Chapter 10

Chemical Potential and Equilibria

amongst Phases of Variable

Compositions

10.1 Chemical Potential

10.1.1 Definition

In Section 1.3, we about thermodynamic

discussed
equilibrium. It was mentioned there that
for
physico-chemical processes and chemically reactive
systems,thermodynamic equilibrium
attainment of
requires physico-chemical equilibrium (also referred to as chemical
besides mechanical and thermal equilibrium)
equilibria. This means that chemical should be
uniform in the entire potential
system in addition to uniformity of and
pressure temperature.
J.W. Gibbs first
propOsed the term 'chemical potential in analogy with other
potentials
(eg. thermal potential and The meaning of
gravitational potential). the term will become
clear as we go along.
In
Chapter 7, a distinction was made between a molar quantity ()and the same for
system as a whole
() vide Eq. (7.5), for convenience of derivation. By adopting this
let us consider a
onvention, system with variable composition.Then Eqs. (5.11)-(5.14) may
be modified
as follows:

dU =TdS - PdV + (5U'"\ dn (SU

on Js.v.
dn t+ dn, +
on Js.V.m 2
Sn, Js.v
except except r
except n
-TdS - *
PdV
n,)s ,m,.excepnpt

159
dn (10.1)
 160

Sumlarty.
dn

i=TS ar (10.2)

4 = - dt- Pd1+
S . SA dr (10.3)

dn
dG= -SdT+ VdP+ d .P.a.exorpt
(10.4)

n.n , n, ... are numbers of moles of components1 2

As defined in sertion 7.2.1. 1s of U'. H.
The last term in Eqs. (10.1HI0.+) relatedto vanaton f, A
i in the solution. of a component
i is the genernl symbol
etc. As usual,
and Gwith change of n.n a component i(4) was
definition of chemical potential of
Gibbs original

sv. (10.5)

Therefore.

dU' = TdS - PdV+24 dn; (10.6)

Again.
dH = dU + PdV + V dP (2.25)

Combining Eqs. (10.6) and (2.25), we obtain

dH = TdS+ VdP + E4; dn; (10.7)

Equating relations (10.2) and (10.7),we get

SH
O s,P.2 exceptn
(10.8)

Similarly, by combining Eqs. (10.3) and (10.4) with

be Eq. (10.6), the following relations can
obtained:

(10.9)
on,
xcept n

4 O r,P..m .except
(10.10)
 and Equilibria amongst Phases of Variable Compositions 161
alPot
Potential
Chemical

the above cquations, therefore,

arefour there different definitions of

In accordar
al
In
thermodynamics,
wc cmploy (ubbs free
energy critcrion for

potential. as
text as well
as in other texts dealing with metallurgical
ypo in this thermodynamics.
Hcnce, as given in lq. (10.10), will be
chemical
lbrium. nehemical potential, employed. This way.
cyillt of as the partial
olar
mol free energy of component i (i.e. in a solution.
G)
the same
definition
thc the in section 7.2.2.
hecomes nd discussed
u and
defincd
as

of Chemical Potentials amongst Phases at

Equality nstant Temperature and Pressure
at Cons
10.1.2
10. Equilibrium

At constant
T and

2 phases
P, Eq. (10.4)

( and
dG =H
l1) in the
may be

dni
rewritten

+ H2dn2
system. Then,
as

+.. + ; dn; + .. (10.11)

Consider

dG = dn; +.+ dn + (10.12)

dG = dn +.+4" dn" +. (10.13)

moles of only component 1 between phases. Then,

Consider exchange of dnj

dG = dn,dG'." =ul dn (10.14)

Since,

dn=-d; = -
Therefore,

where dG is the total free

dG' =dG'l +dG:l =dn,
energy change
in the system as a
(
dn^

-e
result of exchange
(10.15)

(10.16)

of dn

=
I and II. For equilibrium at constant T and P,
between phases

dG = 0, and hence from Eq. (10.16),

(10.17)

with similar arguments.Hence,

can be generalized
for all components
Equation (10.17) then
I and II are at equilibrium,
at constant and P, if phases
(10.18)

at equilibrium as
for any number of phases
Similarly, Eq. (10.17) can be generalized
 and Metallurgical Thermodynamics
162 of Materials
extbook

u=u="=...=
u==" =... =u

where P is the of phases in

total number
the
==
system.
=...

