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TH ER M O D Y N A M IC S

O F SO LI D S

I RIC HAR D A. SW ALI N


I ·.University of Minn esota
l Minneapolis, Minnesota

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....--...- -_
~- ... ·- - ~~ .....-.

Clea._ .... ~?J~.~ _ __


l_ _
fl_'i ~1.Y~.=
Cun . ____
UFSCAR
- -··· .~.:~----
Tombo: ........ Jt~ ...8 f ~f~3 l~:t-

Copyrigh t C 1962, 1972, by John Wiley & Sons, Inc.


All rights reserved. Published simultaneously in Canada.
No part of this book may be reproduc ed by any means, nor
transmitt ed, nor translated into a machine language with-
out the written permissio n of the publisher .

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
.,_.,..,..
.
~,....
-
. .
·.

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)
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

2 The First Law of Thermodynamic s 4


2.1 Heat, Wo_rk, and the First Law 4
5

2.2 · Calculations of Worlc:
2.3 The Enthalpy Function and Heat Capacity 10
2.4 Heats of Formation 15
2.5 Heats of Reaction 16

3 The Second Law of Thermodynamic s 21


3.1 Definition of Entropy 21
3.2 Entropy Calculations for Various Processes 24
3.3 Some Useful Relations Obtained from the Second Law 28
-M The Statistical Interpretation of Entropy 35
~The Free Energy Function 45
4 Some Relations Between Thermodynamic Quantities S3
4.1 Properties at 0°K (the Third Law of Thermodynami cs) 53
4.2 The Temperature Dependence of Heat Capacities 51
t:l
4.3 Gnineisen Relatiqn 63 .,.
-~
4.4 Some Compressibility Relations 65 ~·
:j
4.5 The Magnetocalori c Effect 67
4.6 Heats of Formation of Ionic Compounds: Born-Haber Cycle . 70
4.7 Empirical Predictions of Entropy 76
4.8 Estimation of Heat Capacities of Crystals 81
4~ Heats of Formation of Compounds . 84

..5 1bermodynamic s of Phase J;~ormations and Olemical Reactions 88


5.1 Phase Transitions Classified According to Order 88
5.2 First-Order Transitions 92

ix
X Coateat.

S.3 Second-Order Transiti ons 100


S.4 Chemical Reactions 104

6 Partial Molal and Excess Quantities 119


' 6.1 Partial Molal Quantit ies 119
6.2 Method of Obtaini ng Partial Molal Quantities from Molar
Quantities 121
6.3 Method of Obtaini ng One Partial Molal Quantit y from
Anothe r 122
6.4 Some Relations Between Partial Molal Quantities 124
6.5 Free Energy of Format ion of a Solution 126
6.6 Ideal Solutions 126
6.7 Nonidea1 Dilute Solutions 128
6.8 Concentrated Solution s 130
6.9 Excess Thermodynamic Quantit ies 135
6.10 Effect of Gravita tional or Centrifugal Field on Alloy Homo-
geneity ' · 136

7 ~ermodynamic Properties of Alloy Systems-A MoaeJ Approach 141


7.1 lntrpduc tion 141

. ""
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

9 Free Energy of Binary Systems " 190


9.1 Introdu ction 190
9.2 Free Energy Versus Compos ition for Case Where A and B
Have the Same Crystal Structur e 191
9.3 Free Energy Yenus Compos ition for Case Where A and B
Have Different Crystal Structures 197
9.4 Calculation of Phase Diagram s from Thermo dynami c Data 205
9.5 Relations Between Phase Diagram s of Different Types 210
9.6 Nonuni form Systems 215

J
I
Cooteaa

Thermoclyaamics of Surfac es ud Interf aces no


10.1 Surface Tensi on and Surface Energ y 220
10.2 Aniso tropy of Surfac e Energies 223
230
..
10.3 Surface Energ y Value s for Metal s and Comp ounds
10.4 Intern al Boun daries -Chem ical Disco ntinui ty 2.37
10.5 Intern al Boun daries -Struc tural Disco ntinui ty . 240
10.6 Internal Boun daries -Dom ain Walls 252
10.7 Interfaces Between Solids of Different Structures and
Different Comp ositio ns 254

11 Oassif icatio o of Defects in Crysta ls 259


11.1 Types of Point Defects 259
11.2 Other Types of Defec ts 262
11.3 Stability of Crystal Disor der 263

12'\.Def ects ia Metal s 267


12.1 Vacancies and Interstitials 267
12.2 Defect Complexes in Metal s 277

13 Defects ia Elemental Semiconductors 290


13.1 Electronic Defec ts 291
13.2 Atomi c Defects and Defect Complexes 298
13.3 Intera ction Between Atom ic and Electronic Defects 305
13.4 An llJustr ation Which Comb ines Some Principles of
Chapt ers 1- 13 312

14 Defects in Nearly Stoichiometric Compounds 317


14.1 Types of Defects 317
J4.2 Entha lpy of Defec t F onnat ion 320
14.3 Defec t Nome nclatu re 322
14.4 Electronic Natur e of Defec ts 324
14.5 Equili brium Const ants for Defec t React ions 328
14 6 Some Case Studies of Defec t Crystals 335

15 Defec ts in Noostoichiometric ~ompounds 351


15.1 Cause s of Nonst oichio metry 351
15.2 Intera ction between Defects 357
15.3 The Defec t Struct ure of Fe1 _,0 (Wiistite) 361

Appendix 370

A. Distri bution of Particles Amon g Quant ized Energy Levels 370


B. MaxwelJ•s Equat ions 372
C.teat.
d
C. Derivation of the Tem per atu re Dependence of the Bulk , .{}
374
Modulus
D. Calculation of the Fra ctio n of Ion
ized Defects by usc of
375
.~u
Fermi-Dirac Statistics
E. Ollculation of Defect For ma tion Energie
s in Ionic Compounds 378 ..lt., .
.;
383

'
-)

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

is employed throughout the book. This system is becoming widely accepted


In this system the unit of energy is the joule (J), the unit of force is the
J& 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

Quantity Unit Symbol

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

Consta nt Symbo l Value SI CGS

Speed of light c 2.998 x lOS m/s x 101° cm/s


e 1.602 X to- It e x to-tO cmtltgl ls
Elemen tary charge
4.802 x 1o-1o i:;m3/tgl llfs
Avogad ro number N..t 6.023 3
x 102 /mol x tOts/mo l
Planck constan t h 6.626 X J()SC J ·s x 1o-!7 erg·s
Gas constan t R 8.314 x 100 J{K·mo l x 107 erg/K·mo1
Boltzm ann
constan t k 1.38 X to-13 J/K x to-u erg/K
Gravita tional
constan t G 6.67 x to-n N·m'/kg-~ x to-& dyn·cm1g!
eV 1.602 X to-tt J X Jo-Uer g
Electro n volt
Farada y constant F 9.649 x 10' C/mol x 103 an1 ' ,.·g1 '%fmol
2

The First Law ofTh ermo dyna mics


\

1.1 HEAT, WORK, AND THE FIRSf LAW


' I

In this introduct ion it shall be assumed that the reade·r is generally


familiar with the definition of temperature in thermodynamic terms. ,I
Imagine that two beat insulating bodies A and B are at temperatures T.A.
and T 8 , respectively, where TA > T 8 . If these bodies are placed in contact
as shown in· Fig. 2.1, a temperature T' will ultimately be attained where
T 8 < 'r < TA. In order for thermal equilibrium to be ~ttained, a quantity
of heat must have passed from one body to the other. According to our
convention, heat will flow from the bot body to the cooler one.

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)

It is important to note the sign convention that is employed. Q is defined to


be positive when heat flows to the system from the surroundings, whereas W
is defined to be positive when the system performs work on the surroundings.
Many experiments have shown that the energy of a system is a state ·.
property. That is. the value of l:l.U in equation 2.1 is independent of the
particular pat!! chosen. One may conceive of many different paths for
transferring the system from energy state ul to ut. The individual quantities
Q and W may be different for these various paths but the difference (Q - W)
always yields the same value of au= u,.- ul. It follows, therefore, that
the energy of a system is a single-valued function of the variables that deter-
mine the state of the system and that an element of energy dU may be
expressed as an exact differential. Since Q_R,!ld Jf ~e not state_pr~~es,
elemen~_of heat and w.ork are not usually_exact...differentials although they
may ~ und~iaJ circumstances. As a consequence the firs_! ~! of
thermodyn8;!Dics. may be expressed in differential ~orm as
-dU = DQ-DW (22)

1.1 CALCULATIONS OF WORK

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)

As an illustration consider a displacement in one dimension as shown in


Fig. 2.2. In this iiJustration ~he 9stem expands and performs work on_the
5urround.ings. If the process is permitted to occur in an extremely slow
fashion and if the piston is frictionless, the work done by the system. is•
I

DW = Fdx = pA. dx = pdV


~
. -- (2.4)
where p and V are pressure and volume of the system, respectively. Caution
should be emphasized at this point with regard to sign convention. It is

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

on the surroundings. In the example considered in Fig. 2.2 the system at


pressure p undergoes expansion. In order for the system to expand, the
pressure on the right-hand side of the piston in Fig. 2.2 must be infinitesimally
lower than that on the left. Since dV is positive in sign, DWwill be positive
in sign. For a oomp~ve process, the reverse situation holds and dV will be
negative in sign, thereby yielding a negative value for DW. The first law
may be written in the case of ~versible me:chanical work as " - · -

dU = DQ - p dV I -~ (2.5)

The above process is said to have occurred reversibly if an infinitesimal force


applied in the opposite direction would change the system from expansion
to compression. Under this condition D W may be expressed as an exact
differential. Some reflection will indicate why D W may not be expressed
analytically if the piston is not frictionless and/or if the expansion occurs
very rapidly. ·
Calculatioas of Work ·
7
U
Dhastratloa . -
is !_sothe~~
·- Qilcu late the..work don~ by !1 mole_of an i~ea] gas_ when it
~mpressed from 100 m to 10 m at 500°K... W = J
1 1 p dY and for a perfect
gasp V = nRT. Subs tituti on yield s
lo -dV = ., - ·ju_~. ~~:u.3. .

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

"-i -9500 J - -;-~ -~·::-.:f';"'

- .. .
- ~
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

(unit s of force/unit distance). In orde r to


expa nd the x dime nsion by an
oppo sing surface
amo unt dx, an external force Finfi nitesimally larger than the
surfa ce must be
tensi on must be applied. The total force actin g in this
- . DW = (force) x
slightly larger than ( -aL...). ...Since (dist ance ), in this case
' ('

DW = - 'di dx = -u dA (26)

Note the negative sign in this case.

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)

where Z represents a unit of charge. It is convenient to express the charge


unit in faradays: thus Z = !Fn where.F is the number of charges in a faraday
and n is the number of faradays. Hence

DW= t!!F dn (2.8)

Magn~tic Work

H a substance is placed in a magnetic field a magnetic moment will


generally develop. In expression 2.4 for mechanical work the pressure p is
an intensive parameter and Vis an extensive parameter. In a similar fashion
the expression for work in a magnetic field involves the product of an
intensive parameter and an extensive parameter.
In order to calculate the magnetic work term consider the illustration
shown in Fig. 2.4 in which a ring of magnetic material has a circumference t

Ring of magnetic
material

Yag. 2.4 Changing the magnetization


of a magnetic solid. From M_ W.
Zemansky, Heat and Thermodynamics,
Sth ed., McGraw-Hill, New York, 1968.
Used with pennission of McGraw-Hill
Current i Book Company.

and a constant cross-sectional area .A. • An electric current i is circulated


through the toroidal winding which has N turns. The current results in a
magnetic induction B. A change of current in a time interval dt will result
in a change in magnetic inductance dB, which in tum will result in a back

• 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

The magnetic field inten sity H due to the curre nt is

H = 4.,NA i
v
and upon subst itutio n
DW = - - HdB
v
4.,

In the case of a ring of mater ial, in CGS units

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~

where x is the magn etic susceptibility.


thus
If no material is prese nt withi n the windings, xis equal to zero and
band
M is equal to zero. DW is then given by only the first term on the right-
by 2.9.
side of2.9 .lfma teria l is then place d within the winding, DWi s given
material
Cons equen tly the work done by increasing the magnetization of the
is given by the secon d term on the right- hand ~ide of 2.9 or
DW= -Hd M (2.10)

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

............ __________ _..._,..,..


~-, )

Force exerted on a specimen in an inhomogeneous magnetic field . • I 1


Fig. 25
' .!
:I
hori zontal plane , as illustrated in Fig. 2.5. A force F is generated, which
• I

may be shown by application of equations 2.4 and 2.10 to be equal to


I I
I

F = !xA(Hl2 - H 22) (2.11)


I
The force F is measured by a balance and x may be determined directly if
H 1 and H 2 are known.

2.3 THE ENTHALPY FUNCTION AND H EAT CAPA CITY


J
• I


I
I

At this point, it is convenient to define a thermodyna mic function known


. . I

as the enthalpy. The enthalpy H of a system is defined as


H = U +pV ..(2.12) l

For most of the processes of interest here, it will be convenient to work


with the enthalpy term instead of the internal energy for reasons indicated
I
below. We define heat capacity, C, as 1
C= DQ (2.13)
dT
"'
The heat capacity thus refers to the amount of heat DQ absorbed by a
system which undergoes a temperature change dT. Dividing the terms in
equation 2~5 by dT yieltls
dU _ DQ dV
(2. 14)
dT - dT - P dT

.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

If the pressure is held con sta nt, we


find

(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)

t if the volume of the system is held


Examination of equation 2.5 shows tha
con sta nt
d1J = DQ (constant volume)
.
d.t lis identical to the heat inp ut DQ
and thus the internal energy change
Similarly from equation 2.12
dH = DQ (co nst ant pressure)

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

substanc e can be gained. For purpose s of computa tion, it is conveni ent to Tl


express the heat capacity as an empirica l function of tempera ture. It is
cumbers ome, generally, to attempt to express the tempera ture dependence l
of the beat capacity by a single equation over a very broad tempera ture
range. , I
I
Low-Temperature Specific Heats I
(
I
At very low tempera tures, Cv is approximately given by an expression of
the type 1 I
t

Cv = Cp(Jattice) + Cv(electronic) = K (~J + yT (2.19) II


I
where K is a constan t equal to 1940 Jfmol · K and () is known as the Debye I
I
tempera ture. The first term on the right-ba nd side of equation 2.19 results
from the absorpti on of energy by the vibratio nal modes of the crystal and
the second term is due to energy absorpti on by electrons at the Fermi I I
surface. Inasmuch as the tempera ture is very low and the thermal expansion
coefficient is very small, there is very little change of volume with tem-
perature. Consequ ently at low tempera ture C9 ,....., c,, as will be shown later.
As one reduces the tempera ture toward 0°K, the second term will ultimately 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)

If C 11/T as measured experim entally is plotted versus T\ a line is obtained


which has an intercep t y at 'P = 0 and which bas a slope K()-3. Such a plot
is shown in Fig. 2.6 for VB. Equatio n 2.19 is valid approxim ately up to
0.10; 0, as will be discussed later, is in the vicinity of several hundred degrees
for many substances. Some values of y are listed in Table 2.1 for a variety
of metals.
13
1.3 Tile Eaeh alpy FaD cdoa aDd Hea t C.p adtJ
--~----.---,---~--~
~~--,----r--~----~--~

.. . - -.. ••• •• .• .• . • • •

Cou rtesy of L. E. Toth .


Fig. l.6 Low-temperature heat capacity for VB.

Num ber of Substance,sO


Tab le 2.1 Electronic Hea t Cap acity Coefficients for a
1
>' (mJ/ g-at om · K') Substance , {mJ/g-at om · K )
Sub stan ce

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.

Hig h-T emp erat ure Specific Hea ts


m tem pera ture ) the heat
At high temperatures (normally abo ve roo
an empirical relation of the
capacities of man y substances are expressed by
t~ ' (2.21)
C, =a + bT + cT-1 Jfm ol· K
These con stan ts are strictly
where a, b, and c are empirical con stan ts.
empirica1 and do not have the significance that
8 an4 y have for low-tem-
ety of ~als are liste d
pera ture equations. Experimental values for a vari
d m.p. refer to solid, liquid,
in Tab le 2.2. In Table 22, the symbols s, /,an
of C, and c, upo n T over
and melting poin t, respectively. The dependence
2.7 for cop per. On the scal e
~

a wide temperature range is illus trate d in Fig. I


n from the low-temperature
of this grap h it can be seen that the con trib utio
Tbe Firs t Law of Tbamodynamks
14
Number of Substancesll (J/m ol • K)
Tab le l.2 Hea t Cap acit y Con stan ts for
Tem pera ture
Sub stan ce a b X lOS C X to-a Ran ge( K)
~ .
8.55 1.50 298 -m.p .
Alf..s) 21.2 '
m.p.-1600 I J
Arf..f) 30.5
64.4 298- m.p.
AgBr(s) 33.1
4. 19 -11 .3 29~m . p.
AgCI(s) 62.1
11.9 -10 .2 298-1000
BCJ,{/) 70.4
23.1 -40 .2 298- 1670
CaT iSi06(s) 177
167 0-1 8ll
CaT iSi06(/) 279
34.2 -11 .3 298-848
Si02(qu anz ) 46.9
16.2 -25 .8 298- 1500
Mn Si03(s) 110
don,
From Kuba.schewski et al., Mda llur gica
l Thennocltemistry , 4th e.d., Perg amo n, Lon
1967.
G

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.

l..C HEATS OF FORMATIO N

One of the limitations of thermodynamics is that absolute values of many


thermodynamics quantities cannot be obtained. As a result a reference
state is needed so that quantities can be given in terms of the difference
between the state of interest and the reference or standard state. The particular

Table 2.3 Standard States

Usual Standard States fo r Heats o f Reaction

Solid The most stable form of the element at one atmosphere


pressure and the temperature specified
Liquid The most stable form at one atmosphere at the temperature
specified · ·
Gas One atmosphere pressure' aod the temperature specified

choice of a standard state is therefore arbitrary. The most generally used


standard states for solids, liquids, and gases from the point of view of
convenience are listed in Table 2.3.
It is clear from Table 2.3 that the standard state depends upon tempera-
ture. For example, tin has two aJiotropes. Gray tin is stable below 286°K.
and white tin is stable between 286°K and the melting point. Thus the
standard state for tin would change from the gray tin form to white tin as
the temperature becomes greater than 286~. In some tabulations, however,
diamond is used as the standard state for carbon even though graphite is
the stable allotrope. One must be careful, when us4tg data from various
sources, to see that the standard states are the same. -
It is convenjent to list values of the heat of formation (or enthalpy of
formation) of species at a standard temperature . The common practice is
to use 298°K as the reference temperature. Some typical values of heats of
formation are listed in Table 2.4. The symbol /::Jl1° refers to the enthalpy
or beat of formation of the phase from elements in their standard states at
298°~ The superscript r>refers to standard state.
The values listed in Table 24 are relative to the standard states listed in
Table 2.3. Writing the chemical reaction equation, for the formation of
16 The First Law of Thermodynamics
4
Table 2.4 Heats of Forma tion at 298° K

Subst ance llH1° (kJ/m ol) Substa nce llH1° (kJ/m ol)

Sn (gray) -2.1 H(g) 218


Sn (white) 0 MgO(s) -600
AgCI(s) - 127 Mo02(s) -585
A~0 3(s) - 1670 Si02(quart z) -910
GraP-hite 0 MnSi 0 3(s) -246
Diam ond 1.90 MnO( s) - 384
O(g) 249

Kubaschewski et al., Metallurgical Thermochem istry, 4th ed .,


° From 0 .
Pergamon, London, 1967.

MnS i03 , we would obtain ~· '


Mn{s, 298°K , I atrn) + Si(s, 298°K, 1 atm) + j-0 2 (g, 298°K, 1 atm)
= MnSi 03 (s, 298°K , 1 atm)
when
In the future, the notati on {I atm) in paren theses will be disreg arded
restri ction
solids and liquid s are involved. It will be under stood that this
refers
exists, howe ver. The super script for ll.H/ denot es that the value
0

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.

2.5 HEAT S OF REAC fiON


throu gh
Since thermodyna mic functions are state prope rties, the path
and final
which we achie ve a given reacti on is unimp ortan t. Only the initial
on may
states are impor tant. As 'a resu1, , the entha lpy for a partic ular reacti
involved
be obtai ned from the algeb raic sum of the appro priate reacti ons
in heat of forma tion reactions.
IDustr ation 1
Problem. Find the entha lpy of the following reacti on at 298°K and 1 atm
press ure.
MnS i01 (s, 298) = MnO (s, 298) + SiO:t(quartz, 298)
Soluti on. To find tllr for the reacti on, the stand ard entha
lpies of
MnSi O,
forma tion of MnO and SiOt are added togeth er and that for
2.5 H eats of Reaction 17

sub tracted, using da ta from Table 2.~:


(J) Mn (s, 298) + i0 2 (g, 298, 1 atm) = M nO(s, 298)
(D.H,0) 1 = -384 kJ
(2) Si(s, 298) + 0 2(g, 298, 1 atm) = Si02 (q uartz, 298)
(6. 11/h = -9 10 kJ
(3) MnSi03(s, 298) = Mn (s, 298) + Si(s, 298) + ~ 0 2 (g, 298, I a tm )
(D. H/ h = 246 kJ '1.
Adding these together yields t he desi red reaction V
tl fl 0 = - 1048 kJ

The va lues o f tl H / listed in Ta ble 2.4 represent enthalpies .of reactio ns


involv ing reactions between elements at 298° K. Generally, however, il is
of interes t to know t he enthalpy of reactio n, tl H 0 , at a temperatu re different
from 298°K .
For a substance of a give n composition , its en t halpy is a functi o n of the
sta te variab le ofT, p, and V. These variables a rc no t independent, however,
since an equatio n of state is assumed to ex ist which relates the volume to
the external pressure a nd temperature. For a crystal, we mus t add the
additional restriction that the crystal is in its lowest energy s tate, i.e., that
defects such as g rai n boundaries, excess vacancies, dislocations , are not
impo rtan t. If th is restriction is not placed (at least in principle) the vo lume
will be inRuenced by histo ry and wi ll not be a state property. Since there is a
relatio n between V. p , a nd T, o nly two ca n be co nsidered as indepe ndent
v a ri ub l ~s and thus according to general mathema tica l prin c ipl e~. the thermo-
dynamic va ri ab les themselves can also be exp ressed as functions o f any two
of .the variables. Thus D.H 0 = f( T , p), f( T, V), or f(V, p). The cho ice of
which functio nal relat io n to use depends upo n the particular situatio n
being consid ered . Using H = f( T, p) we obtain , using the basic theo rem of
partial difi'e rentiation,

dHo = (oHo\ dT + (oHo) dp


ar },} aP r
Since C p = (o H 0 fo T)1J a nd the press ure is constant, we obtai n

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

Now bri ng both prou ucts and reactan ts t o SOO"~ K algebraically.

(2) M nO(s, 298) = MnO (s, 800) 800


H 8oo- H ~os = 1 298
(C,J2 dT
I
I,
(3) SiO ls, 298) = Si0 2(s, 800) l

(4) MnS i0 3(s, 800) = MnS i03 (s, 298)


-CH:uo - ll~os) = -i 800

298
(Cv)4 dT

the desi red reaction


Add ing reac tions I thro ugh 4 yield s tl_1e enth alpy of
and is given by I
.I
·soo 1
+ ((CJJh + (C,h - (Cp)4] dT
D.H To = (llfl
0
h 98
J
20S
l 800T
I

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, •

In man y case s, one or more of the com pone nts of a


reaction undergoes
,I
a phas e chan ge between 298° K and the temp eratu
· were the case in the previ ous illust ra ti on the heat
re of interest. If this
capacity o f the low.
l
een 298° K and lhe
temp eratu re form of the subs tanc e would be uscu betw

:!
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

+ } Cl2 (g, 298, I atm) = AgCI(s, 298) 1:1 11I 0


(1 ) A g(s, 298)

Using the algebrai c approac h, we obtain

(2) AgCI(s, 298) = AgCl(s, Tm.vJ

(3) AgCI(s, '/~ 11 • 1 ,.) = AgCI(I, '1; 11 , 1, )

~4) AgCl(/, Tm.pJ = AgC I( I, 1300)


(5) ACI2 (g, 1300, I ul m ) = &C1 2 (g. 298, I alm )
2118

-( ll ~aoo - fl ~us) = i
1
I:JOO
Cv dT

(6) Ag(s, 7~P.) = Ag(s, 298)

(7) Ag(!, T.n.11 .) = Ag(s, T.n.11 )


2'rn . p.
(8) Ag( /, 1300) = Ag(/, Tm. 1,.) -(Hraoo - 1/m.pJ = J:
1300
(CD) 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

re 298° K to temp erat ure


brin ging a subs tanc e from the stan dard temp eratu
T, the follo wing appr oxim a tio n may be emp loye d
7'
0- ell ciT ~ c,,(T - (2.22)
If 7• ~~~us =
J:
!!DR
298)

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,,

joules per mo le.


K as accurately as possible.
2. Calculate !::.H for the fo llowing reaction at 800°
0

3 AgCI (I) + B(s) = BCI3 (g) + Ag(s)


heat of fusior. is 124 kJ/mol.
3. The melting point of CaT iSi06 is l673°K and the
CaJc ulate the heat of fusion at 1073 ° K.
4. Consider a well-insulated calorimeter. A
heating clement is situated in the
n passage of 1.00 ~ of
..,
calorimet er which has a resis tance of 100.0 n. Upo
current for 75 min, a temp eratu re change of +0.4
of crystal A in the ex state which undergoes an allo
7.° K occu rs. A 5-g samp le
tropic phase trans form ation
.,
is placed in the calo rimeter. Upo n reaching the phas
e trans form ation temp era-
and a sudden temp eratu re
.,
ture, o: transfo rms Lo the high-temperature {I form
drop of 0.16 °K occu rs . Calculate the heal of
transformati on. Assume the
•t
molecular weight of A t o be 106.
e be represented by an
'>< 5. Could a polycrystallioe array of a particula r phas
equation of state ? ti
of0.5 J/m2 , calcu late the work
6. Given a liquid phase whic h has a !\urfa ce tension -;:,
from the form of spheres
done by the system if a mole or liquid is converted
0. I mm in diam eter to a thin film I /tm thick.
ity of 103 kg/m3 , a molecular
~ l
7. Suppose that the material in Problem 6 has a dens
l · K, and that the process
v.eight of 102, and a heat capacity of C 71 of 2 9 Jfmo ·: I
re change of the system.
is performed adiabatically. ·calcu late the temperatu
8. A cylindrica l specimen of Pd which is 0.3 m
in length and which has a radius
at one end of the sample
of I0- 2 m is suspended in a G ouy appa ratus. The field
is 103 Oe and at the othe r end is zero. Calcu late the
to tal force in newton s on
d. Assume that the susce ptibility
:J
a thin threa d on whic h the samp le is suspende
3
of Pd is 6 x 10 -~ cm /g.
3
..,.. .. . ··-.

The Second Law of


; ..,
I
Ther mod ynam ics

3.1 DEFINIT ION OF ENTROPY

The second law of thermodynamics is extremely important from the


standpoint of predicting whether a given reaction will proceed. The critcrio'\
of the sign ·~r the ~nthalpy change of a reactjon is not sunicient as one might •.
intuitively. t~ ink. For example, consider the enthalpies of formation of white
and gray tin listed in Table 2.4. If we consider the transformation
Sn(white, 298) = Sn(gray, 298)
implying that
. .. are evolved in the reaction as written,
we find that 2.1 kJ/mol
\

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.

dS = dS...) IJt + dSaurr (3.1)

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

entropy change for a system undergoing a reversible process is given by


t
dS = i
0
(JJ)
l
where DQ is the amount of heat absorbed reversibly by the system !at
temperature T. For a system that has its temperature cha nged from Tt to t1"•
in a reversible las'hl'or;-· f
llS = (T:t DQ (3~.3)
Jr1 T ~ ·
ln spite of the fact that DQ is not a sta le property it may be shown that the
ratio DQ/T is a state property. To illustrate, consider a reversible process
which involves an ideal gas. For a mole of ideal gas
pV = RT (3.4)
and , writi ng the first law in differential form, ·
dU = DQ- pdV (1.5)

Expressing U = f(T, V) yields

dU = (au)
ar vdT + (au)
av c~v 1·
(3.6)

For a perfect gas, the term (oUfoV)T = 0 and thus


dU = Cv dT (3.7)
Substitution of equations 3.7 and 3.4 into equation 3.5 yields

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\

v Fi~. 3. 1 Illust ratio n of a Carn ot cycle .

com pressed isothermally


gas is then placed in contac t with rese rvoi r l and
reservoir. As a fourth step
in orde r to release a q uantity o f heat DQ to t he
ir and co mpressed adiaba-
the gas is removed from cont act with the rese rvo
esen ts th e Ca rnot cydc
ticall y un til T 'J. is ugai n reac hed. Th is r roccss repr
that lhe entr opy changes
and is illustrated in Fig. 3. 1. The read er may sec
associated wit h the fo ur steps are as follows.
Step Reservoir I Reservoir 2 Gas

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.

