grain Boundary
Interface Between Used as a
Comparison "An
System Phase A Phase B In terface, D T(° K)
"n
i
Cu- Znb a f.c.c. Pb.c.c. a/a 0.78 973
Cu- z nb a f.c.c. {J b.c.c. {1/{J 1.00 973
Cu-AI ~ a f.c.c. IJ b.c.c. a./a. 0 .71 873
Cu- Aib {J b.c.c. yc.c.e y/y 0.78 873
Cu-Snb a. f.c.c. Pb.c.c. a./a. 0.76 1023
Cu- Sbc a. f.c.c. fJ b.c.t. a/a 0.71 873
Cu- Agc a (Cu) f.c.c. {J (Ag) f.c.c. {J/ {J 0.74 1023
Cu-Si 0 a f.c.c. fJ b.c.c. a./a. 0.53 111 8
Cu- Sic a. f.c.c. fJ b.c.c. fJ/fJ 1.18 111 8
Re- C 1 a. b.c.c. Fe;, c.o. r. e a/a. 0.93 963
Fc- C' a. b.c.c. )' f.c.c. a./(1. 0.7 1 1023
Fc- C4 a b.c.c. y f.c.c. a/a. 0.74 1223
Fc- Cud a. b.c.c. f.c.c. a./a 0.74 1098
Zn- Snc fJ (Sn) b.c.l. a. (Zn) h.c.p. a/a 0.74 433
4
From C . S. Smith, in Imperfections in Nearly Perfect Crystals, W. Shockley, Ed .,
Wiley, New York, 1952.
b C. S. Smith, Trans. AIM£, 175, 15 (1948).
c C. S. Smith, unpublished.
d J . Van Vlack, J. Metals, 3, 25 1 (195 1). ~
e c.c. =complex cubic; o.r. =orthorhombic.
,.
Problems 257
relative to the free energy of high angle grain bounda ries on these sys tem s.
The energies for the interfaci al energies are found to be very close to the
grain bo undary values.
In Table 10.8 are listed some data for metal-c ompoun d interfac es.
0
M. McLean and E. D. Hondros, J. 'Materials Sci., 6,
19 (J971).
11 D. K ingery, Introduction to Ceramics, Wiley, New York,
1960.
PROBLE MS
1. Suppose tha t a droplet of a liquid substance forms a sphe rical cap o n a copper
su rface with a he ight of w-sm and a contact diameter o f 5 x J0- m. (a)
3
Calculat e the surface tension of the liquid-co pper interface and the liquid-
a tmosphere interface. (b) Ca lcu late the to tal force which would be needed to
remove the drop from the copper. In an experime nt to measure this force,
wha t accelerat ion is necessary for the drop to be removed from the copper ?
2. Is a solid complete ly wetted by its own liquid at the melt ing point 1 Explain
reasonin g.
3. For a low angle crysta l boundar y, would rp' be positive for impurity segre-
gation? Consider both impurity atoms la rger a nd smaller than the matrix.
Explain your answer.
4. Which plane would yoli expect to oxid ize more easi ly for nickel if it formed
the surface. the ( Ill ), ( I00), or (I I0) plane?
5. Suppose that a second phase pa rticle has a hexagon al close-pac ked structu re
a nd the matrix has a face-cent ered cubic structure . What wou ld you expect
the particle shape to be? Why?
6. Estimate the grain boundary energy for nickel and platinum .
7. Suppose that the normal to a high a ngle gra in boundar y in a copper wire o f
t<J4 m diameter is inclined to lhe wire axis at an angle of20°. Upon annealin g,
what would you expect to happen to the grain boundar y? Calculat e the
driving free energy fo r the process.