of chemical potentials of
=4
all comns
(10.19)

is a statement
of equality nents
Equation (10.19) and temperature.
at the same pressure
dnongst all phases at equilibrium

10.1.3 Some Additional Remarks on Chemical Potential

Elucidation of Eq. (10.19)

it does not
one. For application purposes, matter wheth
Equation (10.19) is the most general it is necessary to clarify some confucie
er

or a substance. However, ions.

a phase is a solution pure
and oxygen gas, and find out the chemic al
Let us consider equilibrium between liquid copper
The confusion may be due to the following reac
potential of O,(o,) in liquid copper. ason.
in metals in the atomic state. How can we imagine Ho2 in liquid copper then?
Oxygen dissolves of chemical equilibria, the
The answer lies in the fact that, according to equations
but it can never be zero
concentration of molecular O, in the melt may be extremely small, er
This follows from the equilibrium

2[0] =[O]:K20 (10.20)

Here. []denotes components in metallic solution. K20 has a nonzero value. If it is zero, then

can
AG0 RT R20 would be infinity, which
In is not possible. Thus, [o,] not be zero.
to equilibrium with
To take another example, suppose a piece of pure SiO2 is brought
in SiO2 and Hsi The
a molten Cu-Ag alloy. How can we think of HAR
in the alloy?

with the help of the following reactions:

explanation car be given

SiO(s) + 4[Ag] =[Si] + 2(Ag20) (10.21)

(Ag0)= 2(Ag) + (O) (10.22)

SiO2(s) + 4[Cu) = [Si] + 2(Cu,O) (10.23)

Some would dissolve in the alloy, through

In the above equations, ()denotes oxide phase. Si

be very small. Similarly, through

reactions (10.21) and (10.23). Its concentration would
reactions (10.21) and (10.22),a very very small concentration
of Ag in oxide phase can be
case of O2 in Eq. (10.20).
predicted from thermodynamic equilibria considerationsas in the

4,criteria for phases not at equilibrium

the process
occur, then (dG')T.p < 0. Combining
lT a process is to this with Eq. (10.16),

would take place if

 hases
Phas of Variable
nd Eq
Equilibria amongst Compositions 163
and
Potential
Chemica/

(10.24)

ess under
under
the process
consideration is
ranster
of
component I from phase II to

(10.16). taker taken as positive.

Hence dj is positive, i.e.
phase I receives
For has been
dnj
1. [Nore: it.]
phase ll loses to state that a component would tend to be transferred
and phaseaA can be generalized
nd phase
dn This makes
(10.24, potential. j,analogous to thermal potential
Equation er to a lower chemical, thermal potential (i.e. higher temperature) to lower
flows from higher
heat
For example,
etc.
potential.
thermal
potential
of chemical
calculations are carried out through equilibrium constant as
Application
cquilibrium there are areas of where chemical
chemical 7 and 8. However, application
Overall
in Chapters These are as follows:
rated
ffers
offe advantages.
approach
otential will be illustrated in this chapter itself.
equilibria
,Studies of phase we only. Hence,
are interested in one component
systems, often
2. In multicomponentis to consider chemical potential of that component alone.
an easy approach to which way a species (elementor
(10.24)
allows easy visualization as
2Fauation
qu
would tend to get transferred.
compound)

and activity
Chemicalpotential as
in terms of chemical potential
may be rewriten
Equation (7.16)

4-=RT In
(10.25)

where,

that
= 4; at standard
By universal convention,
we adopt the same standard
state of i.

taken as zero for all phases

is
system.

state in all phases. This simplifies Eq.

(10.25)
in the It also means
into

= RT In a;
(10.26)

of 02 (also known as oxygen potential)

for Eq. (10.20), chemical potential
For example,
may be writen as
at eqnilibrium
in both the gas and liquid copper co-existing

=RT In po (10.27)
Ho=RT In ao,
where Po2 = partial
gas at equilibrium.
pressure O, in
(provided
standard states
that at equilibrium
From Eq. (10.26), we may also conclude
are same in all phases, (say) pure components
1, 2, .., i, ) (10.28)
a =q =...
=
a =..=4
I to phase II, if a >a",
Also, , Species i will be transferred
from phase
 164
-
extbook of Malerials and Motallurgical Thermodynamics

-
10.2 GIbbs Phase Rule and Applications
10.2.1 Derivation of Gibbs Phase Rule
Consider a system at with the following specifications
cquilibrium