3.2 ENTROPY CALCULATI ONS FOR VARIOUS PI{ O CESSES

Entropy of Isotl1ermal P hase T ransitions

Consider a reversible phase transitio n suc h as the conversion of gray tin


to white tin. The transformation temperature is 286°K and hence thi s
process occu rs reversibly o nly at 286°K . At a ny o ther temperatures a t
constant press ure , it is impossible to carry out the process reversibly. Co"nsider
further that the·.process occurs at constant pressure. Since
H = U + pV
and since the process is occurring reversibly, this function may be differen-
tiated:
dH = dU + p dV + V dp (3.11)
Substitution of equation 3.5 into 3.11 with the restriction of consta nt
press ure yields
DQ = dll
Thus from (3.2) we find that
dS = dH (3.1 2)
T
and integrating at constant temperature
white
dS = -
1 Lwhltcd /1
L~trtl~' T ~e rn y
we obtain

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 = dll (3. 12)


T
pro cess
As sho wn in C hap ter 2 for this ty pe of
= Cfl dT (3. 13)
dH
lind for the entropy cha nge of
Subs ti tu tin g eq ua tion 3.1 3 into 3. 11 , we
the sys tem
c (3. 14)
dS = - 1' d T = C, d In T
T
be exp ress ed as an ana ly tic fu ncti o n
Sinc e, as disc usse d in C hap ter 2, C 11 may
ned by integ rati on of equ atio n 3.14.
of tem pera ture , !::..Scan be read ily obta i
the s urro und ings to the syst em,
Since the enth a lpy is bein g tran sfer red by
rou ndin gs) and hence
it is clear that DQ (sy stem )= -D Q (sur
dS(syst em) + dS( s urro und in gs) = 0
in agre eme nt with the seco nd law .

Ent ropy Change for uu Irre vers ible Pro cess

As po inte d ou t prev ious ly, the r elat io n

dS = DQ
T -
26 The Second Law of Thermodynamics

is valid only for a reversible process. To illustrate further the calculation or


the entropy change for an irreversible process , consider the freezing of a
supercooled liquid. We have the following reaction at temperature T 1 < 7 111 • 1,,.
A(/, T 1) = A(s, T1) - L1
For a process such as this it is impossible to freeze the liq uid reversibly,
since the criterion of reversibility implies that at any instant during freezing,
the process may be reversed by an infinitesimal opposing stres.s. Once a
supercoo led liquid begins to freeze, it is, of course, impossible to reverse
the process by a n infinitesimal stress (i.e., in fi nitesi ma l cha nge of tem-
perature). To reverse the process would require bringing the temperature
above the melting point. If the supercooling is substantia l, th is change in
temperature is certainJy not infinitesimal. On the other hand , the situa tion
is considerably different for the surrounding (i.e., heat reservoir). During
the irreversible process described here the system evolves a n amo unt of
heat L1. lf the reservoir is sufficiently large, the quantity of heat L1 is trans-
ferred to the reservoir wi th pnly an infi nitesimal change in temperature.
Thus it may be considered that' the surroundi ngs have a constant temperature
T 1 . Furthermore the heat, even though being evolved spontaneously from
the system, may be transferred in a reversible fashion to the reservoi r. It
should be emphasized that the criterion of reversibil ity means that the process
may be reversed by an infinitesimal stress. If the reservoir is large compared
with the system the beat content of the reservoir is large compared with the
system. Let us now apply an infinitesimal stress to the reservojr (i ncrease
the temperature by an amou nt dT). Beca use of the dirTercncc in size of the
reservoir and system, heat will now flow out of the reserv oir a nd thus may
readily stop the former process. As a res ult, the entropy change of the
surroundings may be calculated directly as done previously, but that for
the system may not since the criterion of reversibility is not met in this case.
Since entropy is a state property, we may , however, carry the system through
several reversible steps and finally reach the end result. Each step, however,
must be capable of being carried out, physically, in a manner approaching
reversibility.
For the reaction under considera tion the following steps arc the obvious
ones: (a) liquid A is transfer red reversibly from T 1 to Tnql. ; (b) at T111 • 11 • the
liquid is allowed to freeze reversibly; and (c) solid A is brought from T10 . p .
to T 1 • Thus
( 1) A(/, Tt) = A( /, Tm.11 J ~s~

(2) A(/, T;n.p.) = A(s, Tm.1,.) b. Sa


(3) A(s, T.n.11 .) = A(s, T1) ~s3

(S um) A(/, T1 ) = A (s, T 1) ~s11ret.


Entropy Calculations for Various Processes 27
3.2

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

/lSl = r Tm.p . ( C1,), dT


JTI T

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 ,
~

If we kn ow L1 , therefore, we shall be able to calculate !1S.,urr· Generally,


howeve r, L1 is not known experimentally at T 1 since it is genera lly measured
experimentally only at the transfo rmatio n temper ature, Tm .p.· We may find
L 1 at T 1 readil y, however, by use of heat capaci lies. Conside r the three steps
discussed above to have enthalpy changes /J.J-/1 , ~H2 , a nd !:lH3 associa ted
with them. By summation it is fo und tha t

and by using principles already discussed

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

Substit ution of ~::!a , fib, a nd fie yields


0
L1 = 11.4 kJ / mol
As a result D
A
uSsurr = -L, = + 11,400 = + 10.6 JImo I·K 0
TL 1073
and the entropy change of the universe is equal to 0
~SAg+ ~Ssurr = 1.4 Jjmoi·K
From the illustrati on , we see that the s um of the entrory cha nge of system
and surro wtding is greater than zero as required for an irreversible process. ..f,

3.3 SOME USEFUL RELATIONS OBTAJNEO


FROM THE SECOND LA\\'

Relation between CJI and Cv

It will be recalled that Cf) = (oH foT),, a nd Cv = (oUf oT) 1. , so it wi ll be


desirable to obtain a rela tion between (oH fo T) 71 a nd (oUfoT)v· It seems
29
3.3 Some Useful Relations Obtai ned from the Second Law

reaso nable to start with the defin itio n o f entha lpy :


li =U + pV
and on diffe rentia tion
dH = dU + p dV + V dp

If we divid e the abov e equa tion by dT,


dJ-1 =dU +pd V + Vdp
dT dT dT dT

Placing the restri ction of cons tant press ure we have

(aH) _ (au) + P(av ) (3.15)


aT ar
p - ar 21 21

We are inter ested incau;aT)v , so it will be necessary to eliminate (aUjoT) 11

in favor of (oUjaT)v . To do this let us express U = f(V, T); thus


d U = (au) dV + (au) dT
av T ar,
Dividing throu gh by dT and keepi ng p co nsta nt , we find

(:~). = (: ~t (:~t + (:~t (3. 16)

Subs tituti on of equa tion 3.16 into 3.15 yield s

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)

and subtr actin g eq uatio n 3. 19 from 3.18 we find

tis = .!. (au) dT


T aT v
+_!_T [(au ) + PJ d v
- aV ·r
(3.20)
MIS a . I O CIE iW¥ &
------~--------~ ~

30 The Second Law of T hermodynamics

Equatio n 3.20 is expressed in terms of dT and dV. Let us now expand


S =f(T, V).
dS = (as) dT + (as) dv (3.2 1)
ar v av T

By comparison of coefficien ts in equatio ns 3.20 a nd 3.21 we sec that

(as)
arv=
1 (au)
T aT v
(3.22)

and

(as)
avT-
__!_[(au)
r av
+ J
P T
(3.23)

The second derivative o f 3.22 with respect to volu me at constan t temperature


and the second oerivative of 3.23 with respect to temperature at constant
volume are equal since
a2s
-
a2s •(3.24)
ar av av ar
and therefore
a (as)1 a (au)
oVoTv=TaVoT v
a nd

:A~~)T ~:A~[ e~t + p])


In view of equatio n 3.24 we find
...
_£_ (0U)
1_T av _£_{1_U0U)
_ ar r av
+ ])
arJ7- P T

and
lr avo•uar-_l[ o•u + (opar ) J_..!..[
r ar av T2 av v
(ou) + J T P
Thus
I

[(~~)T+ PJ = r(~~),, (3.25)

In this way, we have elim inated (oUfoV)r in favo r of (apfoT),, wh ich by


experience we know ca n readily be expressed in terms o f easily measurable
q uantities. Thus V = f(p, T) and

dV = (aV\ dp + (av)
ar ,,
dT
ap J1,
! 3.3 Some Useful Relations Obtained from the Second Law 31

Dividing this expression by dT and holding V constant yields

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)

Substituting 3.26 in to 3.25 and thence into 3.17, we ha ve


C = C + cx.zVT (3.27)
11 v fJ
Eq uation 3.27 shows that c,. may be obtained from C,, of the mola r
volume, compres sibility, and thermal expansion coellicicnt a re available
I. for a substance. For a solid, the heat capacity at consta nt volume, Cv. is
I generally more difficult to obtain experimentally than these particular
t phys ica l paramet ers whic h arc ()b lai ned from s tandard labqralo ry ex pe rime nts.
[n Table 3. 1 are shown calculated values of Cr· for copper based on experi-
mental val ues of C,, p, V, and ex. at various temperatures.
Table 3. 1 Various Properties for Copper"

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

Hill, New Yo rk, 1957.


,
I
32 T he Second Law of Ther mod ynam ics 1
es oc and {3, as well as the
Exa min ation of Tab le 3.1 indi cate s that the valu
erat ure. It is no ted also that
heat capa cities, are rath er depe nden t upon temp
val ues as T - 0° K. This
oc as well as the heal capa citie s app roac h zero
ter. It mig ht be poin ted out
featu re wi ll be exam ined furth er in the next chap
{3, V, and the heat capa citie s
at this time that the pres su re depe nden ce o f oc,
ple, an inc rease in hyd ro-
a re norm ally quit e low. For merc ury, fo r exam
7
kg/ m 2 at 273° K cha nges «
stati c pres sure from atmo sphe ric to 5 x 10
from 181 x 10- 6 K- to 158 x 10- o K- (12.6
1 1 %), P from 3.88 x 10- u
27.9 Jfmo i·K to 27. 5
m2/N to 3.38 x I0- 11 m / N ( 12.9 %), a nd C1l from
2

Jf mo l·K (1.4 %).


Jllus trati on
Problem . Calc ul ate t he wor k don e by the syste m for merc ury whe n the
7 m • Calculate also the heat
2
exte rna l pres sure is chan ged from 0 to I 0 kg/
inter n al energy.
flow out of the syst em as well as the chan ge in
Solution.
t

At cons tant T
- dV = (av\ dp -pv dp
=
()p. JT
Ther efor e

w= -1 v 71

f3 p d p

l f the sma ll pres sure depe nden ce of V and fJ is negl ecte d

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

For a reve rsibl e proc ess


dS= DQ
T
Ther efor e
DQ = -a.V Tdp .
J
and
Q = -~VTp
3.3 Some Useful Relatio ns Obtain ed from the Second Law 33

Substi tution y ields


Q = -68 Jf mol
mole
We observ e that the surrou ndings have perfor med 2.7 J of work on a
ents
of Hg but 68 J has been release d as heat! The differe nce, of course , repres
the chang e in interna l energy of the system with press ure
6.U = Q - W = -68 Jf mol + 2.7 Jf mo l = -65.3 Jf mol

Therm oelasti c Elfcct

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

Since Q is consta nt, DQ is zero and


dU = -pdV
Expressing U = f(T, V),
dU = -pdV =(au) dT +(aav~lr dV
ar v
(3.28)

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

let us express V = f(T, p). Thus

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)

Substituting equation 3.32 into 3.30 and collecting terms, we find

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 \

that continuous temperature measu rement might provide a method of


measuring these stress nuctuations. The recording equipment available is
capable of detecting temperature variations of ±0.001°K. CalcuJate the
minimum stress variations which can be detected by this eq uipment. The
crystal has a density p of I0" kg/ m:t, a molecular weight of I00, a val ue of ex
equal to 4.00 x I0- 6t K , and a heal capacity of 27.2 Jfmoi·K.
Solution. Since the system is well insu lated, eq uation 3.34 may be used
to solve this problem. Equation 3.34 expresses the change in temperature
with respect to hydrostatic pressure applied to the system. Our case here,
however, deals first with a stress of opposite sign and second with a uniax ial
instead of hyd rostatic stress. lt will be left to the reader to show that for an
isotropic substance
3.4 T he Statist ical Interpr etation of Entrop y
35
Bearing in mind the restriction of consta nt Q we may write

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.

} 3.4 THE STAT fSTIC AL rNTEI~PRETATION OF ENTR Ot•Y

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)

• M. Planck, VorleJtmgen ttber die Theorie der WarmeJtrahlung, 1st


cd., Springer
Berlin, 1906.
36 The Second Law of Thermodynamics
1'
where iff' represents the probability that a given state wiiJ exist, k is Boltz-
mann's constant, and S is the entropy contribution to the system due to the
given state. In order to obtain if/, information must be available about the .I
distribution of atoms and molecules in the system of interest; alternatively,
experimental values of entropy may be interpreted in terms of the properties
of the atoms and molecules which make up the system. Until now we have
been concerned with classical thermodynamics. This section introduces the
concept of statistical thermodynamics.
In principle, the properties of a system may be calculated by the sum-
mation of the properties of each individual molecule in the system at a
given time. Obviously, this is a rather hopeless challenge since a normal
system may contain of the order of 1022 atoms or molecules. By application
of statistics this problem can be surmounted, however. For example, as is
well known, the instantaneous pressure of a gas upon the walls of a vessel
can be obtained from a consideration of the velocity vectors of each gas
molecule in box at a given time. It is simpler, however, to calculate time
average quantities. •

Elementary Statistical Concepts

In order to obtain expressions for the entropy in terms of the probabiuty


of a state, some simple statistical consideration will be desirable.
Let us consider first a case where we have, say, eight objects numbered I
through 8, and four boxes. Let us attempt to answer the following queslion:
in how many different ways can these objects be placed in these boxes
assuming that each box is large enough to hold all of the objects? We may
put the object labeled l in any one of the four boxes. Similarly , since each
event is considered to be independent we may do likewise for object 2, etc.
The total number of ways of putting object I in the boxes is four. The total }

number of pbssibilities for object 2 is four, etc., up through object 8. The


total number of ways or complexions of arranging all the balls is therefore
ffi_ 1 4 = 4 . If the objects are put into the boxes in a random fashion,
8

each complexion of the total of 4 8 has the same probability of occurring.


That is to say, there will be an equal probability of finding all eight objects
in box I as in box 2, etc. Similarly, the probability of any one of these
complexions occurring will be equal to the probability of finding balls I and
2 in box l with box 2 being empty and boxes 3 through 4 containing balls
3 through 8, respectively, etc.
In the situations that we will be dealing with (atoms in crystals) we can
differentiate types of atoms. For example, we can in principle distinguish a
gold atom from a copper atom. We cannot, however, disti nguish, within a
given type, one atom from another. The situation discussed above is not
37
of En tro py
3.4 Th e Sta tist ica l Int erp ret ati on
ap pli cab le to ou r cas e: we sha ll no t be int ere ste d in
the refore co mplet ely jec ts
in a giv en bo x, bu t in ho w ma ny of the sam e typ e of ob
which ob jec t is lexion s
h bo x. To illu str ate , let us cal cu lat e the nu mb er o f co mp
are in eac a sta tist ica l
the re are tw o bal ls in eac h box. Su ch a tot al is cal led
for wh ich gin g tw o
we nee d to cal cu lat e ho w ma ny wa ys we ha ve o f arr an
state. Th us ain ing
x I , tw o of the rem ain ing six in bo x 2, tw o of the rem
ob jec ts in bo kin g
etc . Th e firs t ste p is to cal cu lat e the nu mb er of wa ys of pic
i fou r in bo x 3, a
of eig ht for bo x I. Th is can be rea dil y ca lcu lat ed by use of
!J tw o ob jec ts ou t en
sta tes tha t the nu mb er of c9 mb ina tio ns of N ob jec ts tak
the ore m whic h
" at a tim e is given by
N! (3.37)
if!" = Nc n = - - ---
n! (N - n)!
t of a
nu mb er of wa ys of pu ttin g tw o ob jec ts in the bo x ou
As a res ult , the
tot al of eig ht is
C 2 = _j_L_ = 8 X 7 = 28
8 2
2! 6 /
of tak ing
six ob jec ts lef t. Th ere fo re tl1e nu mb er of co mb ina tio ns
W e ha ve
ing six for bo x 2 is
tw o ob jec ts ou t of the rem ain

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

Therefore the probability p of ou r statistical state is

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.

(N0 - 11) A+ nB = Solution[(N0 - n) A , nB]

and is known as the entropy of mixing /iS,. Thus

D.Sm = SA.D- SA- So


3.4 The Statistic al Interpre tation of Entropy 39
SA Sa

Component A Component B
(No - n) atoms n atoms

/
Soluhon
N atoms

Fig. 3.2 Illustration of a mixing process.

,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

(N0 - n)! JJ!


J
I
40 The Second Law of Thermodynamics

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

llSm = Nok[.!!_ In No+ No-" In


N0 11 N0 N0
No
-
J
n
Definjng atom fractions XA and X 8 as [(N 0 - n)/N0 ] and (n/N0 ), respectively,
(3.42)
Equation 3.42 is the well-known .. entropy of mixing'' equution. which will
also be derived in a later chapter by use of classical thermodynamic s. )
From the previous discussion we can see that entropy is associated with
the concept of randomness. The more random we make a system, in general,
the higher the entropy will be. Also our discussion thus far has been con-
cerned \\'ith mixing randomness. There is another type of randomness which
is of interest in the study of the properties of crystals. This we wiU calJ
vibrational randomness. In a c rystal each atom is vibrating about a given )
position and hence there is a rand om ness associated with the position of an
atom at a given time. If we co nsider that each atom is mo ving in a cell, we
should expect the vibrational randomness to be related to the volume of the
cell. The larger the volume of the cell, the larger will be the rand omness and
hence the larger will be the entropy. The diameter of the cell would be )
expected to be proportional to the amplitude of vibration of the atom. This
entropy contribution 'shall be designated by s'l .
Consider the previous discussion. Suppose that A and B had atomic sizes
which were considerably different. Upon formation of a solid solution, t '

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.

Population of Energy States

Up to this point only mixing randomness has been considered in any


detail. Suppose now instead of being concerned with the entropy of a mixture
of various atomic species, we consi,der an entirely different problem. Let
us consider a molar volume of pure crystal. The N 0 atoms in the crystal
have a total energy U. A lithe atoms do not necessarily have the same energy,
however, since thermal fluctuations will occur in the crystal. Let us consider,
however, that discrete energy levels exist in the crystal as shown in Fig. 3.4
and that atoms can have only these discrete energies. In other words, an
atom may exist with energy E 0 , E1o etc., but may have no value in between.
This corresponds to a quanliz~d state. The question then arises as to how
many atoms occupy each state. One might be tempted to argue that the
crystaJ would seek a minimum energy: aU atoms having energy Eo and the
42 T be Second Law of Thermodynamics

f4 ------------ ---------
ta---------- -----------

f2---------- -----------
i
u
fl---------- -----------

to---------------------
Fig. 3.4 Quantized energy levels.

total energy being given by U0 = N0 E0 • Such an argument, of co urse, neglects '


the entropy consideration. The energy states corresponding to E0 , E 1 , E2 1 • • •

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 ••• ,

n 0 , n 11 n 2 , • • • , n.. atoms. Then Sis given by

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)

The internal energy is constant, however, if o ur crystal is at a constant


temperature and volume. Thus U is independent of the value of "• and
r
dU = 0 = 2>: dn
i- 0
1 1 (3.46)
3.4 The Statistical Interpretation of Entropy 43

Since at equilibriu m S is a maxim um, dS = 0, or

dS 0
= = -k ±(1 + In ~)
t- o N0
dni (3.47)

Furthermore, the number of atoms is constant so

(3.48)
and
r
·0 = 2 dtti (3.49)

Substituting equation 3.49 into 3.47, we find

dS =0= - k ' ln .!!J_ dn .


.£... No •
(3.50)

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

fc = !!J._ = exp ( -£a/k T ) (3.51)


N0 L exp ( -£dkT)
{

The denominator of equation 3.5 1 is known as the partition function !Z.

1£ = L exp (-
i
.!1_)
kT
(3.52)

The numerator in equation 3.5 1 is known as the Boltzmann factor.


lllustration
Most solid-state reactions such as diffusion involve an activated state.
That is, an atom, in moving from one site to another, must pass over an
energy barrier of height 6U as shown in Fig. 3.5. The average energy of an
l atom in a normal lattice is U, . In most cases, the energy levels are so close
to one another that a continuous curve may be used to approximate the path
as shown in Fig. 3.5. The purlition funclion :!£ may then be expressed as

~= It exp ( - .!i.)
kT
= r exp ( -
Jo
00

.Y_)
kT
dU = kT

For our calculation not only those with energy


I u?. between u'l. + dU will
44 The Second Law of Therm odynam ics

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

f(U) dU = exp ( -Ufk T) dU


LCl) ex p (- U / k T) d U

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)

Similarly the fractio n of atoms having an energy between U 1 and oo is given


by <O •

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

f* = exp (- ~~) (3.55)


45
3.5 The Free Energy Function
Actually
where flU is know n as the activa tion energy fo r the process.
that the
equation 3.55 is not completel y rigo rous since it was assumed
y. This
number of states available at any energy is independent of the energ
nt. •
is not actually so and entropy consi derati ons must be taken into accou
When this is done equation 3.55 becomes

f *=ex p -flS exp ( -flU)


- (3.56)
k kT
3.56
where flS is the entro py change associated with the process. Eq uation
this
is very impo rtant and we sha ll refer to it throu ghou t the book . From
y state
equat ion, it is seen that the frac tion of particles in a high energ
ases
increases exponentially as the temperature increases a nd decre
ins the
exponentially as the activation energy increases. This equat ion expla
physical
reaso n for the _exponential increase in the rate of chem ical and
les in
reactions as the temperature is increased, since the fraction of partic
to react,
the excited sta te, and consequently the num ber of particles able
increases in the same way.

3.5 THE FREE ENE I~GY FUNC TION

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 shown previously, under isobaric co nditions DQ = dH and


dH
dSsurr = - - (to syst)
T I
dSsyst > dH
- (to syst) I
T
or
\
dH <T dSsyst
or
dH - T dS~~·~~t. <0 (3.57)
Equation 3.57 shows that, for a spontaneous reaction , the enthalpy change I
of the system minus the absolute temperature times the entropy change of i.
the
,.. system is less than zero. Similarly for a reaction at equilibrium, it
foLlows that
dH- TdSaytJt = 0 (l-58)

For a process that ca nn ot proceed

dH- T dS8 y at. >0 (3.59)

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) ~

is known as the Gibbs free energy, dG. Thus I


I

dG = dH- TdS (3.60) 'f


and integra ting yields
G = H- TS (3.6 1)
I
If a process were considered at co nsta nt volume instead of constant pressure, r
)
the relatio n would be (dU- T dS) and it is convenient to define this as the l·
Helmholtz free energy dF. Thus

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

Since dH = dV + p dV + V dp, we obtain upo n substi tutio n


dG=dV+pdV+ Vdp - TdS-SdT
From the first law, dV = DQ - p dV , if only mecha nica l work is being
co nsidered, and o n substitutio n
dG = DQ + V dp - T dS - S dT
'
l f we a re co nsidering a reversible process, we have fro m the seco nd law
dS = DQ/ T, and on substituti o n for DQ in th e equa ti o n above we find
dG = V dp - S dT (3.63)
Simila r steps for the Helmholtz free energy yield
dF=-pdV -SdT .
(3.64)
lt must be emphasized that equations 3.63 and 3.64 a re valid only fo r
reversible processes.
Dividing equation 3.63 by dp and ho lding T consta nt gives

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)

The reader may show that under reversible co nditi o ns

(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,

= .!.(oH) + H[o(l/T)J _ (as) l


[a(G/n]
oT T oT oT oT
(3.72)

By definition
f) f) 11 ll
I
(3.73) I
. ~
Also .
'
o(l/T>J = _ _!_ (3.74)
[ oT JJ T 1

and from the second law


ds
DQ _ dll,,
-_ -
T
--
T
(3.75) '
~
I
Thus C 7 dT = T dS and upon rearrange ment
.I
(as) =
oT, T
C11 (3 .76)
l

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'

or for u reaction having a free energy cha nge

[o(~G/ T)J = ~H
o( I/D ,
(3.78)

Thus if (~G/ T} is plotted ve rsus the reciprocal of absolute temperature,


the slope is equal t o~ // . Ey ualion J.7H is important holh in thermodyna mics
and ki netics. Some idea of the general usefulness of the free energy function
,should already be apparent to the reader. By measuring the varia tion of
~G with respect to temperature at constant pressure, the entropy change
of the reaction ~S may be obtained at a ny temperature from the slope.
Similarly if ~G/ T is plotted versus the reciprocal of the absol ute temperature
at consta nt pressure , the slope is eq ual to the enthalpy change for the
reaction , and if 6(i is plotted versus pressu re, the slope is c4ual to the
volu me difference between products and reactants. A very useful applica tion
of the free energy concept, which pertains to calculations of the equilibrium
constant, will be discussed in a later chapter.

Maxl\'·ell's Equations

Consider the following four equations derived previously, which are


applicable onl y under r~versjble conditions.
dU = TdS- pdV
dH= TdS+ Vdp
dF= - pdV -SdT
dG = Vdp- SdT
As shown in Appendix B, so me relations may be derived from these
equations which are ve ry useful in manipulation of thermodynamic quan-
tities. These are known as Maxwell's equatjons. From the first equation,
,.... ..
50 T he Second Law of Thermodynamics

one may show that

- (~~)•. = (:~t (3.79}


From the second equation

(3.80)
From the third equation

(~~t.= (~~).. (3.8 1)

and from the fourth equation


ov)
(oT -(as)
,.,= op 1·
(3.82)

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= (~~)T (3.83)

Table 3.2 Summary of T hermodynamic l~ clations4

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

where, it will be reca lled , M, the magne tiza ti o n , is analogous t o V in the


work term , and H , the mag netic fi e ld intensity, is ana logo us to -p. Other
relations for electrical work , etc. , may be obtained.
So far many important thermodynamic re lations have been derived.
There are many m o re relations which can prove useful in particular c irc um-
s tances. Li s ted in Table 3.2 arc so me of these. All symbols used have been
previously defined.

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

equation 3.78 fo llows from equation 3.77.


9. By use o f a n emf technique the free energy of a reaction 6G may be directly
obtai ned. Suppose that values o f 6G a re obtained fo r a particu la r reactio n
at several tem peratu res. Dy curve fitting it is found tha t the following equation
fits the data over the temperat ure range s tudied :
6.G = - 1,680,000 - 16.6 Tiog T + 368T 1/ mol
Calculate 6S and 6. /l fo r the reaction at 400° K . Will the reaction proceed
spo ntaneously?
10. Calcu la te 6G for the gray tin to white tin transfo rma tion at (a) 286° K,
I (b) 293° K , (c) 278° K. Assume for the p u rpose of calculations th at the heat

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

dG = V ( iv) T dV +[V ( ir)


P - S J
dT

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

the sign of ( llSsyst + llSaurr)?


18. Consider a crystal containing N sites. Let us fill only N0 sites with atoms, ;,
leaving (N - N0 ) vacant. Calculate the mixing entropy change for this s
process.

·)

}
4

Some R elations Betwee11


Thermodyn amic Quantities

'f; 4.1 PROPERTIES AT 0°K (THE T HlRD LAW OF


THERMODYNAMICS)

Consider the Gibbs free energy of a process as the temperature approaches


0°K. The equation for the reaction is

6.G = 6.H- T 6S

Since T _. 0°K , the term T 6S-+ 0 if it is assumed thai 6S is finite. As a


conseq uence, therefo re , 6G ~ 6H as T 0. One migh t ~sk how 6.G
approaches 6 H as T-+ 0. One could envision two paths as illust rated in
Fig. 4. 1. Jn the process illustrated in Part I (o 6Gf oT) 71 r6 0, a nd fo r Pa th 2
(o 6.GfoT)-+ 0 as T-+ 0. Since 6S = (o 6Gf oT), 6S _. 0 as T-+ o for
Path 2. As a co nseq uence it wou ld be very important to know precisely in
what manner !lG ~ l1 H as T nea rs absolute 0°K . Both LeChatelier in the
'*' latter half of ~he nineteenth century and G . N . Lewis in the twentieth ce ntury
attacked the problem without complete success. ln 1902, F . w._. Richards
took a large step toward the solution of the problem inasmuch 1b his wo rk
gave some evidence that Path 2 was the a ppropriate path . Several other
scientists worked o n the problem and the c ulminati o n was reached by
Nernst in 1906 in what is known as the Nernsl heal theorem or the third law
of thermodynamics. This may be stated in t he fo llowing way.*
As the temperature of a system tends to absolute zero its entropy tends to a
constant value S 0 wlziclz is independent of pressure, state of aggregation, etc.
Thus for a given process ~
l1S = 0 at T = 0° K

• A Sommerfeld, Thermodynamics and Sratistica(Mechan fcs, Springer, Berlin, l956.

53
c Qua ntit ies
54 Som e Rel atio ns Between Thermodynami

Tem per atur e-+


h 6H near 0°K. Curve l, 6S ~ 0 as T- 0;
Fig. 4.1 Possible ways for 6G lo app roac
Curve 2, 6S - 0 as T- 0.

rop ies of sub stan ces mu st app roh cb


Thi s ge neral 's tate men t says tha t the ent
n tha t (S0 ) 0 and (SA)o are eyu al to
the sam e valu e at 0°K. Lt doc s nol mea
the sam e. Since, for the pur pos e of ..
zero themselves, but only tha t they are
cho ose any stan dar d stat e, we sha ll
calculating 6.S for rea ctio ns, we may
our reference stat e. Thu s we shall
arb itra rily cho ose (S 11) 0 = (S A)o = 0 as
of co mp one nts from hea l cap acit y
be able to calc ula te "ab sol ute " ent rop ies
dat a at any tem per atu re from the rela tion

ST =
io
TC
T
-.!! dT + S 0
(4.1)

sinc e S 0 is con side red to be zero .


0 as T-+ 0 mu st be app lied with
The crit erio n tha t 6.S for a rea ctio n-+
ed by Pla nck tha t the Ner nst heat
som e disc reti on, however. It was pro pos
ds. Thi s stat eme nt is too rest rict ive
the ore m app lies onl y to cry stal line soli
in the qua ntu m mechanical under-
in view of the recent adv anc es ma de
Ner nst hea t the ore m holds even for
stan din g of gases, whi ch sho w tha t the J
however. To illu stra te, con side r the
gases. H doe s not app ly to sol utio ns,
ated tem per atu re, let us assu me tha t
pro blem of a solid solutio n. At nn elev
occ ur upo n coo ling.
the solu tion is stable. Tw o things may
stituen t in a crystal generally
l . The max imu m sol ubi lity of one con
and in fac t becomes equ al to zero
decreases as the tem per atu re dec reas es
ute cou ld be feasible .
at T = 0. Hence pre cipi tati on of the sol
es wit h respect to the arra nge -
2. Ma ny sol utions ten d to ord er themselv
er tem per atu res . Ord erin g of the
me nt of ato ms on the latlice site at low
ato m on the lattice cou ld occ ur.
4.1 Properties at 0°K (The T hird Law of T hermodyna mics) 55

If complete precipitation or ordering occurs, the third law would hold


because In rr = 0 and hence S = 0, but since at low Jemperatures atomic
rearrangement becomes difficult, a metastable structure could be "frozen
in." The entropy of this system is not zero, since there will be a randomness
or configurational entropy contribu tion as discussed in Chapter 3. For the
th ird law to hold, process A need not occur but the third ,Jaw would also be
valid if process B occurred, even if the ordered state was not the lowest
energy state. The third law does not specify that the system must be in equilib-
rium with its surroundings in order for it to be valid, but only that the system
must be in intemalequilihrium. As an example, assume that a pu re crystalline
solid is face-centered cubic at low temperatures and body-centered cubic at
temperatures above T0 • Suppose that rapid quenching from the high tem-
perature to a very low temperature does not allow sufficient time for the phase
transformation to occur. At low temperatures the process becomes too
sluggish for the transformation to proceed at a perceptible rate. According
to the third Jaw the entropy at absolute zero of the quenched b.c.c. phase
would equal the entropy of the equilibrium f.c.c. phase since the only require-
ment is that internal equilibrium be attained, not equilibrium with the
surroundings. For the reaction
Phase (b.c.c.) = Phase (f.c.c.)
ll.S = 0 a t T = 0. There is an enthalpy difference between these two phases
at 0°K, however, and 6.// ~ 0.
One may illustrate this by considering the entropy of transformation of
various solid phases from o: to {J. At the equilibrium temperature T. ll.S may
be determined readily si nce 6S...1, = L,/ T,.. According to the third luw
6..SI3. .P = 0 at T = 0. Thus if this is true

=J.T C./ dT -f.


7
D.S (T) = Lt ' C/ dT- 6S (0°K)
a.p e T, 0T 0 T a.p

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

Sulfur Rho m bic-


mon oclin ic 369 10.0 0.08
286 7.80 - 0.29
Tin Grey- whit e
49 15.7 0.04
Phosphin e P-a.
264 31 - 1.25
Cyclohex anol P- a.
ibrium, 2nd ed., Cambridge, 1968.
4 From K. Denbigh, The Principles of Chemical Equil

Starting with the definition


!:lG = tJ.H - T 6S

and takin g the total differential, we have


d !:lG = d 6. 11 - Td !:lS - 6.S dT
Dividing through by dT at constant pressure gives

o6.G) = (o 6.H) _ T (o 6.S) _ !:lS


( or , oT , oT ,
At T = 0, /1S = 0, and the product

ar~J, =
r(06 o

if the term (o !:lSjo T)» is fini te. Since )

_(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

Applying the same reasoning to the equation


G = II - TS
selves becomes zero
we find that the heat capacities of the components them
at T = 0. Thu s
(4.2)

·.
citie s 57
4.2 The Tem pera ture Depe nden ce of Heat Capa

By similar reasonin g we may show tha t


Cv = 0 at T = 0° K
Acc ordi ng to Som mer feld 's
Let us exam ine the ther mal expa nsio n coen icien t.
opy at 0° K is not a func tion
state men t of the third law the valu e of the entr
of pressure . The refo re

(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)

me and com pres sibility do


Cert ain othe r prop erties suc h as the mol ar volu
w from ther mod ynam ics that
not appr oac h zero as T-+ 0°K but one can sho

(of3 )=0 at ooK (4.4)


ar 11

wou ld all appr oac h their


Thus the volu me com pres sibil ity and entha lpy
ner as the temp erat u re is
constant va lues at T = 0°K in an asy mpto tic man
reduced.
, C v• C p, and f3 for copp er
One may see the tren ds with temp erat ure for «
in Tabl e 3.1.

HEA T CAP ACI T JES


/1.2
;"'
THE TEM PER ATU RE DEP END ENC E OF
l ' t iiiSII IIII \'II III IIIt', I fi t• fl'lll
If II :wlid llh:-1\l l h:-1 ht'lll tllldt 'l' \' PIH i ilit~ll' pf
#l'"'t ' llh'd "" lht• llll l!'. llllll t k nl
lht• lh'll l l'llpu d lv < '1 - ·
pt'III IIIH' rl s t• I~
(itU/ i>l'), .. As lllt•ll lltlll \'d J'l'f\ 'lhi\ ISI)', lht• \'l dlll' .. r ( ·, j,. 11' 111 wltt•ll /' . (I t\:f
. .L iQ l( f!!'o!·; ·~ 1 • 1 p•n l"'''l•t'llll I In lt' IIIJ' l' l lllu~t· 11 1u I 1s
tho tl'lllj ll'l'll lure ll ll'rL'I I~t· s Nl g ll .Y• ' ,. 1!'
wlill ll dt•t ' lltlll~ . 'I laiN l ' ttllll ihuli1
111 ,
due Ill t'IH'I/ '.V llhll tllf'l fllll hy lht• t ' lllldt
l lttllllh~tnl tilt' PltT IIIIII IP
1111porlu11t l'ro111 lht• ttlllll tlpo l ulof 'pto vltll u /'. l ul111 rnu
struc ture or solids. is very SIIIU II iu lllll~llllud l' ll lld will nol IH di Hl' ll tl!l~d I IIIIIH·r
r, lh c Ileal cnpu cil y iuc.: rca!o.cS
here . As the tcmp cral urc rises SOill CWhal ru r lltc
at a rapid rate and c,. ~ 1' • At a high er t<.;_mpc
3 ralu rc the rate of increa se ol'
------------------------------------------------------------·

58 Some Relation s Between Thermo dynami c Quantit ies

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)

where n,, the number of atoms in state E 1, is express ed by the Boltzm an n


fac tor, equa tion 3.51. Befo re us ing equatio n 3.5 1, howeve r , the partitio n
functio n

!Z = 2:~ ex p ( - 2)
kT
(4.7)

must be evaluat ed . This may readily be done by subs titution of equ;:.1tion


3.57 into 3.54
"Y' = L~ exp [ -
.;£,
, .. o
(n + i)llv]
J.. T
Upon expans ion

~= exp ( - 2:;) [1 + exp ( - ~;) + ex p ( - !~) + · ·-]


The term in b rackets may be put into the fo rm
4.2 Tbe Temperature Dependence of Heat Ca pacities 59

which is of the fo rm ( 1 + x + x + · · ·). This sum is eq ua l to


2

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

and upon substit utio n of equations 3.44 a nd 3.45, we have

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 .._ .

and substitulion into 4.9 gives per osciiJator

F = ~k7:1n ~ i t._,_ (4.10)

This is a very useful equation in the general applicatio n of statistical mechanics.


We may express o ther thermodynamic func tions in terms of !r a lso. For
example, in the case o f entropy

- 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)

The heat capacity is given by Cv = (oUfoT)v. For the case of a simple


r

I
I

ami c Qua ntit ies


Som e Rel atio ns Between The rmo dyn
60
here,
har mo nic oscilla tor bei ng con sidered
2
k ( 11~) exp (hv /kT ) (4.13)
2
Cv = kT [exp (ltv/kT ) - 1]
cap aci ty per osc illa tor. The re are
3N0
Eq uat ion 4.13 exp res ses the hea t
per mole of sub sta nce is
osc illa tors in a mo le of crystal s, so Cv
:t
C - 3 J&:2J e c. / (4.14)
v- -'\. J(e= - 1) 2 •

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£

ulat ed valu es of Cv for diam ond . h•,/k


= 132 0° K.
Fig. 4.2 Exp erime ntal values and calc odu ction to
180 ( 1907). Figu re from C. Kitt el, Intr
Dal a from A. Ein stei n, Ann. Phy sik, 22, & Sons ,
e PhyJ·ics, 4th cd ., Wil ey, New Yor k, 197 1. Oy perm issi on of J ohn Wiley
Soli d Stat
Inc.

and calcul ated Cv va lues is rea son -


Th e agreem ent between exp eriment al
goo d. At a tem per atu re of 0°K , Cv is pre dic ted to be equ al to zer o, and
abl y
hig h tem per atu res to app roa ch 3R , in agr eem ent with exp erim ent . At
at y
r, the agr eem ent is not par ticu larl
inte rme dia te tem per atu res, how eve
rec ogni zed by Ein stei n as bei ng related
sati sfactory. Th e rea son for this was
have the sam e frequency. Debyc
to the ass um ptio n tha t all osc illa tors
4.2 The Temperature Dependence of Heat Capacities 61
analyzed the same problem by assuming that the crystal has a whole spectrum
of frequencies from 11 1 to "m• where "m represents some maximum frequency
for a particular crystal. The distribution of frequencies depends on the
temperature. As the temperature is increased the distribution of frequencies
is moved toward the upper end. Ultimately at some temperature called the
Debye temperature, 0, vi rtually all frequencies wi ll be close to vm; co n-
sequently above T = 0, the Einstein picture again becomes essen tially valid.
The expression arrived at by Debye from ana lysis of the modes of vibration
in the crystal is

(4.1 5)
where
ltv hl'm
y =- and x= -
kT kT
At low temperatures equation 4. LS simplifies to

(4.16)

This relationship is found to be in reaso nab le agreement with experimental


observation for many systems. The situation at low temperatures corresponds
to large values ofx. At high temperatures where ;c <( l, equation4. 15 simplifies
to
Cv"" 3R
again in basic agreement with experiment. Uy use of equation 4.16, experi-
mental values of the co nstant C may be obtained directly for a crystal, and
hence the Debye temperature may be calculated , since

(} = 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 \

Ag 225 Fe 467 Pd 275 J J


AI 418 Si 636
Au 165 Ge 290 Ti 428 I )

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

Fig. 4.3 The relation between Dcbyc


I'
: )
tempera tu re and physical propcrrics of a
solid- Lindcma nn relation . From M . W. I
Zemansky, Heat and Thermodynamics, 4t h
1 3' 4 ed., McGraw - Hill , New York, 1957. Used
with permission of McG raw-Hill Dook
Compan y.
4.3 Gri.ineisen Relation 63

j 4.3 GRUNEISEN RELATION

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)

Jf we changed the volume o f the crystal unde r isothermal co nditions, we


would expect the Debye temperature 0 to cha nge. Therefo re

( (} F '') ((} F") ( (}{) ) (4 .19 )


a v 1· - ao 7' av 1·

We may express the internal energy U and also Fv as a product of Ta nd some


function of Of T acco rding to the Debye approac h

( 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

From application of 4.19 and 4.20

(oaeF.) v = ![o(F./ T)J = u.


o o(t/T) v e
.(4.2 1)

Employing Gruneisen's assumption


e = constant X v-Y
we find that t

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

Differentiation of this equation yields

(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 [

V(m 3/kg) fJ (m 2/N) a (oK- 1) Cv (J /kg·K) y


Substance

Na 105 X J0- 6 15.0 X tO - ll 216 X JO- G 14 X 102 1.0


Cu 11 0.75 49 3.9 1.9
Ni ll 0.54 38 4.6 1.7
Pb 9.1 2.3 86 1.4 2.4
4.4 Some Compressibilit y Relations 65

a substance. Above the Debye temperature C,. is about equal to 3 R


Therefore (J ca n be accurately estimated if"« is known or vice versa.

~4.4 SOME COI\1PRES JHlLITY RELATION

Adj aba tie Co mpressibility

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)

In experiments that involve the propaga tion o f sou nd waves a dilrerent


definitio n is more useful. In these experiments one is in efi'ect measuring the
co mpressibility under adiabatic co nditions. That is to say, no heat is exchanged
during the duration of a pressure pulse. Since DQ is equal to zero , dS is
equal to zero acco rding to th e seco nd law, and thus one in effect measures
the volume c hange with pressure under the constraint of co nstant entropy.
The adiabatic compressibility is defined as

fls =- _!_ (~~) ( 4.25)


v op s
The quantities flr and f3s a re simply related as show n in the illustration below.
Express Vas a func tion of the two state variables p and T.

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

(aav)s (o0 v) + (oaTv) (aT).


p = p a :s
T II p

From Table 3.2 we see that


oT) _ ctVT
(op .") c,,
We also know from equation 3.2 that
C -C «2VT
, - JT + {31-
66 Some Relations Between Thermodynamic Quantities

Upon substitution above we see that

(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,,

Temperature Dependence of the Bulk Modulus

In many materials applications it is necessary to know the moduli of


materials as a function of temperature. Wac htman et al. * have shown
empirically that a large number of inorganic oxides have values of Y(\.ung's
modulus Y 1 that exhibit a dependence on temperature which may be ex-
pressed as

(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

• J. B. Wachtman et al. , P!tys. Reu, 122, 1754 ( 1961).


..,
t Y. A. Chang, J. Phys. Cheu1. Sol., 28, 697 {1967).
4.5 The Magnetocaloric Effect 67
that the temperature dependence represented by 4.28 may be predicted from
I.
thermodynamic ~~ rgumcnts. From thcr111odynamic arguments, it is shown
in Appendix C that
2y 2f7 '
B8 r-.J B~c;o - - Cv dT ( 4.29)
110 o
The values calculated from equation 4.29 as compared to experimental
values are shown in Fig. 4.4 for MgO.

1.70 1-- -- -- 1-- - - - - - - - - - -


- o = 3.1 = 1/a (dIn 11/d1)
- 0 = 3.06= 2-y

-
N
E
~ 1.60 1------J...A~------1-------1
c
>.
"0

-£ 1.551- -- - - - 1 - -- -·...
~

1.45 '--------- L--- ----1---- --J


0 500 1000 1500
Temperature (•K)
Fjg. 4.4 Comparison of theo ry with exper iment for the temperature <.lcpcntlcnce of the
adiabatic bulk modulus for MgO. From Y. A. Chang, J. Phys. Chem. Sol. , 28, 697 ( 1967).
Experimental points from work of Soga and Anderson.

'f' 4.5 THE 1\ilAGNETOCALORlC EFFECT

A very interesting practical application of the second law of thermo-


I dynamics results in a method for achieving very low temperatures. The
.i
I temperat ures obtained are typical ly below I° K and result from ad iabatic
demagnetization of a paramagnetic salt. In a paramc;tgnetic material each
atom or molecule possesses an odd number of electrons and thus each has a
magnetic moment. These moments arc ordered by the pr<!Sence of a magnetic
field . l n the absence of a field. disordcriu g occurs us a result of l h c rm:d
agitation. This disordering results in an increase in entropy since accordin g
to the second law
S = k Jn W + constant
where W can be looked upon as the d_cgrce of randomness in the system.
68 Some Relatio ns Between Thermo dynami c Quantit ies

From quantu m mechanical conside ra tions each atom or molecule has a


spin J , and calclllations indicate that there are (2J + I) levels.* As a con-
sequence, we need to calcula te the number of ways W of arrang ing N spins
among the (2J + l ) levels. From considerations discussecJ in Chapter 3,
this is given by
W = (2J + l)N
and therefore
S = N kIn (2J + I) (4.30)

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

Fig. 4.5 Entropy of a substance as a function of temperature.

be accomplished by ordering the spins. To illustra te, assume that the


temperature of the salt is T2 . A magnetic lield is applied iso lhcr111ally at this
temperature. As a result of the spins become oriented parallel to the field,
J¥ is reduced, and consequently S decreases as shown in Path I. The sa mple
is now insulated from the surroundings and the magne tic field is removed .
The spins will now disorder again and the specimen will regain its equilib-
rium entropy. This cannot be done isothermally, however, since no heat can
flow from the surroundings (DQ = 0 and therefore from the second law

• 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)

For path I , Tis constant, therefore

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

At low values of H, the temperature dependence of M is given by C urie's


law
M = C f-1
T
where Cis a constant. Thus upon substitution

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

For a paramagnetic sa lt at low lcmpcralurc, th e heal ca pacity is calculated


to be given by
A
C=
., - :!.
T
where A is a constan t for a particular material.
70 Some nclations Detwccn Thermod ynamic Quantitit 'S

Upon substitution we calculat e

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.

f 4.6 HEATS OF FORMA TION OF IONIC COMPO UNDS :


BORN-H ABER CYCLE )

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 d is equal to the sum in brackets and is known as the Madelu ng


constant . .91 is 1.748, 1.763, 1.638, and 1.641 for the NaCl, CsCl, zincblende,
and wurtzite structu res, respectively. When the ions approa ch each other
closely a strong repulsive interaction Ur occurs. This repulsive term is not ·.
as easy to calculate as the attractive term. In order to evaluate this term Born
assumed an exponential relation of the type
B
V=
r -,.
X

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)

Substituting equation 4.34 into 4.33, we find

( 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

Placing the restriction of constant temperature,


dV
dp= - -
(JV
Let V 0 be the volume at zero pressure, and therefore the pressure required
to make a small change in the volume from V0 to V' is given by

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

and upon subs tituti on of equation 4.36


w ~ - .! r (vI - Vo) d v
j;' '

{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)

Jt is convenient at this point to intro<.lut:e Taylo r's theor


em whic h states that
interest, then
if a function f(x) has continuou s derivatives in the range of

In our case· U,' = j(V) , and expanding this abou t V = V0 , I


2

U/ = (UI)V-Vo + (V' - Vo)(ddVU,) + HV '- Vo) 2


(ddVU:) + · · · (4.38) i
~
V = f'o V= Vo

At the equilibrium volume V0 , (dUtf dV)v-v 0 = 0. The energ


y change of the
crystal, [U/ - (U,h ·-v 0 ] , is therefore given by
)
U,' - (U,)v -vo r"J !(V '- Vo)2(d2U') 2
( 4.39)
dV r' -J"o

if high-order terms are neglected . This is justified if (V' - V0


of the first law of thermodynamics, dU = T dS- p dV, but
) << V0 . Uy usc
T = 0°K, and
I
I
hence
dU = -pd V or !l.U = -W

Therefore, equa ting 4.39 to 4.37 we find

(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)

where C is a constan t that depends only on crys tal structure. Since

c1u = ("u)
dV dx
(d..c_)
dV
we find , using 4.41, that

Similarly, the second deri vati ve

( 4.42)

We have deri ved a n expression forB in eq ua tio n 4.34 , a nd substituting this


into equation 4.42, and the n 4.42 in to 4.40, we li nd lhal

9Cx0 4
II = 1+ (4.43)
{Jez.#

Thus 11 can readily be evaluated from extrapola tio n of {J a nd x 0 toT= 0°K.


The quantity 11 would be expected to vary with the num ber of electrons in a
given atom. For elements with high atomic num bers n would be expected
to be larger tha n for elements with low atomic num bers. Indeed Pauling
has determined that n is related to the closed shell co nfiguration of a given
ion. For ions having the closed shell configuration of He, Ne, Ar, Kr, and
Xe, n is found to be 5, 7, 9, 10, anu 12, respecti vely. When ions having two
d iO~e ren t con(igurati ons make up a crystal the ave rage should be taken.
Thus for LiF, the average 11 is 6, si nce n for Li+ is 5 a nd for F- is 7.
ln order to obtain ~H5 two more steps a re needed. We have evaJuated
UL at T = 0°K. In order to be rigorous this Ill liSt be co nve rted into (.lll
enthalpy term, which is then brought up to 2{)~" K rro m O" K . These cor-
rections are second-order terms for our purpo es of c hecking the Rorn-
Haber theory, however, so they will be ignored . In Ta ble 4.4 ~ re listed values
of ~ H/ calculated acco rding to the Born- Ha ber cycle, together with expe ri-
mentally determined values for a variety of compo unds.
-
I

76 Some Relations Between Thermody namic Quantities 1


Table 4.4 Compariso n of Theoretica l and Experimen tal Values of AH,O (kcal/ mol)
(to Convert to kJ, Multiply Values by 4.185)

Compoun d t. Ht 6 H2 !:1H3 t.Hc !:1 H6 !:1H1°(calc) 6. H/ (exptl)

LiCI(s) 38.3 29.0 125.8 -87.3 - 193.5 -87.7 -96.9


NaCI(s) 25.7 29.0 120.0 - 87.3 - 184.5 -97. 1 - 98.7
KCl(s) 21.0 29.0 101 .6 -87.3 - 163.6 -99.3 -104.2
R bCI(s) 20.0 29.0 97.8 -87.3 - 159.0 -99.5 - 102.9
LiBr(s) 38.3 26.6 125.8 - 82.0 - 182. 1 -73.4 - 83.4
NaBr(s) 25.7 26.6 120.0 - 82.0 - 173.0 -82.7 -86.4
KB r(s) 21.0 26.6 101 .6 - 82.0 - 156.8 -89.6 -93.7
Lil(s) 38.3 25.5 125.8 -75.7 - 170.7 -56.8 -64.8
Nal(s) 25.7 25.5 120.0 - 75.7 - 161.4 -65.9 -69.2
Kl(s) 21.0 25.5 101.6 - 75.7 - 150.0 -77.6 -78.3

~ 4.7 EMPIRIC AL PREDJCf iONS OF ENTROP Y


Absolute Entropy of Single Phases and llS of Reactions

Some empirical relati o ns which may be used to predict the entropy of


su bstances were developed by Latimer. • It will be recalled by the reade r that
according to the third law the e ntro py of all substance s, S0 °, in internal
equilibriu m is the same. For a co nvenient reference point this va lue is often
assumed to be zero. Thus the "absolute " entropy at some temperatu re Tis
given by

S~os- So = s~98 = J.TCSI dInT


0

There is an empirical relatio n between s:


98 and the molar weight of various
substa nces. '•
S; 98 = t R In (Mol Wt) - b (4.44)

where b is a co nstant. T he va lue of the term b depends upo n the nature of


c hemical bonding within the phase.
Consider a reaction between a meta l M a nd a no nmetallic s ubsta nce X
to form a compoun d M mX w We may write the reacti o n as

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

D.S~oa = l s:os(MmXn) - m S~ua(M) -


11
s:oa(X)
(m + n) (m + n) (m + n)
Equation 4.44 indicates that D.S~98 is small since the molecula r weight
contri bution is rather small beca use s;98 varies as the logari th m of the
molecular weight. An a nalysis of the entropies of va rious types of reactions
has been made by Searcy.* The results are shown in Table 4.5. This table

Table 4.5 Entropy Changes in Solid S tate Reactions

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.

Richards' Rul e and Trouton 's Rul e

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.~

Table 4.6 Entropy Change for Reactions involving Diatomic Gases

Reaction Type Average 6.S;88 (J/mol of gas·K)

-1.87 X 102 ± 8.4

-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

themselves. One tends , for example, to associate an exothermic reaction


with stability and the converse for an endothermi c reacti on. Stability in
this sense might be reflected in a high melting point, volume contraction , )
high modulus of elasticity, etc. These properties are, of course, only mani-
festations of the fundamenta l binding energies between the atoms themselves )
in the cry~tals. It is therefore of interest to compare experimenta l thermo-
dynamic properties with certain physical properties in order to see how far
.)
these qualitative concepts can be carried.
.)
Two empirical relations are perhaps familiar to the reader. An empirical
relation between the energy of vaporizatio n of a crystal and the boi ling
temperature has been found : this is known as Trouton's rule. Similarly,
a relation between the heat of fusion and the melting temperature of a
substance has been observed : this is known as Richa rds' rule. Such relations
wouJd be expected. The heat of vaporization , L", for example, is the enthalpy
input needed to dissociate the crystal into free atoms or molecules. Simila rly
the boiling point sho uld be directly related to the thermal energy needed
to obtain complete dissociation of the c rysta l; the higher the boiling point , .I
the stronger the binding forces between atoms in the crysLal. The constant
I
.,
4.7 E mpirica l Predict ions of E ntropy
79
of propor tionali ty propos ed by Trouto n is 88. Thus

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

Table 4.7 Entropi es of Vaporiz ation for a Variety of S ubs tances

Substance L v (kJ/mo l) TU.tl (OK) t::.S,, (J/moi· K)

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

the entr opies of fusi on for the


valu e. The reas on for the large va lues of
is easily und erst ood , si nce the
inte rme talli c com pou nds listed in Tab le 4.8
soli d state fo r the com po und is
con figu ratio nal or mix ing entr opy in the
q uite rand om. No orde red com -
zero , whe reas the liqu id solu tio n is alw ays
t the con figu ratio nal entr opy
pou nds exis t in the liqu id state. T o see wha
con trib utio n co uld be per gram -a tom o f co
reac tion whi ch occu rs upo n mel ting o f a com
mpo und , conside r the follo win g
pou nd. • I
( 1)
1
A"'B.,(s) = x A(l) + y B(l) t::..slo
x+ y x+ y x+ y
tical step s:
Thi s reac tion can be brok en into two hyp othe
1 l
(2) - - A:.:B 11(s) = A:.:B.,(/)
x+ y x+ y

(3) I A~Bv(l) x A(l) + ?I B(l)


=
x+ y x+ y x+ y
l mel ting proc ess whe reby the
Rea ctio n 2 corr espo nds to a hyp othetica
the liquid stat e. Rea cti on 3
com pou nd reta ins its orde red structur e in
in the liqu id stat e to form a
corr esp ond s to diso rder ing of the com pou nd
2, the entropy will resu lt from
random soluti o n. Fo r the case of reac tion
ng con trib utio n s uch as fo r the
a vibr atio nal cha nge but not from a mixi
melting of an elem ent. Thu s In ir 0. For reac tion 3, how ever , acco rdin g
r-..J

to equ atio n 3.42 ,

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.

of some nonmetal lic substance s as s hown in Fig. 4.9. Fo r th e substance


shown here many molecula r species exist jn the gas phase in differing relative
concentra ti ons as the compos itio n of the crystal is va ried . Clea rly in thi s
case the net heat of vaporizat ion will be the weighted s um of several con-
tributions and the weighting fact o rs wi ll differ with temperatu re.

f. 4.8 ESTIMAT ION OF HEAT CAPACrT IE OF CRY TALS

As a first approach , if no heat ca paci ty data exis t for a particular crysta l.


reco urse may be made to the Dulong-Petit rule, which states that at hi gh
temperatu res (generally in the vicinity of room temperatu re)

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

extremely strong interatomic bonds, has a value of C P 1n the vicinity of


17 J/moi·K.
Suppose the above equation is rewritten as

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

Tahlc 4.9 Test of Ncuma nn-Kopp l{ult: at 300° K

Compound Sum clJ (experimental)


AZBII x(CP)A 1/(CP) U (J/moi·K) (J/moi·K)

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.

Relation to Mo lar Volume


It will be recalled tha t, a ltho ugh use
ful , the ato mic "size" of a constituen t
can be a ra ther variab le quantity. Th e
" size" of an ato m in a crystal depend s
to a large ext ent upo n its immediate
cnvi ronmc nl. Perhaps the cla s~i<.:
example of this point is the relation
between interatomic spacin g of
car bon ato ms in a hyd rocarb on and
the number of cov ale nt bonds shared
by the atoms. Th e stro nger the bond is
, the smalle r the app are nt ato mic size
is. Sim ila rly in a crystal, the interat om
ic dis tance bet wee n ato ms wou ld be
expectep to depend ma rkedly upo n the
afllnities between atoms. We should
therefo re expect a relation ....betwee n the
molar vol un1e of a crystal and the
heat of formation of the crystal. A
la rge negative value of tl /1,0, wh ich
means tha t energy is evolved upo n fo
rma tio n of the crystal, implies a la·rge
affinity between atoms in the crystal. To
illustrate tha t suc h a relation exists
let us con side r a wide va riety of com pou
nds coveri ng oxides, halides, nitrides,
a nd inte rmetallic compou nds which cry
stallize with either the NaCI or the
CsC I structure. We will take as ou r refe
rence volume the ato mic val ue of the
clements in the pur e sta le. Th us, knowin
g the crystal stru ctu re of a par ticular
com pou nd , a hypothetical unit cell
volume V' or mo lar volume ma y be
calcul a ted , assum ing tha t the ato ms hav
e the same size in the com pound as
in the pure form , by jus t add ing the
volumes of the pure con stit uents. Thi
might be expected to be the case if the s
binding ene rgy of the ato ms in the
com pound is the ave rage of those in the
pur e form . Thi s hypothetical vol ume
V' ma y be compa red with the actual
cell volume or mola r vol um e Vdetermin
by x-ray or specific gravity measurem ed
ents. The difference 6. V = (V - V')
will be com pared with tl H/. Thi s vol
ume c ha rge tl V corresponds to the
foll ow ing reaction:
tl V and 6. H1°
In orde r to calcul ate the hyp ot hetical
volu me V of u unit cell of A.(J3 , the
ato mic volumes of most compounds wer 11
e obt ai'ned from the lattice parameter
me asu rements of element s in the close-
packed sta te. For nitr ogen, oxygen,
and sul fu r, however, a tomic vo lum
es of 5.0 X 10- :10 • 9.0 X JQ- 30 , a nd
14.5 x I0 30 m!l. respecti vely, we re
used. A graph of ~ V versus ~ 11,0 is
sho wn in Fig. 4. 11 , where it is see n tha
t an excellen t cor relation exists. Th e
com pounds for which 6.H,O ~ 0 sho w
littl e volume con trac tio n, as would be
expected. ln the case of very exothermi
c reactions, con sid era ble con trac tion
occurs.
-
86 Some Relations Between Thcrmodyna mk Quantities

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

1. Jt has been shown that the thermal expansion coefficient of a substance is


zero at T = 0; prove that the coefficient of tension defined as ( 1/p)( opf iJT)v =
0 at T = 0°K.
2. Suppose that a random solid solu tion of B in A is coo led rapidly to low
temperatures. What is S0° for this material?
0
3. Calculate tlS for the following reaction at 1300° K .
MnSi03 (s) + 2 AI(/) = Al 2 0:~(s) + Mn (s) + Si(s)
4. Given the compound A 5 B7 , which mel ts at I 000° K, ca lcu late l:lS1 . Consider
the arrangement of atoms in the liquid solution to be completely random.
5. Why would you expect Trouton's rule to apply with better accuracy than
Richards' rule?
6. A compound AB forms which has a value of tlH ,O equal to -20,000 1/ mol.
A and B are both face-centered cubic in the elemental state with atomic
rad ii of 3.52 X w - IO and 4.04 X w - lO m, respectively. The crystal structure ..
of AB is the NaCI structure. Compute the molar volume of AB.
Problems H7

7. Using the Born·Habcr cycle, calcu la te 6. 11/ fo r R b l.


8. For gadoliniu m sulfate, A = 2.66 J ·K/ mo l ami C = 7.85 x 10 ° m ·K/ rno L
3

A mo le of s ubstance is put int o a magneti c field of 104 oersteds at l 5° K .