1.Constant temperature and

pressure
2.
Components are 1. 2. ...i.J
3. No. of
components C =
4. All
components arc independent,i.c. they do not enter into chemical reactior
one another
5. No. of
phases P. =
The of each phase would be determined
state
thermodynamic by temperature. Dreca.
and composition variables (mole fraction, weight % or anything ire
else). The
composition variables to be fixed
independently is (C ). - numher
of
Therefore, the
i.e. C +1
thermodynamic state of single phase
variables. The number "2" stands for
would a
be determined
by (C +2n -
variables. For the entire and P, which T
constitute tu
1

system of P phases, the total number of variables ndepen-dent

All the above woL
variables, however, would not be P(C+1).
thermodynamic equilibrium independent since the re
impose the following restrictions irements for
(i.e.
constraints):
T= T=.. =T for thermal equilibrium
pl =pl= ...
=PP for pressure
equilibrium

where I, II, ... are

=
phases. From Eq.
. = (C-equations for chemical
equilibrium) (10.29)

(10.29),
Total No. of constraints = (P - 1) (C + 2)
(P - 1)
since there are (10.30)
equalities in each line of Eq.
Total (10.29). Hence,
No. of
independent variables = F = P(C + 1)
-(P - 1) (C + 2)
= C - P +2
quation (10.31)
(10.31) is the
famous Gibbs
phase rule.
 .
Datential and Equilibna amongst Phases of Variable
Comoositions
Pote 165
Chemical

of Phase Rule
Application
10.2.2
components

3.
Non-reacting
a1Solid-Liquid-Vapour Equilibria (Section 6.4). If allI
10.1 three-phases co
ENAMPLEP C
= 3.iFor a pure substance, From Eq. (10.31), therefore, F= |-3+
=
eust.

var
0.
then

7 or P
ncans an Invariant

P independently.
cquilibrium with no degree of frecdom at all,
This explains the triple point phenomena (see
i.c.

Fig. 6.4).
we cannot

Alloy Phase Diagrams. Here, the system is non-reactive, the

pL E 10.2 environment
ENAMPLE either vacuum or an inert gas (Ar, He etc.). Again, pressure has hardly any
either
llov being
being
of the alloy into
So. Eq. (10.31) gets simplified

=C - P +1
influence.
F

a hinary system (Cu-Ag, Fe-Ni,

olid solution is present.
then P=l and F
C = 2. Hence,
etc.),
=2. This means both
F = 3 - P. If only liquid or
temperature
(E.10.1)

and composition
If there is a mixture of solid solution + liquid solution, then
an he varied independently.
cand F = 1. This means that if temperature is fixed, compositions of solid and liquid

fixed, and vice versa.

are automatically
Figure 10.1 shows
the binary phase diagram of Pb-Sn system. At 200°C, compositions

of liquid as well as a and p solid solutions can be varied over some ranges. But composition

C Tin (atomic%) F
10 20 0 40 50 60 70 80 90

350327 600

300
L
500
250 232

200
a+L 183 400

61.9 |97.5
19.2 300
150

200
100 a+ß-
100
50
80 90 Sn
60 70
40 50
Pb 10 20 30
Tin (wt.%)
binary phase diagram.
Lead-tin
Fig. 10.1
 166 etthook of Mateials and Motallungical homodynanics

t the solicd solulion on tho solidus

the hqud suvlutuon on qudus and that of solidus are
fixec
these coTIespond to cquilbrium co existence tw phases.
of
since
the cuteetie point, there are three phusCs CO-CxIStng
at
cquilibri
brium.
0 hee, and is an mvarant. 'Therefore

FNAMPLE 103 Nonreacting Ovide 'hase Diagrams, A g00d cxample of

ode phase dagiam is the Si)A,),binary system which constitutes the On-reacling
princi
iaram for ovide systems (lig. 10.2). Tike alloy systecm
stems, herc cipal
retractory also
and pressure are neglected (i.e. F =C -P+ ). the
gas
phase
phase
both temperature and composition ot liquid phase can be varied. huu
Agan,
at a
cmperature, liquidus eomposition is tixed. Solid phases arc pure. Point
nt P is fixed
an
known as peritectie. Here, three phases co-exist at equilibrium
rium (liquid, invariant corundu
Jum,
mullite).
Reacting components
If
components are reacting amongst themselves, then the reaction equilibria
constitute
constraints. However, all
possible reactions are not independent.Only the number additic
ofinden
reactions are to be taken into account. In such a
situation, endent

C N -R
where N is the number of species (elements and (10.32)
compounds) and R is the numberer
independent reactions. of

EXAMPLE 10.4 Consider a system of pure metal (M),

There is oxygen and pure metal
only one possible reaction, viz. oxide.