(a) How much heat is transferred?
(b) How much work in joules is performed ?
(c) What is the change in internal energy ?
(d) Employing the adiabatic demagnetizati o n technique, calcu la te the fin al
temperature.
(e) Calcu lale the final temperature after a second and th ird cycle. Ho w many
cycles would it take to reach 0° K ?
9. For a metal in the superconducting s t« tc. ~h n w t hal the magnelocalo ric
effect is zero.
10. Show that
, VTd 2 (H (/-)
c,,s - C" '' -- - - 2-
8 T - t!T

11 . For a second-order transition derive


dT 6.(1
- = -
dp Arx
5

Ther modynam ics of Phase


Tran sform ation s and
Chem ical R eacti ons


5.1 PHASE T RANSIT IONS CLASSIF I ED ACCORD ING TO O RDER

Phase transitions are generally classified according Loa procedure developed


by Ehrenfcst. Ehrenfesl suggested that a firs t-order trwuition is one for which
the free energy as a functi on of a given state variable ( V, p, T) is continuous,
whereas the first derivative of the free energy with respect to the given state
variable is discontinuous. ln other words at the transition temperature the
Gibbs free energy G is continuo us but discontinuities exist in (oGfoT)p and
(oGfop)T, for example. We are all famili ar with many examples of first-order
transitions. Since
ac), -_ - s
(ar
(ac) _ v
op T

o(G/T)J = H
[ o(l/T) p

there is a discontinuity in entropy, volume, and enthalpy at the transition


t c nt p~~ rn t urn . l ~ x11 111 pl cs of linil-onlc r tra nsitions nrc fusi o n, vapo rizati o n,
and allotropic transformations. The variation of G versus T is illustrated
schematically in Fig. 5. 1 for two phases ex and {J. Delow lhc transition
temperature the P phase is stable, whereas above T tr the ex phase is stable.
According to this classification scheme a second-order transition is one
88
5.1 Phase Transitions Classified According to Order 89

,/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)

Acco rding to Ehrenfest's classification there would be a discontinuous


change at the transition temperature from one finite value of the heat
capacity, for example, to another fi nite va lue of C 1,. for example. This type
of transformation is illustrated schematically in Fig. 5.2. This figure illust rates
that the slope (iJGfoT) 11 is the sa me for bo th a and {J phases at Ttr-
Some examples of second-order transformatio ns are order-disorder
transformation in alloys, onset of ferromagnetism or antiferromagnetism ,
onset of ferroelectricity, and onset of superconductivity when II = 0.
A third-o rder transforma tion according to this classilication is continuous
for example in G, S, and Cp but would be discon tinuous in (oC,/oT)w No
transformations are known that a re third o rder o r hi gher. rf they exist they
would be very difficult to find experimentally since one would need to know,
for example, the curve of heat capacity as ~ function of temperature very
90 Thermodynamics of Reactions

..
tG

t •
cJG\
( iJT )p

T~

t
(a2o),
aT p

Ttr
T~

Fig. 5.2 Illustration of a second-order transition.

precisely in order to determine whether o r nol a discontinuity in slope


(aC,f aT)p exists.
A problem exists with rega rd to Ehrenfest's classification of high-order
)
transitions. For a second-order transformation flC,, for example, is finite,
whereas there is some evidence that flC, is infinite a t Tt.r· In F ig. 5.3 is shown
the curve of hea t capacity versus tempera ture in the temperature region
where quartz undergoes a second-order transition between 0'.-q uartz and
P-cristobalite. There is some evidence that the heat capacity, and thus flC 1,
5.1 Phase Transitions Cl assified According to Order 91

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.

5.2 FlRST-OnDER TI~ANSITlONS

Influence of External Pressure on Transition Temperature


Consider a general first-order phase transition of a pure substance from
the ct. to p phase a t a constant temperature and pressure. At the transition
temperature, 6.G fo r the reacti o n is zero. Thus G11 = G"' or
I . J
dG, = dGo: (5. 1)
I
Since the process is reversible at the transition temperature, we may use the ~

relation derived previously I '

dG = Vdp- SdT ' ..


I I
I

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

Since the reaction is proceedin g a t co ns tant temperat ure and pressu re

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

6.T = (T ~V) ~P (5.4)

This may be seen by carrying out the integratio n rigorousl y, expandin g in


an infinite series, anti neglec ting high-ortlc r terms.

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

kg/m3, respective ly. The molar vol ume change is therefore

~V = M(
1
- -
1
- ) = -4.35 x 10- o m!\f mol
Pwll ILc Pgray

Upon su bstit uti on into equat i.o n 5.4, we have

I o-omaf mol )(I 0


7 2
D. T = 286 K X ( -4.35 X - 1.0 I x I 0'' )( N/ m )
2090 Jj mol
D.T = - 5.95 K
The effect o f pressure upon the trans formnt ion temperatu re depends upo n
the s ign of ~ V a nd ~ II in cqun Li o n 5.4. Cons iu cr t he fu sio n process, fo r
example. The heat of fusion is always positi ve, b ut the volume change upon
fusio n may be positive o r negative. For m eta llic elements c rys tallizing in
the close-pack ed stru c tu r es , 6. V is positive upon fusio n a nd so the melting
point is increased upon increase in press ure.. Fo r elements crys tallizing wilh
94 Thermodynamics of Reactions

open structures, ~ V is often negati ve upon fusio n a nd so the melting po int


is lowered upo n applica ti o n of p ressu re accordin g to equa tio n 5.4 . In Ta ble
5. 1 the influence of pressure o n th e melting p oint is s hown fo r a va riety of
solids. Ac tu al va lues o f ~ T are co mpared with values calc ula ted from
equa tion 5.4 a nd the agreement is excellent.
Eq uatio n 5.4 is accura te only fo r relatively sma ll valu es o f ~ T and low

Table 5.1 The Effect of Pressure on the Melting Point of Solids

~v 6Tfor lOij N/m2 (K)


Trn.v. Lr ( V1 - V,)
Substance (K ) (J/kg) (m 3/ kg) calc obs

H 20 273 .2 0.334 - 9.06 x to- 6 -7.5 -7.4


Acetic acid 289.8 0.1 87 + 1.595 X J0- 6 + 25.0 +24.4
T in 505 0.0585 +0.389 X I Q-6 +3.40 +3.28
BismuLh 544 0.0501 -0.342 X 1Q-6 -3.56 -3.55

values of ~p since, a t very high pressu_res, the dependence of~ V and ~H


upon pressure rnu_st be ta ken into account. From equa ti on 5.2

dT ~v
dp ~s

The c urvature o f the bo undary line is

dT= 1 dT((a ~ V) + 2dT[(a~ V) _ (dT) 6.C'P])


2 2

dl· 6. V(p) dp ap dp ar T dp r 'P

and at very hi gh pressure the curvature may be quite importa nt , as sho wn in


Fig. 5.5. The rela tio n between pressure and melting po int is o ften expressed
ernpirica11y by wha t is kn o wn as the Simon equa tion
)
p -
Po -
(_I_)c
Tm.p. -
l
)
where c a nd p 0 a re co nsta nts and T,"·"· is the melting temperature a t I a tm
pressure. Fo r iro n , for exampl e, c has been empirically determined to be
a bo ut 1.4 a nd p0 is equa l to 430 kbars. Fo r N aCI, c = 2.7 a nd p0 = 16.7
kbars and for LiCI , c = 2.5 a nd p0 = 14.5 kbars.
The applicatio n of high pressure to so lid substances bel ow the m elting
point m ay cause phases to a ppea r that a re not sta ble at atmospheric pressure.
These high-pressure phases ha ve structures which have higher density than
the low-pressure phases. A phase diagram is shown in Fig. 5.6 fo r bismuth.
In Fig. 5.7 is sho wn the effect of pressure on the cx- y transfo rmati o n in iron.
2673
~
/
bT
2473 v
/ f-
~
I
/ l.--p;
~ ~
:l
;;
...
X.
2273
v
. /
v
E v
~

..
aD
c
Qi
2073 v /
::E
~ --
v
__.. ~ ~ ~
1873
v
v
v ./
7

1673
0 20 40 60 80 100 120
Pressure - lOS N/m2

liig. 5.5 Experimental fus io n cur ves.


Based on R. M. Strong, Amer. Scientist,
48, 58 ( 1960).

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.

Transition from Condensed Phase to Vapor Phase


.(
Suppose that the {3 phase represents a vapor in eq uilibrium with its
co ndensed pure phase. Fo r this particul ar case the C lapeyro n eq ua tio n can
be pu t into a more usefu l fo rm . T he 6. V term in equati o n 5.3 is d efined as
Vp - V 11 • When {3 is a gas a t normal press ures

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

Dividing through by p and multiplying by dT,

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~

Fig. 5.8 Vapor pressure as a fu nction of temperature.


98 T hermodynam ics of Reactions

Writing equation 5.8 in exponential form,

p = A exp [ - ~~J (5.9)

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

Table 5.2 H eats of Sublimation in Units of 105 J / mol (at T m. l )


1

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.

7 Effect of External Pressure Upon the Va por Pressure of a


Condensed P hase

Suppose that our co ndensed phase system of interes t is placed in an iso-


therma l chamber as s hown in F ig. 5.9. If the c hamber is evacuated, the only
vapor in the c hamber will be th a t o f co mpo nent 8, a t press ure p and tem-
p erature T . This problem was di scussed in the last secti o n. Suppose now
5.2 First-Order Transitions 99

Table 5.3 Vapor Pressure Cons tants of Several S ubstances (in N/ na 2 ) 0

Temperature Range
Substance a b c X IO:J d (K)

Ag(s) - 14,900 -0.85 14.32 298-m.p.


Ag(l) - 14,400 - 0.85 13.82 m.p.- b.p.
Ge(s) -20,150 - 0.91 15.40 298-m.p.
Mg(s) -7,780 -0.855 13.63 298- m.p.
Mg(/) -7,550 - 1.41 14.91 m.p.- b.p.
NaC1(s) - 11,530 -3.48 22.89 298- m.p.
Si(/) -20,900 -0.565 12.90 m.p.- b.p.

0Based on Kubaschcwski et al., Metallurgical Tlu>rmocllemistry, 4th cd . , Pergamon


London. 1967.

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

Inert gas pressure P


Temperature T

8 in gas phase p 8

Fig. 5.9
.
- - - - -.. .F--=·---
.~

100 T hcrmodyuamics of l~ cactions

given by

Since
dG cond = dG gas
we find
dp Voood
- - (5.10) \
dP V~ens

Assuming the gaseous B to be perfect, pV = RT and

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

5.3 SECOND-ORDER TRANSITI ONS

Many examples of second-order transitions exist in nature. Figure 5.4


illustrates the heat capacity change for a magnetic transition in US at co n-
stant press ure. lf one employs the Ehrenfest approach, the eiTect of press ure
on the transition temperature may be readily calculated. Employing the \
approach used in Section 5.2 one may readily derive that

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 • {Mn Zn) FezO,.


2 • I ao.?r. Srn.21l Mn O:t -
3 • N1
4• 67 Ni 30 Cu
5• Alumel 94 Ni
I 6 •
7•
Gd
64 Fe 36 Ni
f 8• 70 Fe 30 Ni
I
J
..
I

'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

From the combination of the first and second Jaws

T dS = dU + DW = dU- H dM )

Conseq uently under isothermal conditions

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

Gs(lf) - Gs(O) = 112V


87T
Application of a magnetic field increases the free energy of the s upercon-
ducting material. At H = H, . the free energy increase is s ufficient to make
the free energy o f superconducting and n ormal phases equal. This relation
is shown schematically in Fig. 5. 12. As can be visua lized from this figure,
there is a discontinuity in slope (oGfo ii).,. at 11 0 and therefore the transition
is first o rder in nature.

I
I
I
I
I
I
Normal

t
G

Superconducting

Fig. 5.12 Free energy- magnetic field relation between s uperconducting and normal
material.

Suppose, now, a case is considered where H = 0. Below a critical tem-


perature T 0 , the superconducting phase is stable and therefore has lower
free energy. Above Te, the norma l phase is stable. It is interest of to examine
the nature of the transition in this case.
An experimen tal curve is shown in Fig. 5. 13 where the free energies of
'
I
!
I superconducting and no rmal alum inu m are co mpared. Below T,, the material
was put into n ormal state by application of a field. S}nce M = 0 for the
normal material, the field itself makes no con tribution to the free energy.
It is observed that near Tc, the c urve merge , and si nce S = (dG/oT)v, this
indicates that the entropies of the norma l and superconducting phases are
the sa me at T0 • As a consequence, the transition is not first o rder bul is
presumed to be second order.
104 Thermodynamics of Reactions

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.) ·

5.4 CHEMlCAL REACfl ONS

The topic of chemical reactions is of considerable interest to ind ivid uals


wo rking in the area of materia ls science since various chemical reactions are
importa nt in the preparation and purifica tjon of materia ls; conversely
chemical reactions may result in contamination or destruction of ot hcrwise
pure material s. Some examples of useful process which involve chemical
reaction s are as follows:
,
I

• Growth of single crystals


• Epitaxia l depositi on of alloys or compounds of controll ed composition
• Removal of contaminants in a condensed phase through reactions
between t he impurities and a gaseous species. For example, dissolved carbon
may be oxidized to CO or C0 2 and removed as a vapor or the partial pressure
of water vapor in a gas phase may be reduced by reaction with ti tan ium

Some examples of undesirable reactions are as follows:

• Oxidation of metallic structural materia ls at high temperatures


• General corrosio n processes
• Reaction between pure materials and container which result in con-
tamination of the pure material
5 .4 Chcrn icsll Reactions 105

Materials are being increasingly. subjected to high temperatures and


consequently most of the processes (both desirable and undesirable) proceed
at rapid rates. The problems associated with use of materials at high tem-
peratures have been illustrated by Searcy* in the form of two statements.
The 'first " law" is that at high temperatures everything reacts with everything
else. The second " law" is that the higher the temperature, the more seriously
everything reacts with everything else. These statements may appear facetious
but nonetheless the practical problems they illustrate are real. The ability
of scientists and engineers to protect materials and to prepare high-tem-
perature materials in pu re form is seriously impaired by the problems
suggested by the two statements.
From a thermodynamic point of view, the sign of the free energy of a
reaction governs the· feas ibility of the reaction. Thus if !:J.G is negative, the
reaction might proceed. At low temperatures one observes many examples
for which D.G is negative but for which no significant reaction occurs because
of sluggish kinetics. At high temperatures, however, the kinetic terms are
Jess restrictive and consequently thermodynamic considerations become very
important.
The Gibbs free energy change of a reaction is, of course, composed of an
enthalpy term and an entropy term.
!J.G = !J.H - T D.S
At low temperatures T !J.S is often small and the sign of D..G is dominated
· by the sign of !J.H. At high temperatures the T D.S term becomes of increasing
-im porta nee.
Of particular interest to us in considering chemical reaction is the standard
free energy change of the process. The standard free energy change 11G0
refers to a reaction for which all reactants and products are in their standard
states at the given temperature and I atm pressure. It should be emphasized
at Litis point that the sign of !1G 0 for a particular reaction can be used only
as a criterion of spontaneity if all substances are in their standard states.
0
The real significance of ~G lies not in connection with the predictabiljty of
spontaneity but in connection with equili brium constant calculatio ns, as
will be discussed next.
Consider an isothermal reaction between solid phases in their standard
states with a free energy change !1G0
aA(s) + bB(s) = cC(s) + dO(s) f1G 1°

Each of these components is assumed to be in equilibrium with its own vapor

• A. W. Searcy, in Proc. lttt'l. Symposium 0 11 H igh-1'emperature Technology, McGraw-


Hill, New York, l960.
106 T hermodynamics of Reactions

at its particular partial pressure. A s a result we may convert the above


reaction of interest to one involving gaseous components at their equilibrium
pressures , p,0 , as follows:
\
(l) aA(s) +bB(s) = cC(s) +dD(s) liG1o
{2) aA(g,pA j = aA(s) llG2 = 0
(3) bB(g, p13°) = bB(s) liG3 = 0
(4) cC(s) = cC(g, p 0 °) llG4 = 0
(5) aD(s) = dD (g, p n°) liG6 = 0

(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

pA•, p0 •, Pc•, a nd p 1/ . These values will be chosen so that the reaction wi ll


be in equilibrium a nd hence the free energy change of the reaction will be
equal to zero. Thus

(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

Assuming T co nstant a nd considering the vapo r to be idea l (pV = RT) we '


find
dG = RT dIn p
or upon integra tio n

A
f

.,
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'

(LO) cC(g. Pu0 ) = cC(g, Pu~)

(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,

Substituti ng and putting the coefficien ts a, b, c, and d inside the logarithm s


yields

( 5. 12)

The bracketed expressio n inside the logarithm is called the equilibrium


constant K for the reacti on. Rearrang ing we find

6.G0 = -RTin K (5. 13)

It should be no ted from 5. 12 that K is a dimensio nless quantity regardless


of the values of a, b , c, and d.
~ It should be emphasized that it was assumed that the partial pressures Pi
are low enough so that the perfect gas Jaw may be applied. Jf thi s equation
of state is not applicabl e, the co ncept of ful{acity must he introduce d. For
the reacli ons which will be considere d here, il will be assumed that th e
perfect gas law may be applied a s a good app roximatio n . The reader should
note that this ass umption does not imply that the co mponents in a co nden sed
phase behave ideally but only that the va pors in contact with the phase
behave ideall y.
108 Thermodynamics of Reactio ns

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)

we see that Pi is a variabl e and pi is fixed at a given temper ature, si nce it is


0

the vapor pressur e of the pure compo nent. Theref ore

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.

(2) a A(aA= 1) + bB(au = 1) = cC(ac = I)+ dD(a 1 > = 1) ~G o

(3) aA(a~ = aA(aA = 1) llG, = aW•."- G.)= RT In (:J


(4) bB(au) = bB(au = 1) ~G4 = b(Guo- Gu) = RT In (-
1
au
r
(5) cC(a 0 = 1) = cC(a 0 ) ~G 6 = c(Go- G 0 °) = RT In ace
(6) dD(a 0 = l) = dD(a 0 ) ~GG = d(Go- Goo)= RT In a 0 d

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

Ca (a= 0.5) + Si (a= 0.4) = CaSi (a= q.8)

) (d) whether or not the reaction for (c) will proceed


Solution. (a) Since we are interested in a n equilibrium reaction we wiU
use ~Go = - RT In K. From the literature we find that 11G0 for the reaction
at 1000°K is equal to -172 kJ/ mol. The term ~G refers to 0

Ca(s) + Si(s) = CaSi(s)


and we find that
K = ac,\~ 1 = 8.92 x 108
a cna !'\1
Since CaSi exists as a pure stable phase, a cllst = I, and it was given that
aca = 0.5. Thus on substitution, we find that the equilibrium activity of Si is
a51 = 2.24 x · t0- 9
110 Thermodynam ics of Reactions
If the activity of silicon in solution was initially hi gher, CaSi would precipitate
until equilibrium was reached.
(b) H is given that ace. = 0.5. Since ai = p./p,0 we can obtain Pen if the
value of Pio can be obtained. Since our standard sta te for Ca is pure solid at
l000° K, Pca0 is simply the vapor pressure for pure Ca at 1000° K. From the

literature P<:'ao = 14.6 N/ m 2 , and thus on substituting , Pen= 7.3 N/ m2 •
The solution therefore has an equilibrium pressure of calcium equal to
7.3 N / m 2 •
(c) Upon substitution of appropriate quantities we find

~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

0. Kubaschcwski et al., Metallurgical Tllermoc/wm istry, 4th ec.J., Pergamon,


Oxford, 1967.
K. K. Kelley, Bull. U.S. Bureau of A1ines, Nos. 383, 393, 406, 407, 476,
and 477.
R. Hultgren et at., Selected Values of Thermodynamic Properties of Metals
and Alloys, Wiley, New York, 1963.

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

6.G,0 = - RT InK and K= .,


G c;u- • Pnt

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

(- 200 kcal)l - 836 -

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.

At a given temperature T, 6.G/ may be evaluated from the graph and


log Po, determined. At 800°K, for example, the value of Po, in equilibrium )
with Cu and CuO is approximately I0- 5 N/ m2 •
One may envision a simple way of graphically evaluating Po, from
expression 5.20. Suppose a pressure value is arbitrarily chosen. This corre-
sponds to a given value of 6.0//T. The line fo r l0- 6 N/m2 oxygen pressure
..
5.4 Chemical Rea ctions llS

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

equilibrium pressure of VO ·js equal to I Q- 5 N/m at approxi mately 2300° K.


2

If the partial pressure of 0 2 is less tha n 10- s N/ m a t 2300°K YO will be


2

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

2 Ti(s) +0 2 (g) = 2 TiO (s) tlG/ = - 750 kJ

i Fe(s) + 0 2 (g) = i FeOu(s ) (or A Fe 20 3) 6.G,0 = -292 kJ


Subtracting the second reaction from the fi rst yields
2 Ti(s) + A Fe2 0 3 (s) = 2 TiO(s) +' ~ Fc(s) 6.G0 = -458 kJ

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

generalization, therefore, the metallic constitu ent of an ~xide phase which


has a more negative value of ~G,O than a second pbase wiJI reduce the second
phase with concom itant oxidation of the metal.
'-'As another illustrati on from Fig. 5.14 one $CCS that Zn will reduce, say,
NiO below about 1900°K, but Ni can reduce ZnO above 1900°K.
It is interesting to note that most lines on Fig. 5.14 are roughly parallel.
This indicates that l:l.S/ val ues for the reaction s are nearly the same. This is
in agreement with the empirical observations discussed in Chapter 4.
An Ellingham plot for a va riety of materials is shown in Fig. 5.1 5. Both
Al 20 3 and Si02 a re common crucible materials and it is seen from this
figu re that Mg and Ca, fo r example , will reduce either material below 1700°K .
In similar fashion it is observed that AI could not be contained in Si0 2 ,
whereas it could be contained in MgO or CaO.
Examination ind icates that in addition t.o the Poa scale, scales arc given
fo r Pu.IPu,o and P<"o!Pco,· These sales refer to the following type of reaction:
)2
K = _1 l_lt_
2
Puto

M(s) + 2 C0 2(g) = MOls) + 2 _<.:0(~)


uw• liM ' .,...
I

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

_.., 'l. ...~

~.

_.. ~·
,. I
s

I
It '
-u

10... . .
IJI' tq.•
- NO I "
I

-m to•
... ......
-110
It'
1 ...
-ItO
""I

JJ.'" _,.
--~
- 110 I .., 10" II
1

-·.. 4IJ l iJ an ltll IVJ


''"
,_ ...... r~
IVJ IIJJ

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 5.4 Chemical Reactions 117


These three scales enabJc one to calculate the eq uili bri um CO/C0 2 ratio,
H 2 /H2 0 ratio, or the Po, between a pure metal a nd its oxide at any tem-
perature. For the C0 2/CO a nd H 20 / H 2 reactions, the points marked C and
H are employed as the origins, respectively. One finds that the equilibrium
H2/ H20 ratio for the Ti- Ti0 2 reaction, say, is 108 at abo ut II 00°K. This
implies that impure H 2 which contains water vapor may be purified to l part
H 20 to 108 parts H 2 by passing the gas over pure Ti. One also observes that
the temperature of the Ti metal is important. If the temperature is too low
I the kinetics of oxidation will be too slow, whereas if the tempera ture or T i
I is increased the H 2/ H 11 0 ratio decreases also. Conscttuently an optimum
must be reached .
The subject of kinetics is generally outside the scope of this vol ume but
t in the case of evaporation of compounds there is an interesting relation
I between the rate of evaporation and the standard free energy of formation
of the compound .* Following Searcy, consider the evaporation of MgO.
~ This phase dissociates readily at high temperatures according to the reaction

t 2 MgO(s) = 2 Mg(g) + 0 2 (g)


I MgO sublimes congruently, which means that the chemical com position of
the solid phase does not change with time. The term incongruent, on the other
~ hand, refers to a process in which the composilion does change with time.
As a conseq uence, for M gO the nu x J r. 1" is rclalctl to the flu x of 0 2
j
JMg = 2Jo,
f or

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) ~

• A. W. Searcy, in Chemical ami Mechanical Behavior of Inorganic Materials, Chap. 4,


Wiley, New York, 1970.
JJ8 Thermodynamics of l~caclions

At 2000°K, the maximum rate of evaporation of MgO into a vacuum is


calculated from 5.22 to be equal to about 3.3 x I 0- 4 kg/ m 2 ·s. Since this is
a maximum rate, equation 5.22 is useful in order-of-magnitude estimates
of whether or not a given material could have problems due to evaporation
at some particular temperature.

PROBLEMS

t 1. Estimate the pressure needed to convert graphite to diamond at 1700° K.


What assumptions did you make?
2. Calculate the heat of sublimation of BcO(s) at 300° K and 1000°K from
vapor pressure data. Estimate the value a t 0°K .
3. Consider a vacuum furnace containing a crucible of magnesium. What is the
value of the bes t vacuum attainable at 1300° K in the system ?
4. Suppose that t he magnesium of Problem 3 is under a hydrostatic pressure of
108 N/m 2 • Calculate the change in vapor pressure.
5. Would it be possible for ~c;o to equal zero? Explain.
6. Calculate ~(/'for tbe reduction of Si02 (s) by AI(/) at 1200°K. Wo\Jid pure
AI reduce Si02 ?
7. Calculate the equilibrium oxygen pressure bet ween' A 120 3 unc.l AI {I) at l 000° K.
Could a vacuum of t0- 10 mm Hg prevent the oxidation of AI?
8. Suppose CaO is placed in,a_vafuum in' which the.~rtial pressure of oxygen
is to- 6 mm Hg. Will CaO be reduced 7
9. Calculate the equilibrium constant for the reaction
0 2(g, 105 N/m2) = 0 2(g, 104 N/rn 2) . J

10. Suppose t he va por pressure of a specific concentration of Zn dissolved in


Cu. is 3 x w- 3 mm Hg at 600°C. Calculate the activity of Zn in the alloy.
Calculate the free energy change of Zn upo n solution. )
0
11. Using Fig. 5.15, calculate 6G for the following reaction at 1000°K.

f Si(s) + Al20 3(s) = 2 AI(/) +f Si02


Will the reaction proceed to the right or the left if the elements are in their }
standard states? At what temperature, if any, will the reactants and products
be in equilibrium 7 )
12. Suppose that in Problem 11 Si is not at I 000° K but at 800°K; can the free
energy of reaction be calculated? Explai n.
13. What would be the value of ~Go for the following reactions at 298°K?
(a) 0 2 (1 atm) = 0 2(5 alm)
(b) AI = Al(dissolved in Cu, X .AJ = 0.01)
(c) Al(s) + i 0 2(! atm) = Al 20 3 (s)
14. Calculate the standard entropy of fo rma tion of GeO(g) at l000° K.
6

Partial Molal and


Excess Quantit ies

6.1 PARTIAL MOLAL QUANTITIES

Up to the present, all of the discussion of thermodynamic properties has


centered around pure phases. Often, however, we arc concerned wilh alloys
and mixed crystals. As a result, we are concerned with the thermodynamic
properties of a particular component in a soluti on. Such a property is called
a partial molal quantity, o r more convenien tly. partial molar quantity. A
given component will have, for example , a partial molal volume, entropy,
energy, enthalpy, and fre~ energy. From a concepluaJ point of view, the con-
cept of a parti al molal quantity is not difficuJt to understand. For the
purpose of illustration, let us consider the volume, since it is perhaps the
easiest to visuali ze. Suppose we have a quantity or sol ution consisting of two
types of molecules. This solution has a definite volume. T his vol ume may be
thought to consist of the volume occupied by A molecules and the vo lume
occupied by B molecules. The vol ume occue_i~d by a mole of A is designated
the p!irtial molal voJume of A. In order to put it on the basis of a standard
amount of material, the volume is referred to one mole of the given compon-
ent. To formulate mathematically, consider a solution at a fixed temperature
and pressure. ln this case the only variables wi ll be those rel ati ng to composi-
tion. in this chapter, the solid superscri pt(·) will be used to refer to a property
of pure component. Let the volume of solution be V', consisting of n 1 moles
of component 1, n2 moles of component 2, etc. Then si nce V' = f(n 1 , n2 , • •• )
we have
dV' = av')
(anl
- dn 1 + (aw)
- dn 2 + ··· (6. L)
T .11.t1;.n3.. . . • an,... 7'.1l .na, ,3. ···

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

we see that the partial molal volume of component i, designated as il, is


given by
v.- (-av') (6.2) • .J
I
Oni
Thus
t - T.JJ.nl
\
I
I
dV' = V1 dn 1+ V2 dn 2 + · · · (6.3)
I
dG' = C1 dn 1 + C2 dn 2 + · · · (6.4)
dH' = H 1 dn + B2dn2 + · · ·
1
(6.5)

The term Gt is sometimes referred to as the chemical potential of co mponent i.


ln .... _ . . onerations it should be emphasized that the compositio n has been
kept conslam. ::· =ft may be accomplished experimentally in one of two
ways. If V' is small, dn, mott~ tuay u... o:!.._...t,:.d without changing composition,
if dni is regarded as infinitesimal. Similarly &i .;,ji :.... 'zr~e. the composition
may be kept approximately co.ostant if V' is very large. 1 hu;) . ,- c,pe from
equation 6.2, for example, that V1 may be. found by adding an infinitestmal ~
amount of component l , d111t and ~bserv1ng the volume change dV'. Thus
17, is evaluated at a particular composition. At this composition Vl represents
the effective molar volume of component in the solution. If the solution
consists of ni moles of component i, it fo llows, therefore, that the total
volume equals the volume per mole of component 1 ti mes the number of
moles of component L in solution plus the vol ume per mole of componcut 2
in a solution of this composition times the number of moles of component
2, etc., or
(6.6)
Also
G' = C1n 1 + C2n 2 + · · · (6.7)
H' = li111 1 + R 2n 2 + · · · (6.8)
Differentiating equation 6.6 we obtain
dV' = V1 dn 1 + n 1 dll +1 fl2 dn 2 + n.2 dV2 + · · · (6.9)

Comparison of equation 6.9 with 6.3 shows I


(6. 10) I
and similarly
n 1 dC1 + n2 dG 2 + · · · = 0 (6.11) I
n1 dR1 + " 2 dfi2 + · · · = o (6. 12)
I
n 1 dS1 + n 2 dS2 + · · · = o (6.13)
I
Instead of being concerned with an arbitrary amoun t of solutio n with j

volume V', free energy G', etc., it is generally convenient to consider a I


6.2 Partial Molal and Molar Quantities 121

gram-atom of solution. By definition


V' = V(n 1 + 11 2 + · · ·)
where V is the volume of solution per gram-atom. Dividing the equations
by the number of gram-atoms of solution (n1 + 11 2 + · · ·) we find
v= vlxl + v2xz + · · · (6.14)
G = + · ··
C1X 1 + G2 X2 (6.15)
H = R 1X1 + R2X2 + · · · (6.16)
S = S1 X 1 + SzXz + · · · (6. 17)
and
dV = V1 dX1 + V2 dX2 + · · · (6.1 8)
dG = G1 dX. + C2 dX2 + · · · (6.19)
dH = R 1 dX1 + H2 dX2 + · · · (6.20)
dS = St dX1 + S2 dX2 + · · · (6.21)
and
xl df11 + X2 df12 + · · · = o (6.22)

IX,d~, + X,dC.+ ... =0 I (6.23)

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.

6.2 METHOD OF OBTAINING PARTIAL MOLAL QUANTITIES


FROM MOLAR QUANTITIES

As an illustration, suppose that the volume per gram-atom of a binary


solution is obtained as a function of composition and it is desired to obtain
the partial molal volumes of the components. The mol nr volume of a binary
solution of A and U as a function of composilion is shown in Fig. 6. 1. Let
us consider a solution of composition which has a molar volume of V and
find the values of flA and Pn at this composition . Consider equation 6.18.
dV = VA dXA + Vn dX 13
Since
XJ.+X 0 =1,
Thus
122 Partial Molal and Excess Quantities

t
v.·
Va

I
0 a
Xa-+
1.0
.I
Fig. 6.1 Molar and partial molal volumes of a binary system.

Upon division by dXn we obtain


•) '
l
Pn = PA + (~) (6.26) {
dXn
By rearrangement of equation 6.14 we find .J

o - V- PuXo
.f
J' A -
l - X0
and substituting into equatiqn 6.26 we find

fJn = V + (1 - Xu) ( d V ) (6.27)


dX 0
Similarly for PA•
VA = V - XB
·
(j_f_)
dXn
(6.28)

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.

6.3 METHOD OF OBTAINlNG ONE PARTIAL MOUL


QUANTITY FROM ANOTHER
I
Quite often from an experimental point of view it may be easy to obtain
the partial molal quantity of one component as a function of composition I )

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.

Using the relation (XA + X8 ) = I, and rearranging ,

fdflu = -f (I - Xn) dVA


Xn .
(6.29)

Let us find Vn at composition a shown in Fig. 6.2. To do this equation


6.29 must of course be integrated. ln order to solve equatio n 6.29, the
lower limit of integration should be evaluated at Xu = 1, si nce the term
(1 - X 8 )/Xa in the integra l is then equal to zero. Also on the left-hand
side, at the lower limit of integration,

Thus

(6.30)

fl.A is generally not in analytical form, so a graph ical method of obtaining


(Po - V0 ' ) is used. F rom equation 6.30 we see that if Fig. 6.2 is replotted
by plotting the quantity (1 - Xn)/X 8 versus VA, and integrating graphically
between the value of VA, when X 0 = l ahd VA at Xn =a, the desired
..
I

124 Partial Molal and Excess Quantities

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
.•

Equatio n 6.30 can be generalized to the other thermodynamic quantities as


well. For example

6.4 SOME RELATIONS BETWEEN PARTIAL MOLAL QUANTLTIES

Consider, for example, the equation

G' = B ' - TS'


~.
I

where G', H ', and S' refer to the appropriate thermodynamic values for
an arbitrary amount of solution. Keeping temperature and pressure co nstant, J

and differentiating, we obtain

dG' = dH'- TdS'

Dividing both sides by dn., keepin g the other components the same, and
tlte temperature and pressure constant, we find

(oG') (oH') (as')


oni . = ont - T oni
6.4 Some Relations Between Partial Molal Quantities 125

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

o(Cj - G;') = -(S. _ S ") (6.31)


ar , ,
o[(Gi - G/)/TJ = Jl _ u: (6.32)
o(t /T) ' '

o(C,- G,:) = V.. _ v: (6.33)


op , ,
The quantitie's on the right-hand side of equations 6.31 and 6.33 an! known
as relative partlal molal quantities. In the last chapter we derived

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

•"' I G, - a: = RT.Jn a, I p " (6.34)


J26 P~rlial Mola l and Exc~s Quantities

6.5 FIU;: E ENERGY OF FORMATlON OF A SOL UTION

Consider the formati on of a gram-atom of solution fro m the pure com-


ponents in their standard states :

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

Substitutio n of equation 6.34 into 6.36 yields ..


11G 11, = RT(XA In aA + Xu In a 0 ) (6.37)

Similarly we find for the heat of mixing and entropy of mixing


II

1111 m = 2, Xi(Jfi - Hi. ) (6.3H)


i= l

~ 11s,. =I" xi<S~- sa


l~ l
(6.39)

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.

6.6 IDEAL SOLUTIONS }


I

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)

Since X1 ~ f(T) but is any val ue we c hoose, (Fl, - H,·) = 0 , and th us


from 6.38 we see that for an ideal solution , the hea t of mixing ,
If- D.Hm = 0 ?'

indicating that no heat is absorbed or released upon formation of the


solution.
F rom equations 6.41 and 6.37 we see that for a binary solution
6.G 11, = RT(XA.l n XA +Xu In Xu)
At consta nt temperature,
D.Gm = D. ff 111 - T D.S,,
a nd in view of the fact that

we find
(6.44)
P~•rtial Molal autl l~ xc c~s Quantities

Equation 6.44 is identica l with the eq uatio n derived in Chapter 3 by use of


stat istical conce pts. Similarly, it is seen th at for an ideal solutio n

S lllCC

As a result

.111 summary, for an idea l solution

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.

6.7 NO iDEAL UlLUTE SOLUTI ON

For a dilute solutio n, in genera l, the separation between solute atoms is


large, and as n resu lt it is fo und that the int eraction hctwccn solute :1tnllls is
Sllla ll. This sugges ts that the thcnnoJyna llli <.: pro perties or the solute <trc
additive for dil ute solutions. Thus we wou ld ex pect that the solute vapo r
press ure of a solution containing two hundred solute atoms, for example,
would be twice that co utai ning one hund red solute atoms in the sa me volume
of solution. Consequently
p, = bX,
where b is a constant whose val ue depen ds o n th e nat ure of the solute and
solvent. This is known i.IS 1/cnrfs lmr. Fro m lite dclinition or <H.: li vil y we
find that fo r the solute

a0 =(~) Xu
flu
or au = J1 11 °X 11 (6.45)

The general term y is called a n actitJity coefficient. For a n ideal solution,


y 11 = I. The quantity y 11 ° may be less tha n one o r greater than o ne for solu te
in a nonideal solution, but for a given solute it is independent or concenl ration
when the solute concentration is small.
6.7 Nonideal Oilutc Solutions 129

ll is of interest at this point to consider the activity of solvent atoms in


a solution where the activity of the solute foll ows Henry's law.
Let us consider eqllation 6.23.

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

Integrating between the limits X11 = 0 and X 11 gives

fad In a/\ = - f'r" dXu


Jn_l Jo (I - X 11 )
which yields
In aA = In XA
aA. = XA

As a generali zation, therefore, it can be said that for a dilute solution in


which tbe solute follows Henry's law, the solven t in tllrn foUows Raoult's
law. At the other composition extreme when X A «
1, component B will
follow Rao ul t's Jaw. For intermediate composition no simple relationship is
valid and the shape of the curve depends upon the specific system. Thjs
is shown in Fig. 6.5 for both components of a binary system. The composition
ra nge for which Henry's law is applicable for solute cannot be determined
a priori. For one soluti on deviations may begin to be detected at O. l at %,
whereas in another solution the solute may follow Henry's law up to 10 at %
solute. As a generalizatio n , it is perhaps reasonable to say that the greater
the devialion of y 11° from unity for a solute, the more restricted the composi-
tion range will be for which llenry's law applies. ln a later chapter y 11 o will
be interpreted in terms of more fundamental properties of the atoms in
solution.
Applying equations 6.3 1, 6.32, and 6.33 L? the solvent A in a dilute solution
130 Pa rtial Molal a nd Excess Qu.tntitics

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.

~ 6.8 CONCENTRATED SOLUTIONS

Unfortunately no simple ru les can be developed for the treatment of more


concentrated solutions. The quanti ty J'; is now a function of composition and
the exact functional dcpcmlcnce must he determined l'or cad1 ~y~ tcm experi-
mentally. In this range of composition (comprising about 90 ~~ of the phase
diagram) considerable interaction between solute atoms occurs and the
va rious partial molal quantitative arc no longer independent of composition.
The extent of interaction depe nds to a great extent upon the exact nature or
solute a nd solven t.
Certain sol utions (principall y liquids) show a rather in te resting phenom-
enon. The enthalpy of mixi ng of these solutions is din·crcn t from zero
but the entropy or mixing /J.Sm in some cases is the same as fo r an ideal
6.8 Concentrated Solutions 131

solution. That is,


~S,, = - R(XA In XA + X 11 ln X u) (6.4 4)
Such a solution is termed a regular solution and va rious simplifying relations
between some of the thermodynamic quanti ties are obtained. Most solid
solutions do not behave in th is " regular" fashion but nonetheless, it becomes
convenient to study how regular solutions behave as a step away from
I\ ideality. We shall consider these systems in more detail later. Briefly, however,
since ~s." follows equation 6.44, ~Sm. will be symmet ric about X A = X 0 =
0.5. Similarly we shall show later that l:l l/"' wi ll also be symmetric about
XA. = X 11 = 0.5 a nd in fact can be expressed as
(6.47)
where a' is a constant characteristic of the particular system at a gtven
temperat ure and is proportional to T-1 .
More generally, however, D..H 111 a nd D.S,, for most solid solutions are
not given by such simple relations. For a moderately dilute solution t:.. Hm is
sometimes expressed as a power series in X 11 :
D.Hm = a'Xu '
+ bX112 +eX/'+·· · (6.48)
Using a relation si mila r to equation 6.27 we sec that

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

The quantity a' represents the value of (17 11 - / / 11 .) in the composition


range where the solute follows Henry's law, and hus been interpreted to
represent the interaction between solutes. A positive value of b represents
a repulsion between like solute atoms, whereas a negative value of b represents
an aflraclir•e interaction between the solute a toms in solution.
Perhaps it is appropria te to discuss here some of the general methods
used to obtain thermodynamic data for solid solutions. One of the most
useful methods is the emf technique whereby the electromotive force between
a pure clement and the clement in solution is measured. Since
"G --
u - ~ ·~J];"
ll0v· = (C i · - G i ')

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,

Since the compostlton is known the activity coefficient may rcad~y be


obtained. By measuring the emf as a functi on of temperature both {17, - II;')
anu (Si - S/) may be obtaincu ~int:c

and
a[( G.- - G;.)/T] - . a(C/ T)
ar
a(l /T) = ( H1 - Ht ) = - n.':/' a( 1/ T )

Jf these quantities are determined as a functi on of so lution composition


for one component of the binary system, the app ropriate quantities may
be determined for the other component by use of the procedures described
in Section 6.3.
Another technique, applicable when o ne of the components is rather
volatile, is measurement or the equilibrium vapo r pressure of this component
over a solution containing this component. Si nce ar = p,/p/ , the acti vity
may be calculated. Since (c7, - c; ..·) = I~T In a,. the quanti tic-; (S, - s,·)
and (17 1 - He') may be obtained by measurements of a; at vari ous tempera-
<I
tures. ff a i is determined as a function of composition for a binary system, I
tile activity of the other component may be obtained by use of the procedures
described in Section 6.3. Actua lly some sligh t modification of these procedures
is necessary in the case of activi ties. Starting with lhc basic equation
X A dG A + Xu dC 11 = 0
or
(6.5 1)
6.8 Concentrated Solutions 133

If the activity of component B is known as a function of composition we


may obtain aA by integratio n
I

' 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
\

a 0 = Yu Xu and Yn° is fi ni te.) This creates a difficulty, however, since as


0

a 0 -+ 0, In a 11 - ..- - oo and thus the area under the curve of X 0 /( I - X 11 )


'j
• versus In au cannot be accurately evaluated between the lim its imposed,
as shown in Fig. 6.6 for the Cd-P b system. An easy path leads out of this

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.

•· difficulty, however. By definition a, = ytXi, a nd substituting this relation


into equation 6.5 1 we find

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~

and thus the eq uation simplifies to


X A d In YA + Xu d In J' ll = 0

Since a 0 is known as a fu ncti on of composition , /' u is also known as a


function of composition . Thus we may determine YA by graphical integra tion

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------

fig. 6.7 Determination or Yph from


"""" equat ion 6.52. F rom L. S . Dnrkcn and
0.2 0.4 0.6 R. W. Gqrry, Phy.\icnl Chemistry of
log 'Y('.c~ Metals, McGraw-Hill, New York 1953.

A standard method for obtaining heat of mi xing data is by use of a


allorirnctri ~ method . A sa 111plc or solution is dropp<:d into. say. litpt id tin
at a known temperat ure in a system of kn own heat capacity. Jr heat is
evolved the temperature of the system will increase if the calorimeter is we ll
insulated from its surroundings a nd vice versa for an endothermic process.
Thus we have a reaction
Solid solution (XA, X 11 ) = A and B in liquid Sn
where 6H i is the heat of the reaction and C1, is the heal ca pacity of the
system. The same experiment is now performed for a mechanical mi:< lurc
I

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
(

For many solid systems, it is uimcult and time consuming to determine


I thermodynamic properties; as a resuH complete thermodynamic data are

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.

)C 6.9 EXCESS THERMODYNAl\tiC QUANTITIES


...
For many applications it is of interest to know the deviation of thermo-
dynamic quantities from those quantities in an ideal solution. As an example
consider the partial molar free energy,
6.C 1 = C1 - G/ = RTin a 1 = RTin y 1 + RTln X 1

For an ideal solution Yt = 1 and thus


(~Gi)~<tc 1d = RT In X;
Defining the excess free energy

~G/(1\ = ~G{ - (~GJ,dt·l\1


we firid

I Mi,X' = RT In I y, (6.53)

For the case of the free energy of mixing we lwve

D.Gmx8 = D.Gm- (~Gm)td('l\1

and hence upon substitution


(
6.Gm"8 = RT[X A In YA +Xu In Yul (6.54)
I For the case of the enthalpy
(6./1 m)lttcaJ = 0
(6.Hi)1deal =- 0
136

T he re fo re
6. // Ill l{'4 = 6. // til

an d sim ilarly (6.56)

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

For a multicomponent system we have s hown that

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'

Substitution into equation 6.60 yields

aGi) <IX,+ V; dp + M; de/>= 0


(ax ( 6.6 1)
,.7'
)
Multiply both sides by X i and upon summatio n
)
:L x~(acj) c1x, + 2: v. dp + ~ M , tlif, = o
axi
From the Gibbs-Duhem equation
2 Xi c/Ci = 0 or .2: X (aC,) dX1 =0
1
ax,
and therefore
2 X{Vidp +I XiMid4> = 0 (6.62)
Consider as an illustration the case of a binary alloy system in a centrifugal
field . This would typically take the shape _of a cylindrical specimen rota ting
138 Partial Mul:al a nd Excess Quantities .f
about an axis o f rotatio n in such a man ner that the cylinder ax is is no rmal
to the rot atio n axis. The po tential at point r is - ~f•J 2 r2 where <'> is Lite
angular velocity. Fro m equatio n 6.62 we obtain

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)

From equ:ltion 6.64 it is seen that a gr'"1ph of In X, cr~us r 2 yiclus a cul\c


which has a slope equal to th e right-hand side of equation 6.64.
Let us further ass ume that the solute is present in dilute form. The solute
(compo nent 2) therefo re fo llows Henry's Law and the solvent (com po nent 1)
follows Raoult's law. Fo r this case

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

Centrifuge experi ments can therefore be used to provide information


about V'. To a first approximation (if relaxations are neglected) if the sol ute
dissolves substitutionally. V' 1. For an interstitial V' ~ 0, and if the
r-.J

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

Fig. 6.8 The distribution of Au in K afler centrifuging at 40 x 103 r.p.m. From L. W.


Barr and F. A. Smith, Phil. Mag., 20, Ser. 8, 1293 ( 1969).

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).

0. I 0.2 0.3 0.4 0.5

-29,500 -29,700 -29 ,700 - 29,700 - 29,700


- 11 ,970 -9 ,660 -7,320 - 4,940 +500

(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

0.2 0.3 0.4 0.5 0.6 0 .7 0.8 0.9


0. 1

ll H ,, -u.o - IH10
- 1240 - 11 30
(e« l · mo l) - 355 - 655 - 9 10 - 11 20 - 1230

Find f:::.GI(, at X a11 = 0.30.


(a) F ind t:::. R cu and t:::. fi Au at Xcu = 0.3. (b)
alloy cont aini ng 30 at % Cu ,
(c) Calculate the parti a l pres sure of Cu for a n
in equi libri um with Cu in the
70 a t % Au. (d) Ca lc ula te the oxyg en press ure
a lloy in (c) a nd Cu 20.
0 sCil lc in cont act wit h NiO and
4. Jn the prec edin g prob lem supp ose that the Cu 2
0.4. Calc u la te the etluil~briurn
a solution form s so tha t the activ ity of Cu 20 is
oxyg en pres sure fo r this case.
5. Deri ve expressio ns for (flu - Jl u ) and ( Vu
0
- Vu, > for the so lute in a J ilule
solu tion.
•I
I
.I
7

Thermo dynami c Propert ies of


Alloy Systems- A Mc)del Approa ch

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).

a va riety of behavior. From a fundamental point of view , the thermodynamic


be av10r o a oy sys ems IS ve ry 1 tcu o a ·
the general principles may be rather well understood. In forming an alloy
from the pure elements one mixes ions oLthe solute element with ions of
141
1

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).

solvent. ln calculating thermodynamic quantities one should consider the


repulsion between ion cores, the interaction between cores and electrons at
T
the Fermi surface, as well as other eiTecls. Significant steps are being made L )

in calculation of thermodynamic properties from first principles for some


simple alloy systems but as yet no general, easy to apply rroced ure is availahle.
As a consequence, one devises variou" types of models "ltich arc useful i11
providing some understandi ng of ~lloy behavior as well as in correlating
this behavior with other properties. A useful model a pp roach is to assume
that one may treat the interaction between ions in a solute by a pairwise
model. That i s~1e properties of a system may be represented by the sum of I .)
i t actio ns betw~en nei ghbo rin ~ Qairs of ions and any ~licati ons_ill!c
to three~body interactions, .for example, may ~· Some justification
for the validity of this approach is obtained from application of pse ud o~ .-
.. .I
. potential theory.
7.1 Introduction 143

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.

According to this pair potenlial or quasichemical model, in view of the


fact that the enthalpy of interaction of solute- solvent pairs is different from
solvent- solvent and solute- sol ute pairs, a type of orderi ng will occur which
minimizes the free energy of the system. There wi ll be a trade-off, therefore,
between the entropy which has a maximum value fo r complete randomness
and the enthalpy which will ha ve a minimum val ue for a n ordet:ed system.
For some systems, particularly those that involve transition metals, other
factors due to magnetic and electronic effects must be considered.
Jn order to illustrate the pair potential approach consider an alloy which
contains N A atoms of type A and Nn atoms of type B. There will be three
types of interactions to consider, namely, A- A, A- 13 , a nd B- B. Each of
these will be co nsidered to have associa ted with it a mean potential H AA'
144 A 1\lodcl Approach to Alloys

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.

f' I.\IIJ 2PA-\


N
:\ =-- z + - z- (7. 2 )

Silllilarly rur type B ions


1
1.\IIJ
/ 2 /' tlll
N
u
= --
z + - z- (7.3)

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

11 /i,l = II - entha lpy of pure A - cn th:tl py of pure B (7.5 )

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)

7.2 APPLICATION TO IDEAL AND REGULAR OLUTIONS

For an ideal solution ~Hm = 0; therefore from equation 7.7

n= 0 and HAn= HHAA + lfuu)


We see that a solution will behave ideally if the enthalpy between unlike
pairs is the arithmetic average of the enthalpics between like pairs.
In the case of a regular solution it will be recalled that ~Hm :;'; 0 but
/:1S"'xe = 0. This latter restriction implies that the vibrational entropy of
elements rema ins unchanged upon transferring from the pure state to the
solution and further that lhc mixing is completely ramlom. As a result.
Pu•.n 1 can be readily evaluated from simple sta tistical considerations. Let
us consider a gram-atom of alloy. Thus (N A + Nu) = N 0 and X A = N,, /N 0
and Xn = N 11 /N0 • The probability that an ion of type A will be on a given
site is XA. The·probability that an ion of type B will be on a particular nearest
neighbor site is Xn and the probability that both will be on their respective
sites simultaneously is XAX u· Similarly, the probability that an atom of
type B will be o n the former site is X 11 and lhe probability that an atom of
type A will be on the latter site is X A· The probability that they will be on
their respective sites simultaneously is again XHXA· As a result the prob-
abi lity that two sites will be occupied by unlike atoms will be the sum, or
• ' 2XAX11 • The total number of pairs in the crystal is !2N11 , therefore the number
of A- B pairs will be equal to the total number of patr~ multiplied hy the
probability that a pair will be of the A - 13 type. Thus
p(A U) = 2X AXIl . ~ZNu = x .. XuZNo (7.8)

We find thererore that the heat of mixing is


1:1HIIl = x Axlln (7.9)

Since n is independent of com positio n acco rding to the zeroth order


approximation, D.H,, is a parabolic function of composi ti o n.
146 A Model Approach to Alloys

If there is an attrnctive interaction between unlike ions the A- A pair


enthalpy will be more negative than the A A pair enthalpy or U U pair
enthalpy, and hence 12 will be nega tive in sign, yielding a negative value or
the heat of mixing. Conversely if there is a repulsive interaction between
unlike atoms, n will he positive and !1 //, will also he positive.
lf a stron g attractive interaction between unlike atoms exists. f:l/1"' ca n
be made mo re nega ti ve by having short-range o rd er in 1!1e solution , which
means increasing P."' 11 over' the random value. This will tend to make th e
free energy of the solution more negative thro ugh reduction of the D.. lf,,
term . 011 the other hand . howt.·vcr. tht.• mi.\inv. t:ltlropy will dt:l' l l':t-:l·. ~ in n:
fF, the number of w~tys or <Hrangi ng atoms o n the latlice, is less and thus
increases the free energy. (This will be discussed more fully in a later section.)
An optimum value of short-range order will be atlaincd, renecting a balance
between f:llf,, and the T D.S, COJ1tribution . In th e case of a repu lsive inter-
action, D.H111 could be reduced by promoting clustering of like atoms or
decreasing P" 11 compared with the random value. Th is, also, will rcsull in
a decrease in 1r, the number of ways of arranging atoms on the lhtLice, and
hence a tlecrc:tse in 6.S,. Again an o ptimu111 degree of t'/u.\fering wi ll resul t. '

\
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.

17 .\ - II A . = 0.17 t\ = (I - .\' :\ fil (7. 10)


6!'"" (7. 11 )
I
Since 6.S}.!f, = 0,
SA - .\·., · = .1.\, = - N In .\' ,
sll - su· = n.SH = - R In XII
Usi ng the relation
7.2 Application to ldeaJ and Regular Solutions 147

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_ __,

B 0.2 0.4 0.6 0.8 A


xA-
Fig. 7.4 Heat of mixing as a fun ction of composition for a regular solution for various
values of!l. From 0 . J . Klcppa, in Liquid Meta/sand Solidification, ASM, Cleveland, 1958.
A Mode l Appr oach to Alloys
148

fig. 7.5 A cti vity of component A in a


regul ar solut ion as a funct ion of the inter -
action param eter i !. Fm111 0 . J . Klcpp a.
B 02 04 0.6 in Liqru J fllaru l.<r and Sol itlijiC'afivn, 1\SM,
x,. _.. Cleveland. 1958.

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

7.3 NON REG ULA R SOL UTI ON


fro m rando mness,
For syst\!ms in whic h there is considera ble devia ti o n
appl icable. For th ese
th e expressions deri ved in the last secti o n arc no t
, na mely ,
solutions Guggenheim ' has derived a rclali o n fo r P1A 11 1

P t AJJ l = X AX uZ N 0 {1 - X a X 11 [cx p (;~~~) - 1] ) (7. 14)

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

6 11 111 ~ XAA' 11 U(I - 2


X .\ A
ZRT
"u) (7. 15)

\• :! \ ' " 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

In the case where n


in equation 7.14 becomes equal to that in
= 0, P (A.UI

7.8. When n is negati ve in sign (equivalent to attraction between unlike


neighbors), P<Afll calculated from 7.14 becomes greater than the rando m
value expressed by 7.8. For positive values of n, the reverse is true. Thus
equation 7. 14 represents a n attempt to express the conditions for more
realistic situations. In these cases when P<Atll ¢ P< AIIl (random), short-
range order is said to occur. In order to examine this phenomenon further
consider a B ion surrounded by Z nearest neighbors. For a random solution
the probability that a given ion in this shell is an A ion is simply X 1v For a
nonrandom sol ution the probability p 1 wi ll be tl ill'crenl fro m X A· The short-
ran ge order parameter a 1 is defined as
al =1 J!J.. (7. J 8)
XA
which is equal to
a, = 1 - P u. nJ (7. L9)
ZN 0 X AX 11
In principle, one may go out into the second shell a nd ca lculate p 2 and a 2 ,
etc., si nce they will also tend to be diflc rent from random.
For complete randomness a 1 = 0; for short-range order in which there is
a preference for A- 8 pairs, a, < 0; and for clustering a 1 > 0. The reader
should be aware that other definitions of the short-range order parameter
are in use, so cure must be taken when evaluating rcsulls. The quantities
a 1 , « 2 , etc., may be measured in many cases by x-ray and neutron diffraction
techniques. Some· results are shown in Fig. 7.6. This value may be used in
turn to calculate !l from equation 7. 14 and 6 /1 ,.. may be calculated from
equation 7. 15 . If experimental Lhermodynamic data exist for 6 H ,,. a check
on the validity of eq uation 7.14 may be obtained. Such an examination has
been made for several systems. For systems that do not involve transi tion

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

Fil:. 7. 7 Comparison between hc;ll of


mixing in t he AI Zn !\)'~ tc111 C.1lcu l.l tctl
rr0111 X - ray IIIC:I''i\I I CIIICi lh :tiHI din:l.:l
thermodynamic mctho<.J<;. From P. ~.
0.1 0.2 0.3 0.4 0.5 Rud man and n. L. A vcrbach, Acta Mc•t.,
Xz n - 2, 576 ( 1954).

elements there is often reasonable agreemen t with the predictions based on


the quasichemical theory discussed here and experimental structural da ta.
The solid AI- Zr system is one for which rather good agreement is ob t ait~d.
a s shown in Fig. 7.7. It should be observed tlwl if 6//, is pos itive, n is
positive. « 1 > 0 so that clustering occurs in this system .
By use of an approach similar to Guggenheim the following relations ha ve
been derived for the activity coefficients. i
y - + 2 X A]~~
I (7.20)
YA = [
XA(Y + 1)
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

G . B. Stringrellow and P. E. Greene, J. Pltys. Chem. Sol., 30, 1779 ( 1969).