M(s)0(g) = MO(S)
2 (E.10.2)
N 3 (M, O2, MO), R = 1,and P = 3. The
gas phase
variables. Hence, F -
=(3 1) - 3 + 2 = 1. If T is
involved. So both
T and P are
is

M and MO are pure fixed, then Po2 at equilibrium is fixed.

anyway. Therefore, the state of the
fixing 7. Figure 8.I on the system gets fixed completely by
Cu-Cu0-0, system illustrates this.
Suppose, in the above M
system, is
present as a liquid solution M-X, where X is a
metal. Also,
is MO
present as a separate oxide nobie
than MO.
Then, in this case
solution, MO-BO, where is more BO
too, the only stabie
would not form
oxide
significantreaction is oxidation of to
MO.
A M
=
N 5 (M, X, significantly, and BO
would not be reduced to B
O2, MO, BO), R = significantly. Here,
Solution). Hence, F = 1, P 3 (liquid =
metallic solution, gas, liquid cide
3.This means ON
of that even after
phases cannot be fixed. fixing temperature and pressure, tions

cop
Now, in
addition to
fixing T, let us fix Oxide
solution
independently.Then, all three
phase also gets fixed at
compositions of metallic
soluuo
degrees of freedom are utilized, and Po, of the
0a he
constants as equilibrium.This may also be an
follows. For explained from tne ub equilibrium
Eq. (E.10.2),
 ilibria amongst Phases of vanablo Compostions 167
-

(emical
SiO, (wt.
*)
50 40 30 20 10
70 60
80 1724 7TT
NT O SII K A CRIS1OAITTh.
U'NDEM), 2050 C,1722T
(CORUNI
QLANMINA
NLIINUINI 2050
2000

(YRINTM
LIQID
LIQUIN 1900

3LE|
3400 1800

200 1700
3135 A1,O 2SiO,(MULLITE+LIQUID
CORUNÓUM
2903°H 1600
000 3A1,0:2S10
5.5TAIO (MULLITE)
94.5% SiO,
2Si0, (MULLITE
CRISTOBALNE+
3AI,O, 1500
2800 2578°F

71.8%Al,0 1400
2600 3A1,0,2Sio, (MULLITE)
TRIDYMITE 28.2% Sio

2400
L 10 20 30 40 50
60 70 80 90 100
0
Al0, (wt. %)
Fig. 10.2 Silica-alumina binary phase diagram.

K= (Mo) (E.10.3)
tauPo]
and Thus, from
Kis fixed by temperature, aMo and am are fixed by temperature composition.
is
automatically fixed.
Eq. (E.10.3). (Poz )eq

EXAMPLE 10.5 Dissociation of limestone

CaCO (s) = CaO (s) + CO,(g) (E.10.4)

N=3 (CaC0, CaO, COj), R = 1 (i.e. Eq. (E.10.4), P = 3 (CacOs. CaO. gas).

Hence,
F =(3 1) -3 +2 1. If temperature is fixed, then (Pco»)eg is automatically fixed,

thus the
fixing state of the entire system.
Figures. 10.1 and 10.2 have presented phase diagrams of Pb-Sn and SiO,-Al,O3 binary
and
Siems, respectively. These are examples of condensed phase systems(i.e. solids liquids).
wnich also negligible (unless the pressure is
are nonreactive. The influence of pressure is
 168 Textbook of Materials and Motallurgical The modynamics

very high. of thec order of thousands of atmospheres). In

contrast,
construction
stablty diagrams for reactive has to consider the
reactant
systems gas phase if thcro o ph
phase
(s) and/o
product In Scction 8.3.2, we have alrcady provided
on
(s).
some Base
The thermodynamic basis for finding out Po2
this.
PcoPco2 and
cquilbrum with mctal and metal oxide also have becn Cxplaincd. FurtherPa,lpi.a SS1ons
exa atios
presented in
Chapter 11.
he
EXAMPLE 10.6 ()Caleulate the chemical potcntial of carbon of a gas mixture .c
=
.

e.
CO: at 100G K and 2 atm. total pressurc. Assume pcoPco2 10°.
(1) Suppose this gas mixture is brought in contact with zirconium
metal, would
ZCform
Solution () For the reaction:

2CO (g) = CO, (g) + C (s)

(E.10.5)
AG can be obtained by combining the following reactions:

C(s)+50(g) =CO(g) AG=-199.4 x 10" J mol-

(E.10.6)

C(s)+Op(g) =CO2(g); AG=-395.1 x 10" J mol-l

(E.10.7)
The values of AG., AG have been obtained from the data table in the
Appendix.