1
J )
2 Jl. L . Averbach, in EnNgetics in Metallurgical Phenomena, Vol. II, W . M . Mueller, ·_j ··:~
Ed ., Gordon and Breach, New Y ork, 1965. X
. 1 :.1
j . }
7.3 Nonregular Solutions 151

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 --

__Q_ = u + j(X) + g(T)


ZN 0
F or the free energy o f mixing , by employing 7. 14 and 7. 15 we may write
f1G m = P.udu + j(X ) + g(T)] - T !!l.Smc
where t1S,11 c is the co nfig ura ti ona l e ntropy . O the r entropy co ntributi ons are
obtai ned from di ffe rentiatio n of the first term on the right-hand side with
respect to temperature since S = -(aGfaT),. Now
l:lsmc = k In ·rr
and the numb er of ways o f a rra nging A- A , A- 13, B- A , and B- 8 pa irs is

,.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

Solving for /!:,.Sn/ and recalling that

we obtai n

6.5,,/" ~ IO'.j kN0 (XAln X,..+ Xu ln .\' 11 j - {a~. lZNu.Y".\' 11 ( 1


and also
/::,. 1{ 111 = 6 11 ,/~.s = ZN 0 XAX 11 ( 1 - cx)[u + j(X)]
For sma ll derivations from ideality

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

assuming that « = 0. a. is then calculated from the sum fu + j(X)] + J!.T


and substituted back into the expressions for 6.11,, <.llld 6S"""' in 01 dcr to
calculate [u + j(X)] and g again-;- This process is repeated until consistency
is attained. The comparison of thermody namic calculation with x-ray .

results is shown in Table 7. 1 fo' several solid a lloy systems.
7.4 Order- Disorder T ransitions in Solids 153

Table 7. 1 S hort-Rang e O rder Ca lcul a Cio nsa


(l
Mole
System frac. f::.Hm flsu N 0 [u + j (X)) Nog
(A- B) B (kJ/mol) (J/mol· K) (kJ/mol) (J /moi ·K) 0 /ZRT (Thermo) (Jt-ray)

AJ- Zn(650°K) 0.2 2.2 0.54 1.2 -0.50 0. 17 0.06 0.13


At-Zn(6S0°K) 0.5 3.3 0.63 1.2 -0.46 0. 17 0.09 0. 16
Al- Ag(820°K) 0.10 +0.84 0 .42 +0.77 -0.38 0.07 0.01 0.15
Al- Ag(820° K) 0.815 -1 .05 4.2 -0.52 -2.3 -0.36 -0. 11 -0.09
Cu- Au(720°K) 0.50 -5. 1 -0.08 - 1.48 -0.23 -0.27 -0.1 4 -0.13
Cu- Au(720°K) 0.75 - 4.4 0 - 1.76 -0.29 -0.33 -0. 12 -0.15
Au- Ni( II 25°K) 0.5 7.) 2.9 2.5 -1.1 0. 13 +0.06 0 ±0.05
9
Au- Ag(800 K) o.s - 4.6 -1.4 - 1.4 0.25 - 0. 18 - 0.09 - 0.08

• From B. L. Averbach, in Energetics in Metallurgical Plumomttna , Vol. II , W. M. Mueller, Ed., Gordon


and Breach, New York, 1965.

It should again be emphasized that the use of pair potentials is only a


convenien t way to represent in a statistical sense the gross thermody namic
properties of an alloy. The use does not imply that there are actually covalent
bonds between pairs si nce the terms u and j(X) for a metal include energy
contributions from electronic interactio ns near the Fermi surface which
belong to the crystal as a whole as well as ion- ion contribution.

t 7.4 ORDER- DISORDE R TRANSIT IONS I N SOLIOS

Atomic Order

Various types of order-dis order reactions may occur in crystals. There is


a second-order magnetic transition , for example, in some solids in wh1ch a
ferromagn etic or anlifcrrom agnetic substance become paramagn etic as the
temperatu re is raised above the critical point As discussed earlier there exists
a change from a supercond ucting state to nonsuper conductin g state for a
large number of materials. These processes result from the alignmen t of
magnetic moments in the case of ferromag netic materials and electron spins
in the case of superco nductivity In addition to these kinds of processes ,
long-ra nge atomic o rdering processes occur in several alloys. A t high
temperatu res in these systems, the crystal exhihits o nly sho rt-range order ,
whereas at low temperatu res, the atoms may order themselves in a long-
ra nge ma nner.
Consider as an example a n alloy of composit ion 50 a t % A and 50 a t % B,
which tends to form a n ordered phase. That is, the A atoms tend to order
themselve s on one type of si te, q., a nd U a tom s tend to order themselves o n
another type of site, {), as shown in Fig. 7.9 for a body-cent ered cubi c
structure. Let us denote by '~ the fraction of ex sites occupied by the right
atoms (A atoms) and by rp the fraction of {J sites occupied by the right
atoms (B atoms) in an ordered system. The fraction of ex sites occ up ied by
154 A Model Approach to Alloys

a '
a
a

/a
{3 13
a a

/ / a /
a

Fig. 7.9 Long-range order on a b.c.c. lattice.

wrong a toms (13 atoms),


t.
~~"ex• will be give n by I

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

,97 = ,.« -XA


(7.21) .
I - XA 1,
or, considering disorder on the fJ sites,
f'P _ l"p - ){II
J (7.22)
1 - Xu
From eq uations 7.21 a nd 7.22 we see tha t, for complete disorder, ,97 = 0
and, for complete order, !/' = I. For a stale of order given by 0 ~ //' < I,
the fraction of A ato ms on ex sites is '~~· Considering N total sites, there are
(N/2) (J. sites and (N/2) fJ sites. Thus the total num ber of A atoms on ex sites
is r«(N/2). Substituting in equation 7.21 for XA = Xu = ! yields

No. of A atoms on ex sites = y)N


(1 ~

No. of B atoms on fJ sites = C: 9') N


7.4 Order -Diso rder Trans itions in Solids 155

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

No. of A atom s on {3 sites = (


1-
4
.9') N

No. of B atom s on ex sites = (


1- y)N
4
to ex
Jn the body-centered cubic crystal, fl si tes will be nearest neighbors
A- U
sites. Let us now evaluate the num ber of A- A pairs, B- 13 pairs, and
pairs for a n ordered struct ure with long- range order parameter Y.
The probability that an A atom will be on an a. site is r,., and the proba
bility
unded
that an A atom will be on a fJ site is wp = (l - r p) . Each a. site is surro
an A - A
by Z {3 sites, but each pair is count ed twice, so the probability of
pair is
Zr ( 1 - r) = Z(L + Y)(l - sP) = Z(l - .9'2)
• p 4 4
the
The total number of pairs P A A. is the probability of an A - A pair times
number of A atoms or
2
_ Z( I - 9' ) • N _- ( J - Jc.o2 ) N
PAA-
4 2

since Z = 8. Similarly the total number of B- B pairs is found to be

Pun = ( l - Y' 2 )N

For a solution containing 50 at %A and 50 at % B, the numb er of A - B


pairs is

The enthalpy for a gram -atom of solution is


2
H = No(l - 9' )( f/A A + Huu) + 2No(l + 9'2) H An
The configuration entropy is given by
S cant = k In 1r
where
if/'= _ __ _ _ __ (_N--'-/2_)_! - - - - - -
(No. A atom s on ex sites)! (No. B atom s o n oc sites)!
(N/2)!
.. X ------------------~~----B -------------
(No. A atom s on {3 sites)! x (No. atoms on fJ sites)!
156 A 1\todcl Approa ch to Alluys

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

Scone = .R{In 2 - H ( l +!/') In ( I + .$1') +( I - .Y') In ( I - ~Y')j} (7.2J)

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

G = No(l - f/2)(/zA A + /t1111) + 2No( l + Y'2)hAII


+ .9') In (I + !/) + (I - .Y') In (I
0

- RT{In 2 - i[{ l - .9")]} - N 0 1's


(7.24)

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

2[2/t \11 - (, t\ J\ + , 1\ll) j


T
c
=- --------~~--~~
k
(7.25) .'
157
7.4 Orde r-Dis order Trans itions in Solids
1.5 . . . - - - - - - , . - - - - - - - - .

~ J.O
.:
Ql
....
"'U
0
Ql
00
I cIQ
....
00
c
~ .3 0.5

0 o.____ __ _0_..5_ _ _ _ __.1.0 Pig. 7.10 Long-range order parameter


,,,.. versus temperature for an A B sol ution.
'- / A C

and at any temp eratu re differ ent from Te,


( 1 + 9') = 2!/T c
_ ___;; (7.26)
In
( I -Sf' ) T
orde r appro xi-
This deriv ation is know n as the Bragg-\Vi ll iams o r ze roth-
matio n. At low temp eratu re .'/' is very close to I, and as
T incre ases towa rd
coo perative
Tc, 9' decreases very rapid ly. This beha vior is typica l of a
ti cally to crcutc
phen omen on. When o rder is perfect , it is dillic ult e nerge
eds, hov.ever,
disorder (to excha nge A and B atom s). As diso rder proce
eti c poin t of view
the process beco mes progressively easie r from a n energ
beco mes zero for
and finally, in the case of comp lete disor der, the energ y
upo n Sf'.
the excha nge process. The diso rderi ng energy thus depe nds
lo ng- range o rder
As Fig. 7. 10 indic a tes, acco rding to thi s calcula tio n the
a co nseq uence the
param eter c hanges over a range of temp eratu res. As
ity, Cll, may be
trans form a tion is no t first orde r in nature. The heat capac
entha lpy. U pon
calcula ted by ta king the te mpera ture deriv ati ve of the
as expec ted fo r a
perfo rming thi s oper atio n , a di sco ntinu ity in C,, is found
a nd meas ured
second-ord er tran sition . The co mpar ison betw een calcu lated
n alloy of 50 % C u,
va lues of f/ as a func tion ofT is show n in Fig. 7. 11 fo r a
expe rimen tal heat
50 % Zn , a nd a comp a riso n between calcul ated a nd
ca pacities is show n in F ig. 7. 12.
d iiTere nt crystal
Orde r- di so rder tra nsfor matio n s may occu r in many
system such as
systems. For exam ple , there a re tran sform a ti o ns in the f.c.c.
75 at % Au . These
in Cu- Au alloys at abo ut 25 a t % Au, 50· aL % Au , and
1
--~ -
~!periment
approx.

""'\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

Fig. 7.13 Long-range order param eter !/' for an A3 B


alloy. From F. C. Nix and W .
Schockley, Rev. Mod. P!Jys., 10, I ( 1938).

it S"- Tcur ves


trans form ations appe ar to be first order in natur e and exhib
is inade quate in
of the type shown in Fig. 7. 13. The Bragg-Wi lliam s theor y
be secon d-ord er
treating these for trans form ation s since it predi cts them to
rathe r than first order in chara cter.
do not have
One may readjly show that order-diso rder trans fo rmati ons
r over a comp ositi on
· to occu r at precise chem ical comp ositio ns but may occu
ideal , howe ver,
interval. The furth er the actua l comp ositio n is away from the
ple, S" obvio usly
the lower will be the maxi mum value of 9' and Tc. For exam
is differ ent fro m
canno t have a value of unity if the comp osi tion of the alloy
for every one
25% A, 75 % B, say, since there are three face-centered sites
, for exam ple,
corner site in the f.c.c. struc ture. In a 20 % A , 80% B alloy
ple is shown in
so me B atom s must by necessity resid e on A sites. An exam
and T 0 is abou t
Fig. 7.14. Note that the maxi mum value of Y' is abou t 0.8
that for an alloy
640°K . This transition temp eratu re is 20°K lowe r than
which conta ins 25 at % Au.

1.0
l
-
,-
)(- )(- )(
0.8 i"'--x j(
X

0.6
,!Jl
0.4 - \- )<

~
0.2 ~\
'
100 200 300 400
Temperature (•C)

fig. 7.14 Long-range order param eter as a fun ction of


tempe rature for an alloy con-
C. ll. Sutcliffe, A cta M et., 2,
taining 80 at % C u and 20 % Au. From F. E. Jnum ot and
63 (1954). -
- - - - _ _ _ , .lioliil
, l

160 A Model A)lproach to Alloys

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~ -~

Fig. 7. 15 MagneLi?aLio n versus reduced temperature for a fcrro mugnctic- parumagnctic


transition. Tc is the Curie temperature.

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.

7.5 SOME GENERAL CONS IDERATION Oft ALLOY SYSTEMS

ln a general sense the thermodynamics properties of an alloy will be the


sum of several contributions. The configurational contribution has been
1
H . Sato, in Phy:rical Chemistry- An Aduanced Treatise, Vol. X, W. Jost, Ed .. /\Q dcmic
Press, New York , 1970.
2 R . Weiss and P. Tauer, Phys. Reu. , 102, 1490 ( 1956).
161
7.5 Some GeneraJ Considerations of Alloy Syste ms
are electronic
discussed a t some length in this chapter. In addition there
vibrational
contributi ons, magnetic contributions (disc ussed above), and
iple be equal
contributi ons. The entropy of mixing, therefore, may in princ
to the sum of these four contributions.

6.Smxs = 6.s;:n r + 6.SmtLIC + 6.Svlb + 6.Sel


sent excess
Excess symbols are left off three of the terms since they all repre
contributions.
rtant in
The magnetic and electronic contributi ons may be very impo
gurational
alloys which involve one or more trans ition meta ls whereas the confi
equation for
and vibrational terms are generally prese nt. An approximate
6.Svtb at high temperatures may be readily derived.
crystal at
Let us consider the vibrationa l entro py contribution to a
close to "'m·
elevated temperatures. For this situation most frequencies are
the Einstein
Conseque ntly, it will be a reasonable approximation to use
is given by
approach. As we have shown earlier the entro py of an osciJJator

S = k In fl' + kT(0 In !!l')


ar v
where
;;r = exp ( - hv/2k T)
1 - exp ( - lwfk T)

Expanding 1Z in an infinite series,


!Z = 1 - {lzv/2k T) + l(h1' /2kT)
2
+ ···
(llvfk T) - !(hvf kT) +
2
···
At high temperatures hvfkT << I, and hence high- order terms
in the infinite
series may be neglected. Thus

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)

and since the Debye temperature 0 is equal to In 1•/k


(} XA·(} Xu
6.S = 3R In A n
y o·.
Consequently, the vibrational contribution to the entropy of mixing may be
"' estimated if the relevant Debye temperatures are known.
The electronic contribution 6.S~. 1 at high temperature may be estimated
from the low-temperature heat c<tpacity. )'· It will be recalled that the heat
capacity at very low temperatures is due to absorption of energy by clcl:trons
near the Fermi surface. On the basis of rigid band calculations
3y
N(U) = ')
27T2k-
where N( U) is the electron density of states.. For an alloy containing a tran-
sition metal, y and thus N(.U) may va ry considerably with composition, as
shown in Fig. 7.16 for the Cu-Pd system.
lf the rigid band theory is employed the electronic entropy contribution
is given by
7'
S,,1 =
J:
0
y dT = y T

or fo r the formation of an alloy


6.Sct = (YtLIIny- (X.t\YA + XuYu)JT
where y A and Yu are the val ues for the pure com ponents.
For any given alloy /::,.Smx11 would normally be dominated hy one or two
of these four contributions. Calculations for the Cu-Pd system arc shown
in Fig. 7. 17. Comparison with Fig. 7.3 shows rather good agreement with
thermodynamic dala.
I I
10.0 I I 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

The electronic contribution to the energy term may be si mply obtained


from the y quantities if available.
l

This term is calculated to be as large as - 15 kJfmol in the Cu- Pd system


and would not be counted in a calculation based on pair potential concepts.
Thus the degree of short-range o rder would be overestimated from thermo-
dynamic data if all of the large va lue of 611,, shown in f-ig. 7.3 was ascribed
to the [11 + }(.\')] term am.! D.U,.1 wa s not removeJ fr<.'lll 6. // 111 before
calculation.

PROBLEMS

1. .I n a face-centered cubic lattice containing 40 al % A and 60 at ~~ Bin tbe form


of a random solu tion, calculate the number of A - A pairs, B B pairs, and ~ - B
pairs in a gram-atom o f solution. ·
2. An f.c.c. alloy of cn mpoc;it inn 40 °~ A and 60"~ 13 s how~ c;ub,tan tial shoJI -
range order. PAn is found from x-ray measurements to be 1.05 times the va lue
for a random solution. Ca lcu late P... i\ and P 1111 in a gram-atom of alloy.
3. For Problem 2 calculate the configurat ional ent ropy of mixing. Ca lcu late the
c'ccss conliguratinnal Cllll'\lPY tlf •nixing. Cakulatc th~: t.:lllha lpy l'l' 111i-.:i11g
and the excess free energy o f mixing. as'\uming that the therm ouy n~tmi\!
properties are governed by the configurational cont ri bution.
4 . For the Cu- Pd sys tem, calculate the electronic contribution to the energy of
mi"ing. Es timutc th\.! difTcrcncc b \.!twccn the enthalpy of mi·<in~ ami cncr!!Y nf
tni-.ing. With a t11.:g.11ivc heal ol' mi.·dng a" sho" 11 in I ig. 7 . .1. woul d it be
possible to have clustering instead o f shor t-range oruer?
5. Supposing that the short-range order parameter i.n a 50 °{, Cu. 50 ~~ Pd i'
equal to 0.04, calculate the excess configurational enlropy. ompare wi th
D.S., and ~Sd presented in Fig. 7.17. • •
6. Calculate the maximum value of the long-range order parameter in an f.c.c.
alloy which conta ins 15 ~{, A and 85 ~~ B.

)
r
I'
~~
8

Equilibrium Between Phases


ofVa riab le Co1nposition

8.1 GffiBS PHASE RULE

In this chapter we shall show how, in special cases, useful thermodynamic


data may be obtained directly from phase diagrams. In addition the relation
of extent of solubility upon factors such as external pressure and particle
size wilJ be investigated. Before examining these topics some consjderation
should be given to the Gibbs phase rule. This rule, presented by J . W. Gibbs
in four pages of a paper which had a total length of I 30 pages, has had a
significan t influence on phase diagram construction and the relationship
between phases. ll is ironic that, allhough the paper was puhli~hcd in 1876,
it wasn't until about the yea r 1900 that i ls importance was recognized. Prior
to 1900, many published phase diagrams were fundamentally incorrect and
the phase rule provided useful rules about the construction of these diagrams.
Before deriving the phase rule let us consider one importan t property of C1
when component i is present in different phases. For si mpl icity let us con-
sider two phases. The arguments, however, may be readily extended to
more than two phases.
Consider very large amounts of two phases, both of which contain
component i as shown in 1-ig. 8. 1. Compone nt i in the a phase will have an
activity a/X., and in the f3 phase it wi ll have an activity a/. Let us transfer a
gram-atom of i from ex to fJ al a constant temperature without changing
composition. The original quantities of a and (I are so large that the com-
position is changed only infinitesimally. The reaction is
i(a = i(tl)
11
) ~G
Component i in fJ will have a partial molar free energy given by
CI P = GI · + R «f In a I P
165
166 Phases of Variable Composition

Phase Phase
a {3

Component i .. Component i
-f-
Activ1ty n i a Achv1ty a, 0

Fig. 8.1

and in oc it will be given by


C/' = G,· + RT ln at
The free energy of the reaction will be given by
a/
6.G = RT In -
ll ,~
(X. I )

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

must be remo ved


this diagr am is obtai ned at cons tant press ure, this varia ble
from cons idera tion and
f=r -cP +I
The numb er of comp onen ts is two. Thus
/=3 -c/>
eratu re
At point 1: cP = 1; therefo re[ = 2. We may indep ende ntly vary temp
er of phase s.
and co mposition withi n the necessity of cha nging the numb
temp eratu re
At point 2: cP = 2; f = I . We may indep end e ntly va ry only
for exam ple, the
or comp ositio n singly. If we chan ge the temp eratu re,
phas e boun darie s.
comp ositio n of the two phas es must vary along the adjac ent
no degrees of
At point 3: cP = 3; f = 0. At the eutec tic poin t we have
destr uctio n of o ne
freed om. A chan ge in Tor com positio n will res ult in the
or more phas es.
t

168 Phas es of Variu blc Com1wsiti un


The example used above no dou bt seem s simple and
obvi ous to the
reader. Prio r to deve lopm ent of the phase rule, however
, such dedu ctions
were not at all obvi ous and the phase ruJe was most usefu
l in settin g up rules
for phase diag ram cons truction . ft is useful even today
in o rdering in con- ,.
struction of complicated phase diag rams in which there are
several components
and phases. In some of these situations , problems arise
as to determination
of the actual num ber of components present. Consider
, for exa mple, the
additio n of BaO and NaC I to a sol vent. Thes e cons titue
nts may reac t to
give NazO and BaC1 2 ; for example,

Thus we,would seem to have a to tal of fi ve compo nent s


( UaO , Na CI, lla 12 ,
N a20, solve nt) instead of three . This is not correct, how
ever , since the a bove
equation may be considered to prov ide a restricti ve equa
tion as well as the
relation that

The five varia bles therefore arc red uced to three.


In usi ng the phase rule, one mus t be careful to consider a
ll cons titue nts and
poss ible relations between them .

8.2 CALCUL ATI ON OF T II EnM OU\ 'NAM IC QUA


NTI H ES
FRO M SJM PLE PHA SE DIAGRAMS

B Is Soluble in A but A Is Inso luble in 8

Let us consider this simple case first fo r the purposes of


illus tratin g some
of the principles . Com pone nt B is considered to be solu
ble to the exten t of
x~(Silt) in oc at a given temp eratu re Tj , but
A has an infinitesimal solubility
in B. Such a situa tion might be represented by the phas
e diag ra m shown
in Fig. 8.3. Thus at equilibrium at T , for any com
1 positio n X n where
Xo<sat) < X 13 < 1, pure B will be in equilibrium with
B in the ct. phase a t
com position Xu<saL), or for the reac tion

U(s) = Up; r\(>mtJ) ~G = 0 (H .4)


Thus the .chemical potential p, is governed by the following
relalion: l
and

au = aaucsn.l.)
Since pure B is defin ed as the standard slate , a • = I, and
11
If the oc solution is dilute, compone nt B may be assumed
thus a'j1<1111 o = I. ..
to follo w Henry's

1. 8.2 Thermodynamic Quantities and Simple Phase Diagrams 169

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.

Jaw, and as a result YJ:J o may be evaluated since

a ll(llaL) = 1 = }' 1J oxllU(81\L)


Ql

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

Phases of Variable Co mpo~ iti o n


170

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

From reaction 8.4, it is seen tha t 6. Fi 11 co rrespond s to the enthalpy cxpcmled


in transferring pure B to the dilute solution . This is the relative parlial
molal en thalpy. For a dilute solution in which the solute is fo llowing ll cnry's
law, 6.fiu is independen t of co mpositio n. ll is dear that, il' Lh c phase diagra111
for an actual system is of the type shown in Fig. 8.3, /J.I7 11 may be obtainetl
-

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

l\Sn = - k In Xu+ tl.Suxs


where l\Snxs is the sum of magnetic , electronic, and vibration al terms.
In addition, upon transfer of an atom from pure B to the solution, there
is an enthalpy change l\R 8 . The chemical potential change per atom is
given by
flu - P..u· = tl.fin - T tl.Su
or
(8.H)

At equilibrium , of course, JJ-n = flu' for composition Xll<saL) < X 0 < 1,


and the mole fraction of B in a. is X~(snt->· As a resull we find upon rearrange-
ment of 8.8 that

Xij 1, ." = exp r'~•") exp ( - ~;) (8.9)