G =AG - 240 = + 3.7 x 10

Hence
ce,

.
J moll = - RT In
Ks

- RT In
Pco X
(E.10.8)
Jeq

Noting thatpcoPoco2= 10°, Pco2 atm, Pco2 = 1000

00 500
atm., and substituting these
values in Eq. (E.10.8), we get

ac activity of carbon at equilibrium of reaction (E.10.5) = 7.78 x 104

Hc RT In ac = -59.52 kJ mol-
[Note: Actually, RT In ac = Hc
Eq. (10.26)]. Also, as elucidated
Hc. However,
in
- by convention,
section 10.1.3, although carbon is not
is zero
in
|see
the
present
gas, there will be a finite value of the gas.)
Hc in

(i) For, Zr(s) + C(s) =ZrC(s); AG = -41.5 kJ mol at 1000 K (E.10.9)

Again, AG(ZIC) = -RT In azrc (E.10.10)

azr x dc
)eq
 of Variablo 169
amongst Phase Compositions
and Equ Equilibria

Potential
that the activities of ZrC and Zr are | since they
Cheical noting
and notin
ions,
and
cquation
above 41.5 kJ mol-
the Zr+ZrC
Hc)atcq with
Weget
mbining RTIn(ac)eq
pure, ZrC will not form
m.
ane \c)Zr+ZrC
(cco-co2gus
Since

Basis for Binary Alloy Phase

rmodynamic
Thermodynamic
10
10.3 Diagrams
In section 10.2.2, we have made some
Pb-Sn phase diagram.
the binary he basis for understanding
diagrams.Phase diagrams provide
ws
se di
on thesee are very important in
Figur observations as well as ceramic materials. Hence, they
neliminary of
of alloys,
and these are typically taught in detail in
separate courses.
behaviour materials science, for
the
basis would be presented briefly binary systems only,
metallurgy the
bdynamic etc. will be omitted.
es. Ternary diagrams
Therefore,
with
some examples. is traditionally reserved for metallic systems. However, all
along alloy' condensed systems as wel. Therefore, for the sake
terminology
leito nonmetalliethe
The
are applicable
heading of this section. Incidentally, nowadays,
it
is used in
discussions
the word 'alloy'
rity materials also, e.g. ceramic alloys.
ofclari
used for nonmetallic
is being

Free Energy vs. Composition Diagrams-General discussions

10.3.1

As elucidated
in Section 5.7,
state
. any system tends
corresponds to minimum (G)T.P.
to lower its Gibbs free energy

Therefore, the
at constant

nature of
T, P.
a phase
The equilibrium
on variation G with composition at various temperatures. As discussed
diagram would depend
the constant pressure restriction is not important.
times earlier,
several
9.2 has
Section
thermodynamics of binary solutions. Figure
9.5 has dealt with
schematically

AS"" with mole fraction for an ideal binary solution at

variation of AG", AH",
shown variation of 4G" for regular
shown
9.6 has schematically
constant temperature. Figure

solution for both positive and negative va!ues of a.

binary
of the two
For a solution A-B, where A and B are general symbols
regular binary
components. From Eqs. (9.86) and (9.89), we have

AG =AG+G =RT (XA In XA + Xg In Xg) + RTaXAXB (10.33)

i.e.

AG"
XA
RT
In X^ + Xg In Xß + aX^XB (10.34)

can be calculated for different

of mole fraction
rrom Eq. (10.34), AG"/RT as function

dvalues of a. This shows that, if a> 2.0, the curve exhibits the maxima-minima
with respect to Xß = 0.5.
Or Ihis is shown in Fig. 10.3(a). The curve is symmetric
 170 of Matenials and Metallurgical Thermodynamics
Textbook

=0.5
X= Xn

Rcgular
+ve An arbitrary solution
solution (a> 2.0)

G HA

a+B
B b
stable Lstable
-stable ******

-ve (a)

(b)

aB

ap

dA

o A
Xp
"- J
B
(c)

ies o
A and B, and (C) acuvnim
Fig. 10.3 of: (a) free energy, (b) chemical potentials of
variation
and B, at constant temperature, for binary system A-B exhibiting max
A
type behaviour in 4G" (schematic).
 of Variable Comnocitio ons
amongst Phases 171
and Equilibria
Polential
Pole
Chemical

nasitive departure
from Raoult's Law (sce section 9.7.2). An arbitrary
a
means positive
departure but
is not a
rcgular solution, would not be
Positive bits such positive
10.3(a) also shows such a behaviour schematically.
which
acnectto XR =0.5. Figure
common tangent anmb to the curve mpn. Let us consider an
solution,
wit
ruct the
sVmmetric noW constru for the solution. Point q is AGm for a mix ture
AG"
Let us ion X.
Xp. 1
The point p is
composition. are fixed at m and n, respectively. Sinc is lower than q
arbutrary whose compositions than the solution in this
a + B would be stabler region.
f
two phases,
of mixture
ace
B of and G
pure A and
the values
the two-phase at pure provide G
p. of the tangent
The intercepts
Therefore,
vely
(see
Section 9.5.3).
to m = Ga for P-phase at composition
respecti at composition corresponding
for a-phase
i.e.
to n,
coresponding
(G am = (G")g a
a n (10.35)

Similarly,
(Ga ai m = (G%)gat (10.36)

As discussed
in Section 10.1.3, =0=4.Hence,
(10.37)

to (10.37), we get
Combining Eqs. (10.35)

(Aa at m =(4A)B atn (10.38)

(10.39)
n
(4Baat m =(PB)p ai

at
phases for
of chemical potentials
of equality have
This is in conformity
with principle the mixture would
it is confirmed
that the two-phase
(Section 10.1.2). Hence, solutions would
that only a
equilibrium or B single phase
of a and B. It also follows than straight
lines
Ixed compositions curves are lower 4G"
since the
at the two-terminal regions
Sla0le in the regions
'am' and "nb. mixture.
two points on the curve in two-phase
ong any
and (10.39),H and
should be constant the two-phase
also should
be constant in 0 =
TOm Eqs. (10.38) and ag be noted that 4a
of Eq. (10.28),aA
arly, on the basis and 10.3(c).
It may
10.1.3.
Figures 10.3(b)
P.
A HB
These

=0
are
at
shown
XB = 1,
in

as per convention already

discussed
in section

with Miscibility
Gap
10.3.2 Phase Diagrams the thermodynamie
illustrates

The free of Fig. 10.3 schematically formation of a + ß two-

Ey
energy compositiondiagram
Vs. a and B and
solutions as 'miscibility gap'.
basis
of the two-terminal what is known
regardin stabilities
diagrams
which exhibit critical temperature
7
above the
This
This is
res.There are phase in Fig. 10.4(a). Here, is transformed
into two-phase

the single phase

schematically
lly illustrated
there below Ter
mix
is
One
only
which is the
But
phase.
miscibility gap AG" is given by
Eq. (10.33). Differentiating
AGm

to be regular, = - dB)
= - XB,
the solutions
Assuming
ne I
and dXa
w.r.t.
Xp, we
C obt
obtain (noting XA
 172 Textbook of Matenals and Metallurgical Thermodynamics

(a)

Ti

Single phase

Ta
Phase I Phase II

Phase I
T +
Phase II

A B

B
(b)

+ve

at
T T2

Common| tangent
atT Ter
-ve

at T =Ti

XA =Xg = 0.5
Fig. 10.4 (a) Phase
diagram, and (b) for a
binary system exhibiting corresponding free energy-compositiondiagrams
miscibility gap, assuming regular solution behaviour chematic).
 of Variable Compositions 173
Dotontial and Equilibria amongsi Phases
Chemical

S(AG")-RT|In a(X Xn (10.40)

S(AG)RT + 2a (10.41)

sa)RTEX (10.42)

we get
S(AG") =0 at XA = Xp = 0.S5.