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

Excess entropy lactor


I 10 100
--~~~
~~~~~~~~
0 r-~~~~-n~

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 ( % )

d a~t:o• uing It' n p e:t lHIIl X tJ " ' a ' 111


Fig. 8.5 Solub ility o f solut es in alum inum plotte
rei a t ivc partiu I mo la r cnte opy c harge.,.
obtai n relati ve partia l mola r heats o f solut io n aml
llurgy . ASM , Clcvc la ml, 1950 .
From C. Zene r, in T!term odyna mic.r in P!tysi cal Meta

. ms . how ever , i nvol vc a n


in a lumi num plott ed in this way . Thes e syste
iate phase ra t her than
equi libri um betw een ex. solid solut ion and an inte rmed
r t he valu e of 617 1,, the
pure B. It will be note d th at, in ge neral , the la rge
e si nce often the m o~ t
high er the va lue or 6S11 x • This is untlc rstan dabl
11

asso ciate d with a s twin


impo rtan t co ntrib utio n to the heal of sol uti on is
8.2 Thermod ynamic Quantiti es and Simple Phase Diagram s 173

energy contribu tion, and therefore a large value of 6R 11 is oflen associated


with a large misfit of solute into the crystal, which lowers the vibrational
frequencies of neighboring sol ute atoms and results in a positive contribution
to .1S11 <D> a nd thus to llSnxs.
Some excess entropy data obtaine d from a variety of systems are tabulated
in Table 8. 1. In some of these systems the solute solubility is quite high, and

Table 8.1 Excess Partial Molar Entropie s for Some


11
S imple Eutectic Syslcms

Solvent Solute t;:,.Su'{"/1.. tin ulk


Cu Ag 1.4 4790
Ag Cu 1.4 3960
Ag Pb 2.5 4320
AI Si 1.7 5120
Au Co 2.5 5900
Pb Sb 0.77 2170
Eu Co 0 .64 511 0
Cu Fe 3.0 8520
Ag Ni - 1.1 4530
Pb Ni 1.8 5480
Pb cu 0.81 2160

a From J . F. Freedman and A. S. Nowick, Acta Met ., 6,


176 (1958).

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.

Case where E lements A and 8 Are IVIutually Soluble in Each Other


to a Limited Extent
The phase diagram appropr iate to the situatio n is shown in Fig. 8.6. This
situation is only slightly different from that discu sed earlier. At temperature
T\) for composition x~ (lllLI) < X n < x~{tlat)t phase <X is in equilibrium with
phase {J, which means that the chemica l potential or A is the same in both
saturated phases and also that the chemical potential of 13 is the same in
174 Phases of Variable Compo~ ition

LIQUid

I
I
1
T
I I
a+IJ

XB

Fig. 8.6 Phase diagram showing limited mutual solubility of A and B.

both phases. Using component U for our calculations as before,

~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

Thus the eq uilibri um consta nt K is


~
K = 2.34 X to- 8 = aNI X P Ot
aNw
The
The activit y of NiO is J, si nce il is presum ed lo form as pure NiO.
proble m then is to find the acti vity of nickel in a I at % soluti on. The
ac-
, the
tivity for pure nickel is I , and in the nic kel-ric h termin al soluti on
where
nic kel will foll ow Raoul t's law. Thus the activity at the solvus line,
n.
XN 1 = 0.94 , is 0.94. This phase is in equili brium with the A-rich solutio
0.94.
(oc co ntai ning 4 a t % Ni) so the activity -o f ni ckel at X Nl = 0.04 is
176 Phases of Variable Composjtion

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

B(Xu0 = 0.99) = B(X 11« = 0.0 1) 6G , + t!:.Gt + 6G:, = /'11« -/tu1'


Upon addition of l he J'ree energy te rms,
AG a fl JJ , . J
(0 · 0 I )X 11ll (..,ul I
Ll = ,,,II - I ' II = ' 1 11 -
( 0 . 9()),\~I (NII I
Thu s
a(j, 11a/T) a(p../fT) _<:.>( - 11 = R a In X 1/l( ..,u 1 _ H a I n ,\ ~1(,_, 11 . 1
o(l/T) - o( l / T) = //H - /-/ 11
Since component 13 follows Raoui Cs law in phase#, 17./ = 1! 11 · ,
a( I / T)
1
a( I / T) i
o In X7,,,.,lLl aIn xriCsall - (u17,t)
o(l/T) o(I / T) R
..

8.2 Thermodynamic Quantiti es and S imple Phase Diagrams 117

Repeating the same procedures for component A, we obtai n

OIn ( l - Xfut~ntl) 0 In ( L - x ll(!latl) /). flAll


=-
o( l / T ) o( l / T) R
The term 6.H11"' correspo nds to the enthalpy expended in transferring pure
component ll to dilute ex; hence it is the relative partia l molal enthalpy of
B in ex. Similarly 6.Rl corresponds to the relative partial molal enthalpy
of A in 13. Solving the above equation s we fino
x~I(Hnt.) = A cxp ( - - -)
/:l/711« (8.1 4)
X~cso.t> RT

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.

Solubility of Gases in 1\tletals

Consider a ,diatomic gas such as H2 , 0 2 , N2 , etc. The solubil ity of these


gases is often very small and as a consequence Henry's law is followed .
There is evidence that the solutes generall y exist in monatomic form. The
overall reaction for oxygen , say, going into solution in crystal A is
0 2(g, p) = 2 Ocsatl (in crystal A)

The equili brium constan t will be


2 2x2
K =au =Yo Ol~<•lll (S. I6 )
Po" Pot
Since we ass ume that Henry's law is followed, at constan t tempera tu re
K IA
X Ocl!o.t.l =-Po , (8.L 7)
Yo
This equation is known as Sievert 's law. For a mo natomic gas, the exponent
in equation 8.1 7 has a value of one. Further , if the gas dissolved was in
.
1'1 '

17H Pha W'\ uf \'a riulJic ('ompu'>i liun

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)
·.

8.3 EFFECT OF PRESSUR E ON SOLUBIL ITY

Consider as a ri rsl example the erTccl of an externally applied pressure on


the sol ubility of a gas in a met:ll . In the la~t section it was shm 11 that lh ~.,·
solubility is dependent upon the partial pressure of the gas itself but we might
ask how the solu bility at constant partial pressure of the gas in questio n is
influenced by applica tion of hydrostatic pressure or tensile stress for example.
We. might expect the ciTect to be rather small. To calculate the efl'ect or
pressure we start with the r~ lalion
dp.t = fl, dp - S, dT
where pis the upplicu pressure. We ha ve shown I hal
d#, = R Td In at
Therefore at constan t te mperature
P, dp
dIn a. = - -
1 RT
Since a 1 is related to X1 by equation 8. 16 for a diatomic gas, we may wri te
dIn ai = d In X;(~<nt.l ·

if the partial pressure of compone nt i, f'; , is held consta nt. Therefore


iii dp (8.19)
d I n X ilsn,t.l = RT

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

1 H . A . Wricdt and R.. A . Oria ni , Acta Met., It« , 753 ( 1970).


8.3 E ffect of Pressu re on Solubility 179

solid, the term (p - l) r'-1 p is related to the stress a by the following:


(J
p= -
3
Thus
In XHsn.tt) = aVf
Xi(fl4t..cr - o) 3RT
where 0' is positive for compression and negati ve in sign for a tensile stress.
Data for the Pd- Hg system are shown in Fig. 8.8. The appar ent disco ntinuity

Stress 10 spec1men (ksi)


-25 - 20 -15 -10 -5 -0+0 + 5 + 10 + 15

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

-100 - 80 - 60 -40 - 20 0 + 20 +40 + 60 +80 + 100


Load-cell reading (lb-force)
specim en at 75"C
Fig. 8.8 Effect 'of elastic stress upon equilib rium hydrog en conten t of
Mer ., 18, 753
under 102 Torr of hydrogen gas. From H. Wriedt and R. A. Orrani , Acta
(1970).

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

Vapor phase ( 1 atm inert gas)

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,

Fig. 8.10 Element of the surface of a spherical parliclc.


182 Phases of Variable Compu~ iti un

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

d(dA) = dV11 -2,.


Also - dA · dn = dV1" since the total volu me of gas pl us par ticle is consta nl,
a nd substitu ting into equation 8.24 we find

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

At constant temperature the chemica l potentia l change is

dp. = vu· dp
We find

(8.26)

Also P.oo = f.J. u· , a nd hence a 00 = 1. The solubility of B in ct. is consi<.l erctl to


be small , so Henry's Jaw is fo llowed by the solute , and th us

aoo = l = Y n ox«IH!<nU

The chemical potential of atoms in a particle of radius r is given by


l'r = /t il . + RT In ar
and upon substitution of equation 8.26 we find

RT In a = 2 avo· .J
r
r
.I
8.4 Solubility of Small Particles 18J

Since Henry's law is followed by the solute,

and thus
ln (X~<a"u),. = 2uVn.
X Blllntl T Rr
The quantity Va· = M / p, and

In [X~(IInt.dr = 2M 0' (8.27)


[X U (tJn.t.) J rRT p

Equation 8.27 is known as the Tlzomson-Freundliclz equation. It ind icates


that the solubil ity of B in <X at a given temperature depend s exponen tially
upon the particle radius r. The smaller the radius of the particle, the hi gher
the chemical potential of atoms in the particle will be, and hence the higher
the sol ubility will be. Physical reasoning would suggest th at this effec t due
to the interfacial free energy would be important o nly for particles having a
large area to vol ume ratio, which corresponds, of course , to very small
particles. T o illustrate, let us consider the ratio (X~<snt.> ),. for a typical
4
material with a n atomic weigh t of 50, a density, p, of I0 kg/ m 3 , a nd a n
interfacial free energy of 0.5 1/m 2 a t 500°K . The solubility rati o is plotted
versus rad ius r in Fig. 8. 11 . From this figure it is observed that the eiTcct of
particle size on solubility is significant o nly for particles less than about
50 A (5 x 10- v m) in radius.

12.0

10.0

8.0

[X~<s.t) J,. 6.0 \ --


Xa(nt)

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

This discussion is intended to illustrate an im portant point, namely, that


there is no such paramet er as a maxi mum sol ubility hy itself. The maximulll
solu bility of one substance in another occurs only when the chemica l potential j
of the substan ce in solution equals that for the external phase. The chemical 'i

potentia l of the compon ent in the external phase is governed by many


factors, one of wbich has been treated in this section.

8.5 EQUILI BRIUM OETWE EN A SOLID SOLUTION


AND A LIQUID ALLOY

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

At this tempera ture, pu re 8 is a solid; therefor e this is the normal sl<llldard


state of LJ . In the liquid phase , howe ver. B is present as a liquid . In o rder to
consider the problem 4uantita tivel y. we shall assume Uwl liquid bdw vc~ as
a regular solution an d we s hall neglect the small changes in enthalpy with
tempera lure.
The chemica l po tential di n·crcm:e between pure Band B present in satura ted
r:t I S

= 1:117 n« - T D.S11 "'

11S11 a = - R In X fst;;,~~~ + !J.S11 x" (8.28) ~

Upon substitution we (ind


'
l~T In )'~t<.t> = D.J7 11a. - T !J.S 11 ' " .•
The next step is lo consider the chemical potential or 13 in the liquid pha"c.
The followin g reacti on is of interest : 1
( I) U(s) = B (in liquid <tll oy )

Let us consider the reaction in two steps:


(2) IJ(s) = B(/)

(3) U(/) = 13 (in liq . alloy)


. --
8.5 Equj(jbrium Between Liquid and Solid Solutions 185

The free energy change for reaction (2) is

P.nl- p. 8 • = L1c81 - T l1S1 cn 1 ~ L1(1 -


T.n,p.
_I_)
and for reaction {3) the following holds for a regular solution.

,U~(Ant.l - P.o' = l1fi n' + RT ln Xti<sat.>


Therefore the chemical potential change for reaction I is

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).

of l3 in the (X phase. As a result this retrograd l! so lubility phenomenon will


ge ne ra lly on ly be observed in systems exhibiting low solubility. Most
systems involving germanium and silicon as solve nts are of this type. This
type of solubility has importan t practical consequences since Gc or Si thal
is in contact with impurities at an elevated temperature may dissolve a
ra the r large concentration.

( I
8.6 SOLUOlLITY Of A METASTAULE PI-lASE

Consider the problem of the saturated {3 phase in co ntact with saturated rl .


Suppose that fJ does not have its equilibrium structure but rather is in a
metastable form . ln particular, suppose that solid tJ is superheated above the
1
eutectic temperature. The question then arises as to wha t is the composition I

I

of (X in equiubrium with this metastable fJ above the eutectic temperature.


The relative partial molal entha lpy of component A in the (J ph;1se. 1117/,
for example, is the same above the eutectic as below. Simi larly 6 17 11 is Lllc /Z
8.6 Solubility of a Metastable Phase 187

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).

same above ·the eutectic temperature. T hus the quanlity

oIn X~csat> oIn Xfuso.Ll = 11R 11a:


o( t/T ) o( t/ T) R
remains unchanged above the eutectic. This means that the solvus lines
above the eutectic temperature are extensjons of th ose below. As a general-
ization, therefore, the lines on the phase diagram are continued as shown in
Fig. 8.14. At temperature T 1 , {J of composition b is in metastable equilibrium
with oc of composition a. At temperature T 2 , a of composition c is in metastable
equilibrium with liquid of composition e, and liquid of composition dis in
metastable eq ui librium with {J of composition f It is seen from F ig. 8. 14
that the solubility of a metastable phase (fo r example, superheated {J in rJ.
at T1) is larger than that of the eq uilibrium phase at this temperature (eutectic
liquid). That this should be so is apparent since the chemical potential of B,
for example, in superhea ted {l is higher than the chcmic<ll potentia l of B in
the stable phase of eutectic liqu id . (lf it were not, fJ would be stable at T 1 .)
Plmscs of Varia ble <..:ompo~ifion
188

A
Xa-
or phase boun darie s imo metas table regi on~.
Fig. 8. 14 Phase diagr am showing exten sions

will he large r in this


Hen ce according to equa tions 8. 11 throu gh 8. 13, X~<sar)
..
case tha n in the case of the stable phase.
~ is prc<;cnl in th e
As a'nother example sup pose that {J al lcmpcr;tlu rc 7
c stnrc tur c ll:t": lin.:
form of a mct<t sla blc crys tal !:>lru<.:l un:. Si 11 t'~ l11 e st;~hl
nts hatvc the lowe st
Jowc st free energy, and thus the individua l com pone
larger for the meta-
chemical potential s, the value of X~c~:u) will again he
stab le st ructure.
lt is dear from this brief di!\CUS!\ion that a phas
e has no fund.11ncntal
expresc;ed in tcnm of
solu bility for anot he r clement. The solubility must be
he mad e, however,
the natu re of the phase dissolved. The genera lizat ion may
that tltc !\tllu h ilit y of' a 111c tasta hlc ph ~a <:t: ;._:al ways hi ghe r lh.t n th e soluh rlity
or a sta ble phase.

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

Bi11ary Syslc tns j I

( I

I I

9.1 JNTRODU CTfON

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
\

ClGm = X A.D.fiA + XnD.RlJ + RT[X A In


X"+ X 11 ln Xn]
- T X A ClSA xM- T Xu6.Snx" (9. 1)
' i:
if short-range order is not important. Differentiating 6.G,L with respecl to I l'
Xu al constant temperature and pressure, we find

a ClG"' = -6.17 A+ 6. 17 11 + RT In (~'-) - T 6.S,, "" - ·r uSu'" (lJ .2)


axlJ 1 - xu
Considering a dilute solution of component l3 in A, we may say that 6. 17 A
and 6SA = 0 a nd (I - X11 ) ~ I . Thus
.
l
0 !:lGm ,....., 6.fi + RT In X 0
0 - T uSlixl! (9.3)
ax a
In equation 9.3, 6.fi 11 and AS 11 will not depend on co mposition in lite
'%H
I 'I
dilute range a nd hence the val ue of (o 6.G,,/oX 11 ) will uepend on composi tion
190 ,
IYl
9.2 Free Energy Versus Composition
etllwLion.
only, throu gh the secon d term on the right-ha nd side or the
will always
Regar dless of the sign of l:if/ 11 and l:iSna:a terms , (o 6.G,. /oX0 )
as Xu-. 0.
be negat ive at sufficiently small value s of X 11 , since In Xu-- -co
a decre ase
Thus the introd uctio n of a solute into a crysta l will alway s result in
anoth er
in free energ y of the system ; hence a p ure phase in conta ct with
usion has
const ituen t is always therm odyna mical ly un stable . This concl
ss of manu -
impo rtant ramif icatio ns in co nnecti o n with the impo rtant proce
s tend to
factur ing hyper pure mater ials , si nce pure mater ial will alway
onme nt.
become impu re by the process of absor bing impur ities from its envir
le mater ial
Thus if a pure material is being conta ined in a crucible, the crucib
t.
will tend to dissolve in the pure mater ial, at least to a limited exten

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

T !1Srn term will be mo re impo rtan t tha n at low temperatures; hence it is


possible at high temperatures th at the curve D.C.,, versus X 1, wil l be concave
d ownward at all compositions, as shown i11 Fig. 9.1. As the temperature is
lowered, however , the llH., te rm will begin to dominnte in the free energy
expressio n) and the !1G"' versus Xu curve will tend to be positive. As dis-
c ussed in Section 9.1, !J.G 111 nea r the ends of the bina ry is always negati ve,
so the complete curve wi ll have the shape shown in Fig. 9.2. If the solution
is regul ar , the n1inima a re sy mmelric abou t Xu = 0.5 and ha ve the same
value of tlGm.

t J.La- JJ. a'

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.

Consider now an alloy o f composition a. ll will ha ve a va lue or 6.G 111 equal


to tlG(t which is in sign negative. This solution , thcrcro re, is stable relet live lo
pure A a nd B. The same is true for alloy t. Consider alloy .r, however. It
might have a negative va lue of D.G,, bu t we have to question whether or no t 1
I
llG, 1 co ul d be reduced further by dissociating the solution. Suppose the alloy
dissociates into two solu tions having co mpositions d and e, respectively.
The free energy of the system now will he th e free energy or solutio n of
com position d gi ven by JJ Limes the a111ou nt or so lut io n uf thi$ cnrnposi tio11 .
plus lhe free energy of soluti on or composition e given by CLimes th e anwunl
of the solution. The fraction or the system wh ich is solution of composition
dis obtained from the lever rule, and is equa l to (c - .r)/(e - d) . Simi la rl y
the fracti o n or solutio n of COill[ll)Si ti o n (' i!i (x - d)/ (c - d). Th us th ~,; va luc
of tlG"' of th e whole system is

(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

At a temp~ralure dirferent from T111 • 1,.

Neglecting the small temperature dependence of L1 and liS1 , we find on


substitution for liS1
(9.4)

In the case of component B at Tt we are interested i.q the reaction

B(l) = B(s) D.G = - 6.G1 = - (t.t 11 " - !'H.)= - D.L, ( I - T ..,.,•.,,7 '1)

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.
- - - -,----
........ .......

196 Free Energy of Uiuury Systems

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

T =2X t/( l -Xn°)i~ l 9 .(•)


c R

~ 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

solid solutions. Jn addition a curve is shown for a hypothetical in termedi~t~


phase. The question arises as to what the phase diagram looks. like for this1
situation . Does fJ exist as a stable phase at this temperature? It might be
noted that llGm for the fJ phase of composition c is negati ve, so clearly fJ is
more stable than pure A and B. It must be asked , however, whether or not
some other combination of phases might not be more stable. From examination ,

·'

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

(a) Xu < X UC11at>• a. phase is stable I j

(b) x~I (Fat) < X < b, n a. + {3 coexist


I
(c) b < X n < c, fi phase is stable

(d) c < X n < X~csatl> {3 + y coexist


(e) XB > X1 cs,~t.l • y phase is stable
9.3 Free Energy Versus Composition 199

Fig. 9.8 Free energy versus cOmposition diagram showing intermed iate phase.

It should be noted that even though the composition limits of fJ may be


small , a very large variation in p. 0 - P.u·, and hence au. may occur across
the composition range. As shown in Fig. 9.8, the value of (p. 8 - p. 8 · ) in fJ
at the composition where oc and fJ are in equilibrium is considerably different
from the value when p is in equilibrium withy. In fact an order of magnitude
change or more in an may result across a narrow composition range. Jn
Fig. 9.9 is shown the diagram for aA and an versus composition derived from
Fig. 9.8.
The phase diagram correspo nding to F ig. 9.8 is shown in Fig. 9. l0.
From Fig. J9.8 we see that the more negative the value of the free energy

a • a } ( + 'Y ') 'Y


I I
1.0 N
I a,. I I ~
I I
I I I I
I I I I
I I I I
I l I I I
I as 1 I I
I I
~ I I I
I
I I I
I I I
I I I

~
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. "

of formation of the intermediate phase, the more restricted the terminal


J
solutions cx. and y will tend to be. ln other words, the intermediate phase
might be said to form at the expense or the terminal solid solutions.
Lt is often dcsirublc to kn ow the a~tivily or so luLc in a lcrmin:ll solid
solution for systems which involve one or more intermediate phases. I f the
curve of 6.G,n versus Xu for the intermediate phase shown in Fig. 9.8 is
known, no problem is presented, since from the shape of the curve, (11 11 -1t 11 ")
corresponding to the maximum solubility of {J in ex. may be obtai ned from the
slopes as shown in Fig. 9.8. Thus the activity of component fi in saturated a
solution may be readily evaluated. If the a solution is dilute, Henry's law is
followed by component B and hence the activity may be evaluated at any
composition. Often , however, the curve of f).G, (corresponding to 6.G/) 1
versus Xn is not available for the intermediate phase , but for some phases a
more or less average value of l::iG/ correspond ing to some composition
iI
between band c is available. Jf this datum is ava ilable, a close approximut ion
of au in a may be made through the methou uescrihcd below. Let both cc.
and y be restricted solutions so Henry's law is followed by the solu te and
Raoult's law by the solvent. Since we supposedly know f).G1° for the inter~
mediate phase adjacent too: on the phase diagram, this is the logical reacti on
to consider first, since this phase is in equilibrium with saturated a.. Since we
are going to need (u 13 - P.u") in saturated a. in order to obtain on and hence
Yn° in a, let us assume that 6.G/ for the intermediate phase of composition
b is the same as the average val ue which has been measured. f).G," for the ·1
9.3 Free Energ y Versus Comp ositio n 201

saturated ex. sol ution is given by

RT[( l - x~ (!u~t)) In (l - x;Heat)) +X H In On] (9.8)


flGm « =
comp ositio n a in
Ther efore the slope of llGm versus X 0 for the ex phas e at
equil ibriu m with the inter medi ate phas e is

allG m = [(LlG ,0 - a.6.G ,«)] (9.9)


axu b - X 11 <antl
We have show n that
0
P.n -PH. = 6.Gm + (l - X u) [ 6.G""«]
oXn
Upon subst itutio n we find
AG
• u. o+ (1 b) [IJ..G / - a.IJ..G n/~J = RTn
I au
P,u- tJa= 1 -
b - X U (s &t.)

For a restri cted sol ution , lflG ma.l «


I6.G/ I and so will be neglected. Thus
since on in the inter medi ate phase at b is the same as au
in satur ated ex, we
find

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

6.C 01 = fJ- 01°


R T In Po!
2f.lo - = I I
For phases that exist over a ra nge of composition, 6.G 0 , may be determ ined
I I I
as a functio n of composition.
In Fig. 9. 11 , 6.G 0 , is plotlcd vc rsu-. the 0 / M rat io in :1 con1po und I I

(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 -

- 200 L---------~--------~----------~--------~--- -----~


500 1000 1500 2000 2500 3000
Temperature (•K)

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.

based on the U0 2 structure a nd 30 % of the ca tio n sites are occupied by Pu.


The compoun d has a rather wide range of stoichiom etry. The precipitou s
change in ~Co, in a narrow range of 0 / M values should be noted. This is
due to the very large change of slope of the 6G"' versus composi tion curve
· for the compoun d. In Fig. 9. 12 are shown values of llC 0 1 as functions of
temperatu re and deviation from stoic hiometry . ln this figure the valence of
4.000, for example, co rresponds to perfectly stoichiom etric (U0 . 85 Pu 0 . t 5)0 2+x
where 0 / M equals 1.00. When X is positive , the effective va lence of (U, Pu)
is greater than 4 .00, and when X is negative, the effective valence is Jess than
4.00. It sho uld be noted from this figure in agreemen t with Fig. 9. 11 that a t
a given temperatu re, the ability of the compo und to oxidize an a lloy such as
stainless steel varies markedly with co mposition of the compou nd . The
curve labeled stainless steel represents the va lue of (~C 01 ) in equilibriu m
with the oxide and metallic co nstituents of the a!Joy. Therefore when (~G 0 ,)
in (U, Pu)Ot+X has values grea ter than th ose for the curve labeled stainless
steel, oxidation of the alloy will occur. Conve rsely when the va lue is below
204 Free Energy of Binary Systems

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.

I labeled H 2/ H2 0, CO/C0 2 is so low that the reacti on of the type


.I M + H 20 (g) = MO + H 2 (g)
., must be employed in order to determine LlC 0 l. For oxides that have
equili b-
re may
rium pressures in the range la beled direct control, the oxyge n pressu
'J

:t be direclly controlled experimcnwlly.


be
As discu ssed earlier, every intermediate phase or comp ound must
ple, the
stable over a range of composition. fn the case of oxides, for exam
as com-
composition range is often rathe r wide fo r transition metal oxides
ositio n
pared to alkaline earth oxides. Table 9.1 lists some values of the comp
oxygen
range of va rious oxides a long with the equili brium partia l press ure of
al the minima and maxima.

9.4 CALCULAT ION OF PHAS E OlAG RAM S


FROM THER MOD YNA MIC DATA
ms
In previo us sections some general relatio nships between phase diagra
may, of
and free energy consideration have been discussed. In principle one
exist.
course, calculate phase diagra ms if appro priate therm odynamic data
nts have
As an illustra tion let us consider the simplest case in which two eleme
206 Free Energy of Binary Systems
Table 9.1 Homogeneity Range and Oxygen Pressure Range of 3d Oxides (MO x)•
------
Stability Rang,e log p 01 Range
Oxide
Xmln xlll t\lC 6X Max Min 61ogp 0 ,

TiO 0 .80 1.30 0.50 44.1 41.5 2.6


Ti 20 3 1.501 1.512 0.011 41.5 30.1 11.4 )
Ti0 2 1.992 2.000 0.008 25.7
VO 0.80 1.30 0.50 34.5 33.2 1.3
M nO 1.000 I. I 8 0.18 34.7 10.7 24.0
FeO 1.045 1.200 0. 155 20.5 19.2 1.3
Fe30 4 1.336 1.38 I 0.045 19.2 14.0 5.2
CoO 1.000 1.012 0.01 2 14.5 2.5 12.0
NiO 1.000 1.001 0.001 16.5
Cu20 0.500 0.5016 0.0016 9.6 7.0 2.6
..
4
From T . H . Reed, in Tire Chemistry of Extended Defects in Non-Metallic Materials,
.
L. R . Eynng and M. O'Keefe, Eds., North-Holland, Amsterdam, 1970. .
the same crystal structure and form ideal solutio ns in bo th the liquid and
solid states. There are a few real systems which approximate this ideal
behavior. Intuitively one might expect, for this type of example, that the
liquidus and solidus lines merge together. This is not actually the case,
however.
Consider the free energy curves of liquid and solid solutions below the
melting point T for component A but above the melting point for component
B. Thus our reference states arc pure solid component A and pure liquid
component B. The !:::.G m versus X .u curves for the two phases are shown in
Fig. 9.15. We may now derive analytically the curves for each type of solution.
Since the liquid sol ution is ideal, we have for the reaction
XA moles of A(/)+ X 8 moles of B(/) =liquid solution (XA, Xn) (9.11) )
The free energy of mixing is
'
b.Gm = RT(XA In X A + X 11 In X 11 )
Since our standard state is solid component A , instead of liquid, we must
consider the following reaction in order to obtain the equation fo r the
curve on Fjg. 9.15:
x~~. moles of A(s) = XA moles of A(/) 6.G = X A 6.G1.A
Adding equation 9.11, we have
XAA(s) + XnB(/) = liquid solution (XA, Xu)
6.Gm' = XA' 11G1 + RT(XA' In XA.' + Xut ln Xut)
A
9.4 Calculation of Phase Diagrams 207

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.

Similarly for the solid solution,


XAA(s) + XnB(s) = solid solution (XA, Xn)
6Gm = R T(XA. In xA· + Xn' In XH')
Xu B(/) = XnB(s) D.G = -Xu• 6G1 e_,

XAA(s) + XuB(/) =solid solution (XA, Xn)


6G 111' = -X 11' 6G1 II + RT(XA•ln XA' +Xu' In X 11')
ln a previous section we showed that if the small heat capacity corrections
to D.H1 a nd D.S1 are neglected
6G 1• = 6H1A ( l - T. T ) ·
m . p . A.

At equilibrium, the chemical potential of component B is the same in liquid


and solid, a nd lhus the slopes are equal, or

a6G ,~/ - a6Gmt


oX 11 oXu
·Performin g the differentia tio n , equating, a nd rea rra ng ~n g, we lind at a
given temperature

- ln Xo'+lnXA'=l:iH,A (~ - l ) - /:1H/n (~ - 1) (9. 12)


X Dl XA' R T T01• 11. A R T Tm.J•-u
rI
208 Free Energy of Binary Systems

The equation above co ntains two unknowns, so appeal ·must be made to


I
other considerations in order to solve. As we approach T111 • 1,.A , X A' a nd
XA'-+ 1 and hence In XA'/X.At-+ 0 . The seco nd term on the left-hand sid e
of equation 9 .1 2~ 0 and, since 1/ T--+ 1/Tm.p.A' we have the relation

(9.l3)

D oi ng the same thing at the other end of the diagram, we have

(9. 14)

Solving equations 9. 13 and 9. L4 as a fu ncti o n ofT yields a phase diagram of


the type shown in Fig. 9.16. Thurmond, 1 using such an approach, has'
I
I
I
Liquid I
I
(

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).

transfor mati o n which ha!; the (X. slrUt;lurc to the fl slrUt;lurc or


or cl ement A
element B must be determined as a first step , and similarly the free cncq,'Y
of transformati on of sPto a« must be determined. As a second step some
information about the nature of the solution between A and B must be known.
A few systems behave in idea l fashion. fly thi.s is not meant that Aa dissolves
ideally in BP but rather that AP dissolves ideally in BP, and B"' dissolves
ideally in Aa. Many systems behave approximately as regular solutions but
for the majority of sys tems more complex thermodynamic relations exist.
A large num ber of calculations for metalli_c systems have been performed
1'
I

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.

by Kaufman and Bernstein 1 and the free energies of structural transfor-


4
. •
~

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'·

a eutectic phase diagra m. Thermodynamically, however, these diagrams


may represent only differences in degree and not necessarily fundamental
differences in the nature of the components. We have just considered the
phase diagram resulting for components forming an ideal solutio n in the
liquid and solid states. Let us remove this restriction and consider a general
case for which !:1H111 is negati ve. Consider further that tl.lf,. is more negati ve
for the solid than for the liquid soJution. At a temperature T 1 welJ below the
melting points of either component, the free energy versus compositio n
curves would appear schematically as shown in Fig. 9.l9. Above the melting
point of both components at temperature T2 , the curves would appear as
shown in Fig. 9.20. The curve for the solid reaches a lower value than does
that for the liquid since ~Hm' is more negative in this case than ~Hm'·

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.
.. ...~
••

212 Free Energy of Binary Systems

The lowest free energy of the system is attained if when


(a) Xu < a, liquid solution is stable
(b) a < Xu < b, liquid and solid solutions coexist
(c) b < Xn < c, solid solution is stable ...
(d) c < X 11 < d, liquid and solid coexist
(e) X0 > d, liquid solution is stable
t
'I
This gives rise to a melting point maximum a nd a phase diagram ~ts shown
iu Fi~ 9.? I . )

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

re T2 .below the melting point of both


Fig. 9.23 Free energy of liquid and solid at temp eratu
component s.

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~

(a) (b) (c)


. )
Fig. 9.26 (a) Phase diagram for an ideal sol ution. (b) Phase diagram for case where
6H,.' > llH,.' > 0. (c) Same as (b) except that fiH,. is more positive. iJ 1

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)

m for case where


Fig. 9.27 (a) Phase diagra m for an ideal solut ion . (b) Phase diagra
e.
D.Hm' < AHm' < 0. (c) Same as (b) except that 6//m is more negativ

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.

9.6 NON UNifi ORM SYST EMS


o f thi s
The gener al subje ct of phase deco mpos itio n is o utside the scope
a lio ns in
book bul it is releva nt to consi der the subje ct of comp ositio n fluctu
of interfacial
soluti ons. This treatm ent will set Lhe stage for co nside ration
be of intere st
free energ y, which will be discu ssed in the next chupt er and will
j I

216 Free Energy of Binary Systems Jl


11
to the reader who perhaps might be interested in kinetics of phase decom- I.
position . The subject of composition fluctuati o ns has been treated by severaf
writers but a particularly fruitful approach has been developed by Cahn
and Hilliard in a series of papers. Following these authors1 consider for sake
I ' I
of simplicity a binary solution A - B. It is assumed that the local free energy
, I
per atom fin a region of nonuniform composition depends both on the local
composition and on the composition of the immediate surroundings. If this is
true the free energy is th e sum of two contributions. The first is a function
o nly of the local composition and the seco nd is a function only of the
derivative of the local composition. lt should be emphasized that the
existence of a gradient term is strictly an assumption and does not have an
obvious justification from the Jaws o f therm odynamics. f is co ntinuous in
both composition and distance and if the gradient is small relative to the
reciprocal of interatomic distance, f may be expanded in a Taylor series
about fo, the value off in a uniform solution. Thus

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--

1 J . W. Cahn and J. E. Hilliard, J . C/rem. Phys., 28, 258 (1958) .


2!7
9.6 Nonunifor m Systems

and equa tion 9.16 redu ces to


= / 0 (Xn) + K1 V2Xn + K 2 (VXn) + · · · (9. 17)
2
2
J(XB , VXB, V XB, ...)
be obta ined by integ ratio n
The Helm holt z free ener gy of the tota l syst em may
over the volu me V :
(9. 18)
F = NJ. fdV
v
Inte grat ion yield s
where N is the num ber of atom s per unit volu me.
(9. 19)

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

fo =J( Xo) +( X- Xo) ~I +(X -; Xo)2:~o21


r

.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)

ositi on curve as shown in


Con side r a bina ry syst em with a free ener gy-c omp
Fig. 9.28. Ouls idc of the spin odal poin ts (o2fu
/oX 11 2 ) is positi ve a nd the
spin odal poin ts (a' - b')
solu tion is stab le tow ard fluc tuati ons. With in the
o ns are stab le, and deco m-
the term has a nega tive sign and thes e fluctuati
ua tion s whic h have wav e-
position may resu lt by increase in amp litud e fluct
h fluc tuat ions will disa ppea r.
lengths grea ter than ,lc, whe reas shor t-wa vele ngt
218 Free Energy of Binary Systems

'
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.

Outside of the spinodal points, decomposition of an unstable solution must


occur by nucleation and growth processes, whereas inside the spinodal
point, classical nucleation and growth need not occur.
The above calculations are idealized to sume extent inasmuch as it was
tacitly assumed that no volume change occurs in the solution as a result of
the fluctuations. This constraint may be removed. For solid solutions the
presence of the compositi on gradients may result in substantial coherency
strai ns if the atoms A and D have different sizes. The presence of these
strains would tend to move the effecti ve portion a' and b' in Fig. 9.28 toward
one anoU1er. The critical wavelength is now given by

(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

For purposes of discussion it is convenient to classify interfaces or surfaq;!s


into two general categories: (a) external surfaces, and (b) internal surfaces.
Specifically, the former category pertains to the interface between the solid
phase and the vapor phase, or between the solid phase and a liquid phase.
The Jatter category is conveniently subdivided into (I) interfaces between
crystals of the same phase, called crystal boundaries or grain boundaries,
and (2) interfaces between phases of different structure and compositi on.
Before proceeding to a discussion of these specific types of interfaces, it
will be worthwhile to discuss some general aspects of the thermodynamic
properties of interfaces.
'
.J

10.1 SURFACE TENSION AND SURFACE ENERGY

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

case of ene rgy as


These excess qua ntiti es are defined in the
1
dU n= dU - dU a- dU
the syst em incl udin g the surface ,
whe re dU is the total vari a tion in ene rgy in
t he cr. and {J pha ses, respecti vely.
a nd dUa and dU refe r to the cha nges in
11
k phases
4, We have previo usly sho wn that for the buJ
dU« = T d S« - p« dV« + L f.J-t dnt
i (10.3)
dU 1i = T dS 11 - p 11 dV /1 + 2, J1. dn /1
i

and ther efor e upo n substitu tio n


+ + p 11 dV 11 = u dA ( 10.4)
)du - T dS - L /J-i dn 1 pa dVa

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

uxsfA, etc., we obtain i

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

dcr = - rA dp.A - r n dp.JI :\


The exact position of the boundary is somewhat arbitrary. For the sake of jl
convenience Jet us define mathematically the boundary as being that plane ~ I
where r A = 0. If this is done " '

(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)

log Pos· From F. H. Buttner et al.,


Fig. 10.1 Surface energ y of silver as a function of
J. Phys . Chem ., 56, 657 (1952) .

'
..
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.

W.l :\Nl SO l'IH W\' OF Sl llU•'A('l•: EN I•:tu. : ll•:S


e. The geometric form of a body
Con!'idl.'l' the equilibrium shap e of a phas
P''sscssin ~ the smnlkst urea per unit volu
me is, of course, a sphere. As a
t o assu.mc a spherica l
rt.•sull. Olll.' "''luld l.'~pcd that obje cts Wtlt lld tend
f the phas e. Fam iliar exam ples
s hape i11 on.J cr to ltlWCr the total free energy o
of merc ury, oil, etc. This does
or this arc tl u.: formatio n of sphericnl droplets. how
1111 1 llt'l.'<'ssnril~' ,w~..· ur
ever. Suppose that a single
wi th a t' r.v:-ta llinc so lid
clcva(l!U tem-
! crys tal is CUI iu I he hll Ill oJ' It splll.'l'l.'
ing a spherical shape,
ll l h .l !hell hcH(l.'d (O !Ill

perature or imm ersed in an acid . Lnstead of maintain


10.3 for germ anium. The
crystalli,ne faces begin to develop as shown in Fig.
tal orientation but is
reaso n for this is that a is not independent of crys
hic planes forming the
strongly dependent upo n the types of crys tallograp
d a nd solid is unde r-
interface. This diiTerence between the behavior of liqui
s is identica l on any
standable since, for a liquid, the packing of atom
ever, the arrangement
arbitrary plan e cut through the phase. for a solid, how
ents are show n in Fig.
of atoms is a func tion of the plane. Se~era l arra ngem
1800
~ Fe- c
1600
- ~
--
E
u
c::
>.
"0
1400

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

Fig. 10.4 Atom ic arran gem ent on (a) (100)


face, (b) (Ill) face, and (c) {110) face for a
face-centered cubic struc ture.

that the arra nge men t of atom s


10.4 for a face-centered cub ic crys tal. It is seen
s. One wou ld expe ct that the
is cons ider ably dufe rent in the vari ous face
end stro ngly upo n the efficiency
energy of the atom s at the inte rfac e wo uld dep
rs. Nor mal ly the mor e close-
of pack ing and hen ce of bon ding to neig hbo
Jow est values of u and henc e
pack ed plan es wou ld be expe cted to hav e the
elop as inte rfac es. On the basis
these wou ld be the plan es mos t like ly to dev
diffe renc e between solid s and
of this disc ussi on we may stat e an imp orta nt
the interfacial tension between
liquids in the follo win g man ner: the value of
the indices of the planes of the
a solid phase and another phase is dependent on
solids forming the interface.
in ener gies asso ciat ed with
A qua ntita tive exam ple of the diffe renc e
aniu m in an acid env iron men t.
different planes is the etch ing rate of germ
it is con ven ient to thin k in
Ger man ium is u cov ulen t sem icon duc tor nnd
ace may be con side red to have
terms of chemicaJ bon ds. The atom s at the surf
free chem ical bon ds. The (100), (110), and
(Ill ) plan es of germ aniu m hav e
bon ds/ m 2 , respectively. The
1.25 X wn, 0.88 X 10 ' , and 0.72 X IOU free
1
.89 . and 0.62 , rcspectively ,
1
e etc~ 1ing rute s urc foun d to be l.OO, 0
rel ativ
bon ds and indi cate s that the
which js cons isten t with the num ber of free
) plan e for exam ple.
energy of the (100) plan e is high er than (111
py of surf ace ener gies is by
A con venient way of repr esen ting lhe anis otro
ted as a func tion of orie ntat ion
use of a Wul ff plot . In this type of plot u is plot
shap e of the crys tal may be
as illus trate d in Fig. 10.5. The equ ilibr ium
vect ors are constru cted from the
obta ined from this type of plot . Firs t radi us
s are then draw n thro ugh the
origin to a plot as show n in Fig. J0.5. Line
c h arc nnrm al to the radi us
poin ts of inte rsec tion of radii and a plot whi
imu m val ues of u delineate the
vectors. The lines that pass thro ugh th e min
ple show n in Fig. I 0.5 is one in
equ ilibr ium shap e of the crys tal. The exam
s. The se give rise to plan ar
which ther e are cusp s at vari ous ori enta tion
ch u is a min imu m at cert ain
surfaces. fn Fig. 10.6 is show n a case for whi
type of situ atio n , a barr el
orie ntat ions but con ta ins no cusp s. For this
equi libri um shap e is obta ined .
a in Mate rials Scien ce, Vol. 2, Plenu m,
H. C. Gatos et al., in Fundamental Phenomen
l
New York, 1966.
',
' .
..
......' ~'"
'

·. '
'
'

- - Polar plot or surface free energy


----- Samples of planes normal to radius vectors of this plot
- - - Equilibrium polyhedron
Fig. 10.5 Wulff plol. From C. Herring, in S tructure and l'roperties of Solid Surfaces
R. Gomer and C. Smilh, Eds., Univ. Chicago Press, Chicago, 1953.

10101
J

Fig. 10.6 Wulff plot for [1 00] orien tation


(no c usps present). From J. P. Hirth in
Energetics in Metallurgical Phenomena,
Vol. lV, W. Mueller, Ed., Gordon and . )

Breach, New York, 1968.

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

(cr, 11 - C1a1 COS cp - a11 1 COS 0)


and hence the free energy cha nge from this contribution is
)
dF 1 = (a, 11 - a,., cos 4> - ap 1 cos O)(OP x L) (10.12)
In addition there will be free energy co ntributions resulting from the o rien-
ta tion cha nge of the o:- y and {1- y boundaries. These will be

dF2 = (oa0 ; 1 )-
0</J AP XL ( t0.13)
t''
and f

dt·3 = (i);;•6/f>) BP X L ( LO. l4)


I"
1C. Herring, in Physics of Powder Metallurgy, W. E. Kingston, Ed ., McGraw·llill,
New York, 1951.
229
10.2 Anisotropy of Surfa ce Energies
differ ences (4>' - ¢)
The angle chang es o<f> and oO are, from Fig. 10.7b , the
ified by expressi ng
and (0' - 0), respe ctive ly. Thes e expre ssio ns may be simpl
I AP and BP in terms of OP. To do this let us consi der Fig.
10.7b in mo re

r detai I. The angle 0 P A is equa l to 180 - 4>' and thus the


to ocp. As a result, from trigo nome tric consi derat ion,
angle 0 AP is equa l

sin (ocp) _ sin cp (10.1 5)


OP
- A-P
Since- c~cfo is infinitesim a l. sin (,~q.) ~ t~q.. and upon rea rra nging e<1ua tion
10. 15 we find
- sin 4>
04> = OP -
' AP
Simil arly angle OBP is equa l to{/J and
- si n 0
IJO = OP -
AP
U pon subst i tutio n we find
-
dF2 = oal%7 ;. · OP x
-si n 't'
aq, L (10.1 6)

oa(l y -
cl F..I =- sin 0 · 0 P X L ( I 0.17)
(}{)

'I , 10. 16, and 10.17


) .I The total free energ y c hang e is the sum of equa tions 10.12
l and
elf • -
- = (a« 11 - a 47 cos cp - ah cos O)OP
L
0(1«7 - OUpy -
+ - sin c/> · OP + - sin 0 · OP (10.18)
acp · ao
At equil ibriu m, dF = 0 a nd thus .
oall., OUpy
ao.p - <T117 Cos cp- O'p 1 cos 0 + - sin c/> + - sin 0 = 0 ( 10. 19)
aq, ao
ion of o rient atio n ;
Jn t he speci al case of a liq uid , the bou ndary is not a funct
to I0.11.
thus oufoO is zero a nd eq ua tio n I0.19 becom es ident ical
facial tensi on
For most intern al boun daries in solid s the change of inter
xima tion in these
with angle (oaforx) is small, so 10. 1 Lis also a good appro
a speci al type the
cases . Whe n the boun dary betwe en two phas es is of
y boun dary such
si tuatio n m ay be diffe rent. An exam ple is a very low energ
case a may chan ge
as represente d by a cohe rent twin bo und a ry. F o r this
dary is lost very
very rapid ly with o rie ntati o n si nce co heren cy at the boun
rapid ly with miso rient ation . -
230 Thermodynamics of Surfaces and Interfaces

10.3 SURFACE ENERGY VALUES FOR METALS


AND COMPOUNDS

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 ~·

at U,- TS; '. I

- I 1
a1 U 1 - TS 1 I
I ) )'

Table 10.1 Surface Entropies for Solid and Liquid


Metal4

Solid- Vapor Liquid- Vapor · ' I


Metal Ss (mJ/ m 2 ·K) Ss (mJ/ rn 2 ·K) 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 ')

Ni 1.1 ± 0.8 0.98


Fe 1.5 ± 2.0 0.43, 0.5

° From H. Jones and G. M. Leske, Metal Science J., ,I


1, 211 (1967).

I )
10.3 Surface Energy Values for Metals and Compounds 231

Table 10.2 Surface Free Energies for Solid-Vap or


Interface at the Melting Point0

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

° From H. Jones, Metal Science J., 5, 15 ( 1971).

• 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

Table 10.3 Probable Values of S 1 /U1 and U1 / U2 for Zn and Cda

f S(lO.O) S(IO.O) U(IO.O)


S(OO.J) (10- 3 K- 1) -,....-- (I o-a K - 1) S(OO. l ) U(OO.I)
Metal U(OO.l) U(OO.l)

Cd 1.3 1.8 1.38 1.33


Zn 1.0 2.2 2.2 1 1.94

4 From H. 0 . K. Kersheoer and G. A. Chadwick, Phil. Mag., 22, 44a (1970).


t
I •

232 Thermo dynami cs of S uTfaccs and Interfac es

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

Let us consider a face-centered cubic crystal for which a surface is created


by cleaving the crysta l, a nd consider that the surface is fo rmed alo ng a ( Ill )
plane. Each atom in the (Ill) plane is bonded to 6 neighbors in the plane,
3 below the plane and 3 above the plane. Upon formation of the surface,
.I
i
I I
~,
1 C. H erring in Metal/uter faces, ASM, C leveland, 1952.
234 Thermodynamics of S urfaces and Interfaces

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

Since N is equal to ( Vf N 0)'lA, we calculate that the enthalpy per gram-atom


! I
of surface is equal to 0.25L8 . This compares to experiment where the surface
free energy _is fo und to be equal to 0. L5 L 8 . Values of fls per unit area are I \
i
calculated to be 1. 14, 1.55, and 1.38 Jf m2 fo r silver, gold , and copper,
respectively. Values of Us obtai ned from Tables 10.1 a nd 10.2 a re 1.61.., 2.06, t l

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

is the area under curve or


Work =JeD! dx
:z:o

To perform the integration analytically the equatio n for f as a function of


x must be known. To a first approx imatio n the major part of the curve may . ·; ..
be approx imated by a sine function (dashed line in Fig. 10.10b) . Thus the
functio n f = f(x) is given approximately by "
. [27T(X - X0)]
f = / 0 sm A
The work per unit area in separating the crystal is given by
2
[211( A/0
J
«o+.J./ . X - X 0) ]
W = fo Sl n dx = - .3
xu A 1T I

Two surfaces of uni t a rea are formed thus


A/o
Us= ·~w or Us= -
21T
This needs to be put in more meanin gfu l terms from the point of view of
performing calculations, since the force / 0 is difficult to obtain direcUy.
Near x 0 , Hooke 's law is obeyed , a nd hence

where Y is Young 's mouulu s. Thus at small strai ns

and we obtai n
df [21T(X - x0)] --....
- =/0 COS j
d.c A
Upon substitution


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

germani um and propose a 2 x 8 surface unit mesh on (111 ) planes in which


some top layer atoms a re raised relative to their normal positio ns a nd so me
are lowered . Upon depositi o n o f sodium on the surface th e 2 x 8 structure
disappea rs and it appears tha t the presence of the impurity relaxes the su rface
to its bulk structur e. On (111) surfaces the impuriti es appea r to be distribu ted
in a diso rdered fashion, whereas o n (100) surfaces well-ord ered overlaye rs
appear to develop . These example s indica te thal simply stalistical models
can yield only approxi mation results at best. They seem at t his point funda-
mentally incapab le of predictin g the atomi c nature o f equilibr ium su rfaces.

10.4 INTERN AL BOUND ARIES- CHEMI CAL OlSCON TlNUJT Y

Suppose that two phases of differen t compos ition meet to fo rm a n interface.


Two types of disconti nuities may appear. lf the phases are o f different
structur e or differen t lattice paramet er for the same str ucture, a geometr ical
disco ntinuity will occur. If the phases are of differen t compos ition a cltemical
disconti nuity will occur. Discussi on of geometr ical disco ntinuities Wi ll be
deferred lo a later section. Let u s co nsider th e problem of the c hemical dis-
continui ty here. It is temptin g in this case, but not accurate , to rep resen t the
composi tion of, say, compon ent B as a function of distance no rmal to the
plane of the boundary as shown in Fig. I 0. 11. In o ther words the interface

1 P. W. Palmbcrg and W. T . Pcria, Surface Scie'llce, 6, 57 (1967).


238 T hermodynamics of Surfaces and Interfaces

l
~
1
-
CD
0
c:
0
+:.
a (J
10
!:1
c:
Q)
u
c:
8
cD
u rBoundary ~

Fig. 10.11 Idealized composition of phases •


Distance ___.. a and Pnormal to the plane of the boundary. !

would appear as a abrupt chemical discontinuity. In order to illustrate the


diffuse nalure of the interface the approach employed by Cahn and Hilliard
will be employed. 1 Consider isotropic phases ex and fJ of compos~t i o n X 11«
and Xu". rn this example only a chemical discontinuity will be considered.
The free energy of material near the boundary will be assumed to vary with
composition with the form illustrated in Fig. 10.12. If y represents the I

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

Fig. 10.12 Free energy func tion as function of concentration.

1 J . W. Cahn and J. E. H illiard, J. Cltem. Plrys., 28, 258 ( 1958).


.I ·~

I
10.4 Internal Boundaries- Chemica l Discontinuity 239

neglected one obtains

F=AN [~o(Xn) + x(d~nn dy


The free energy of the two phases on either side o f the boundary may be
written as

The excess free energy is the ditrerence a nd conseLJuentl y we ob tain

( 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

Substitution of the integrand of equatio n l0.20 into the Euler equatio n


indicates that
u)
dX
6.f(Xn)- K ( dy = 0
2
(10.21}

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

10.5 I NTERNAL BOUNDARIES-sTRU CTURAL DISCONTI NUITY


1
r
As discussed previously, the interfacial energy is a positive quantity and~
hence, thermodynamically speaking, internal boundaries are ·unstable and
tend to adjust themselves geometrically in order to minimize their total free
energy. It might be expected from this that a single crystal of a single phase
would be more stable than a polycrystaJline array of the same phase. This is
generally true but Fullman 1 has shown that there could be exceptions to
this generalization . The total interfacial energy is the sum of the surface
energies and the energies of the internal boundaries. For a crystal with
anisotropic surface energies, Fullman has shown that it is possible for a
polycrystalline array to be arranged in such a way with regard to internal ..
and external surfaces that the total interfacial energy is Jess than for a single
crys tal of the same to tal volume. Quantitative verification of this theory
has not been performed because of the Jack of experimental information
concerning interfacial energies as a function CJf orientation for real materials.
It is convenient for purposes of discussion to divide internal boundaries
into two classes: (1) internal boundaries between crystals of the same phase,
resulting therefore from orientation differences (hereafter referred to as
grain boundaries), and (2) internal boundaries separating phases of different
structure or compositions or both.
In order to assist our understanding of grain boundaries it will be worth-
while to examine some special idealized boundaries first. These are low angle
boundaries of the pure tilt type and the pure twist type. These boundaries
may be considered to consist of regions of perfect fit and regions of misfit,
resulting in the formation of dislocations at the boundaries. The tilt and twist
boundaries are shown in Figs. 10.14 and 10.15 and may be considered to
1 R . L. Fullman, Acta Met., 5, 638 (1957).
10.5 Internal Boundaries-Stru ctural Discontinuity 241

,..- 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)-·

Ill II 11 ~4ff 11 ll1 JJ \I


.& .I -P
~}~ ·~
., .,
vJJ
"-f
1 '..L
.l .UJ 'l(1 11
lb.
iL ~[ y~I.JJ 11 J
' l "I ~ 1
/ j
f, I
'•
I
''

Fig. 10.15 Low angle twist boundary. From W. T. Read, Dislocations in Crystals,
McGraw-Hill, New York, 1953.

length of a single edge dislocation has been derived to be


2
U J. = Gb ln _8 +B ( 10.25)
417'(1 - v) b
where G is the shea r modulus, vis Po isso n's ratio, B is a constant (a measure
of the core energy of the dislocation), and R is the dista nce th e elastic stress
field ex tends away from the core. The ex ten t of the stress field .of an edge
dislocation R has been shown by Read and Shockley 1 lo be eq ual to Lhe I
dislocation spacing D. Therefore, upo n substituti on of equa ti on I0.23 into
10.25, we find
I
U J. = Gb 2
In (l)
- +B ( 10.26)
47T(l - v) 0 ll
I '

as the energy per uni t length of dislocation. The number of dislocations per

1 See W. T . Read, Dislocatlons i11 Crystals, McGraw-Hill, New York , 1953.


10.5 Internal Boundaries- Structural Discontinuity 24J

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)

Equation l0.27 may be put into the form

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

An eq uation identical in form to 10.28 is obtained for twist boundaries with


U0 and A given by
_ Gb
Uo -
277
A= 2178
Gb 2
These derivations, it must be emphasized, are applicable onl.y to low angle
boundaries. In the case of high angle boundaries, lhe disloca tion spacing
is decreased to ~uch a small value that the concept of the boundary as bei ng
composed of separate dislocations becomes meaningless. This is illustrated
quite lucidly by the bubble-raft models shown in Figs. 10. 16 and 10. 17,
showing the comparison between a low a ngle boundary and a high angle
boundary. In addition to this important factor, the eq uality between R and
D in equation 10.26 is valid only when the dislocation spacing is large. This
assumed equality between R and Dis in error to the extent of about 10 %
for a 20° boundary, fo r example. The general theory has been improved by
van der Merwe 1 by consideratio n of the forces between a toms adjacen t to
the boundary in a more rigorous fashion than discussed here. The predictions
of the two theories are shown in Figs. l 0.18 a nd l0.19 for tilt a nd twist
boundaries as a function of misorientati on. From these fi gures, il is observed
that the grain boundary energy is z.ero at 0 = 90°. This is physically reasonable
since as 0 increases from 0 to 45°, the dis registry between the crystals increases.
Between a misorientati on 0 of 45° and 90°, the disregistry decreases for a

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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·:·:·:·:·:·: ·: ·:·
·:·:·:·:·:
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··.·
··
..... .......... ...••...••...••.••.••.••.••.•••.
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.· ·· ·· ··
.·.·.·.·.··· ·:·:
··.···.·······
•..·=..·=•·=..·=....·=. ..
••
........
··~·~·-:·.~·-~ ....... .· .· ··

·~ :·
. .•:
~-.~·~:·
~~ ~. ~· :~ -~·-~· :~ -~
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·:·:·
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=·:.:·:::· =· :· :·:; ::::::::
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~.

:· . . .
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. • ••• •• •• . .••••••• ·:·:·:
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~~·:·:·:·:

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.....-:. ·:·:·:·:·:
·:·:·:·:·:
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• • • • • • • ••·~••·-~·:·:·:·:·:·
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...•.•.•....•••.• •••••••
•• ••
• • •• •• ••
••
~ .-•-.•~.•·.•······
. .
••••••••••••••:·••:·:·:·:·:
•••••••••
....................................··....··..··..··..··..··..··..················..··..··..··.
• ••

·~··~··~·:~ •• • • • • • • • • •··•···· • • ·· ·· • ··
• • • ••• ••·· • ··
• ··
.·..••~..•.......·•...·'·. ••.··..·•.. .. .......... .··..
~~·:·:·:·:·: • • • • •
.··.. .. ................
·: •• ·:·:···:·:·: •
'•
·~··
·:·:·:·:• •••
·:·:·:·:
·~··········
. .
·• ·•.·•.··. . . .··.··.··..··..··.... . . \
~
·······

·~··:·.~··
.....
•• •• •• •• •• ••
•• •• ••·•
••··
••·•••·• ·· ·· ·· ·· ·· ·· . . . . . . . . . . ... . .
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

Crystal ub (J/ m2) cr/asv Reference

Copper 0.6 0.36 N. A . Gjostein and F. N. Rhines, Acta


Met ., 7 , 3 19 ( 1959)
y-lron 0.85 L. H . VanVlack , J. Metals, 3, 25 ( 1951 )
ex- Iron (4 % Si) 0.76 0.55 L. H . Van Vlack, ibid
Lead 0.20 K_. T. Aust and B. Chalmers, Proc. Roy.
Soc. (London), Ser. A, 204, 359 (1951)
Tin 0.1 K. T. Aust and B. Chalmers, Proc. Roy.
Soc. (London), Ser. A, 201,210 (1950)
.' Silver 0.4 0.35 A. P. Greenoug h a nd R. King, J. lnst.
Met., 79,41 5 ( 195 1)

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

Table 10.6 Interfacial E nergies for Cr ystals in Twin Rclationship 0

Crystal Reference

Cu (coherent) 0.025 R . L. Fullman, J. Appl. Phys., 22,448 ( 1951)


Cu (noncoherent) 0.44 R . L. Fullman, ibid., 22, 456 ( 1951)
Fe (coherent) 0.187 C. G. Du nn, F. W. Daniels, and M. J. Bolton,
J. Metals, 2, 368 (1950)
Fe (noncoherent) 0.70 5 Ibid.
•\
AI (coheren t) O.l20 R. L. Fullman, Table Ill in article by II. Orooks I

in M eral lnletface, ASM, 1952

° From D. McLean, Grain Boundaries in Meta ls, Oxford, London, 1957.

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

Fig. 10.22 Noncoherent twin bound-


I I
ary. Dashed line represents twinning,
plane and solid tine represent actual
boundary. I I

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

rapidly as 4> increases. As a result, the boundary energy increases rapidly


and there will be a large value of oufocp, which would lead to a la rge force •I •

tending to pull the boundary into a low energy position.


Let us now consider briefly a method that is so metimes used for measuring
boundary energies. This is the result of an interesting phenomenon that
10.5 Interna l Bounda ries-Str uctural Discontinuity 249

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

Fig. 10.24 (a) Grain boundary in a


crystal. (h) Same bounda ry after heaLing
(b) Lo-an elevated tempera ture.
250 Thermodynamics of Surfaces and Interfaces

'

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

u 11 - .Jsv cos</> - Cfsr cos</> =0


or
(]b
= 2 cos 4>
-
asv
This particular relation is widely used for obtaining boundary energies.
The angle </> is measured by use of the interferogram and if u.sv is known,
a 11 may be evaluated.
As one might envision , adsorption of impurities will readily occur at given
boundaries inasmuch as q will be reduced upon absorption or most impurity
10.5 Internal Boundaries-Structural Discontinuity 251

Crystal Crystal
1 2

Fig. 10.26 Force diagram applicable to Fig.


10.21b at equilibrium.

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

For a binary system, from the Gibbs- Duhem relation

XA dfLA = -Xu dfLu


Combining yields

(~) = -rn + (Xu) r~


OP,a T XA.
For a dilute sol ution of B in A which follows Henry's law, we obtain from
above
f' 5 = - _ l ( au ) + X B.A.
r
RT ol nX13
For a grain boundary we can not usc the criterio n o f choosing the plane
where r .A = 0 for defining the location of a boundary since segregation of
impurity is expected to be symmetric on either side of the boundary and

1Based on presentation of J . Hirth, in Energetics in Metallurgical Phent;711ena, Vol. IJ,
W. Mueller, Ed ., Gordon and Breach, New York,- l965. •
• i

252 T hermodynam ics of Surfaces and Interfaces

! ..

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

10.6 INTERNAL UOUN DAIUL~S-D OMA I N WA L LS

In the last two sections, boundaries involving c hemical and structural


singularities were di scussed . Typical values of the energies of these boundaries
are 0.1 - 0.5 Jfm2 , depending on the exact nature of the boundary. There is
another type of boundary which does not involve di scontinuitie s of a structural
253
10.6 Intern al Boun daries -Dom ain Walls
en regions
or chemical natur e. These bound aries represent the interface betwe
ial, or
of differing magn etizat ion direction in the case of ferromagnetic mater
example.
differing net polar izatio n in the case of ferroelectric mater ials, for
develop
In the case of ferromagnetic mater ials, the doma in bound aries
in walls
as an attem pt to reduce the overall energy of the crystal. The doma
ase in
themselves cost energy to form but nonetheless there is a net decre
a mag-
magn etizat ion energy. One may caJcu late that a single crystal has
1

netiza tion energy of

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

Fig. 10.28 The structu re of the Uloch wa ll separa ting tlomai


ns. In iron the thickness of
Introduction Ia Solid
tl1e transit ion region is about 300 lattice co nstants. Fro m C . KiUel,
or J ohn Wiley & Sons, lnc.
State Physics, 4th cd., Wiley, New York, 1971. By permis sion

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.

walls has been calculated to be approximately

( 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 •

10.7 INTERFACES UETWEEN SOLIDS OF OIFFEHENT STRUCTURES


AND DIFFERENT COMPOSITIONS

In previous sections we have presented a general discussion of cases in I.,


which solids have the same structure hut differ in chemical composition and
also for solids which have the same composition but differ in structure. The
energy of a general interface may therefore be considered to consist of a
I
chemical term and a structural term. Very little detailed theoretical work has .1
been done on cases of this complexity. For situations in which we have a
I .
10.7 Interfaces between Solids 255

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

The problem of calculati ng U is the sa me, to a first approxi matjon, as th at


of calculat ing the energy of a low angle grai n boundar y of dislocat ion spacing
D. For the case of the copper- silver system with a ( 111) interface , aA~ =
10 m. Thus d = 0.12. This corre-
2.88 x lQ- lo m and a cu = 2.55 x I0-
sponds to a dislocat ion every 24 x 10- 10 m or about 8 atomic spacings.
From equation 10.23 we see that this match correspo nds to a low angle
boundar y with an angle 0 of 0 . 12 rad ia ns or 7°. From Fig. 10.20 we find that
2
thi s correspo nds to a value of u of about 0.25 J/ m at 1338° K
H is not obvious a priori, however , Lhat the interfac e has a dislocal ion
256 Thermodynam ics of Surfaces and Interfaces

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.

Table 10.8 Relative lntecfaciaJ Free Energies

System a (J/ m2 ) Ref.

Pt(s)-AI 20 3(s) 1.05 a


Pb{I)-AI 20 3(s) 1.54 b
Ag{I)-AI 20 is) 1.77 b
Fe(/)- Al 20 3(s) 2.3 b
Cu(s)-Na 2S 10 3( /) 1.5 b
Cu(l)-Ti C(s) 1.23 b
Cu(s)- Cu 2 S(/) 0.09 b

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.

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