From Eq. (10.42),

Since
at T= Te. both
s(AG)
Svand
s(AGandX
8x
2 )should
(4G) h be zero, the maxima of the miscibility

a one.
occur at XB = 0.5, provided
the solution is regular
gap would
Putting XA
= Xg = 0.5 in Eq. (10.41),we get

(4)-0 2a at =4, i.e. a =2 (10.43)

Since RTa = 2,
(10.44)
Ter 2R
solution. of temperature
for a binary regular independent
we see that, since AHm is
approximately of either
From Eq. (9.89),
a and not as a function
2 be taken as constant, been
may It has already
al a fixed composition, regular
solution.
for a particular binary
or composition
Lemperature
emphasized once,
and concluded that

a On the other hand, at T<Tr

which is the same as equation (9.92). is single phase.
shows the AG" vs. XgB

Cu
at> Ter a<
2, and the solution
the miscibility gap appears.
Figure
10.4(b) schematically

Curves at different
temperatureS
Diagrams Involving
3.3 Free Enerqy vs. Composition
Statee
of Standard dard states for
for both

In
Figs. 10.3
A and
Were
3 Change
and 110.4, in

taken as the
the free energy
same (either both
vs. composition
solid or
curves,
both liquid).
the standard
In actual phase diagrams.
 174 T0xtbook of Matorinls nnd Motnlluglenl
Thomodynnmien

iquid
solutio (14)

(a)
Solid

(A)
A
Noution

Unmixed
i)
+Ve solids Unmixed
liquids

(b)

-ye quid
utio
pIOS
ionnros

ATTol Solid
SS
(c)

Liquid
SS

Niquid
S At To

(d)
aA
Solid
SS

B
10.5
Fig. (a) Phase diagram, (b) free energy-compositiondiagram at
=
T= lo and th activity

Complele
composition diagrams of B and A, respectively at T To.
for system wiu
miscibility in
liquid and solid phase (schematic).
 Fauilibria amongst Phases of Variablo Compositions 175
and Equilibr
Potential
Chemcal is liquid and the other solid at the same
1ere one of them
where
situations where at temperature To. pure A is liquid, but pure
ter
is Fig.
10
r
10.5(a),

)
cnco free encrgy-compositiondiagrams, conversion
construction of
weoflenurc. An cxample would be required. The thermodynamic
a situation,
iauid to solidsolid or vice-versa
tem In such from liquid
Sohd. ccither now.
BIs statc is derived
the same solid i Is
G (S) and that of pure liquid i is G) at
at
ofstandard
for doing scrov of pure
free
Suppose 7. Then,
RT In la, (s)]
= G - G (s) (10.45)
temperature

RT In la, (0]
=G - (10.46)

of in the solution with respect to solid and liquid

refer to activity
i
nd a.()
and
where
a;(s)
states, respectively and (10.46),
we get
standard Eqs. (10.45)
Combining

RT In 4=)C)=
4,0J
- AG (10.47)

of pure i upon melting

at temperature T. Now,
the free energy Cchange
here AG is

- TAS
AG=AH (10.48)

At equilibrium
melting temperature 7
AG =0, As AH (10.49)
T
Again,

AG (at T) -AG (at 7m) =AG,

=AH (at T)
- AH (at T,,)

- TAS T) (10.50)
(at T)+T,As (at

i.e.

-
AG = IC,) C,(6)] dr +7,As (at T,)

-T|As (atT,)+ ) IC,0-Coar T

(10.51)

into

C,) = C(s), then Eq. (10.51) gets simplified

t is assumed that
AH (at Tm.(T. -T) (10.52)
AG As (atT)(T
T)= T
4 changes linearly with change of temperature
 Tettd Maeials ant Themodynamice

.
Motallunylcal
176 of

EXANPLR 10.7 Gold and mutally insoluble in the solid

silicon ae
of te
binary eutectie system with eutectie temperature o.6k nc comnposition of andform
and Nau 0S14. Caleulate the tive eneIgy of the eutectic mclt relative
ive to
to S a =
(i)
pure) sold Au and sold Si, and (ii) unmixed liquid
Au and liquid Si. unmixe0.86

) mcCp
Assume
tor sold and both Au and Si.
i8the
lhquid tor
same
Solution Frve energy of the cutectie mclt, relative to pure Au and
pure Si
at o3o K. is .1", where solids

M =NAu u (eut)
-Gu)]+Xsi[u (eut) - G()

=X (ut)
- )+ Xs:4u (eut)-,6)|
(E.10.11)
Since the eutectic melt co-exists at equilibrium with both solid gold and solia
636 K. d silicon at

Au(eut) =4 (). si (eut)=us,(s)

sG" = 0. (E.10.12
Therefore.
(ii) For free energy of the eutectic melt relative to pure Au and
liquid pure liauid o
at 636 K. Si

AG" =XAuGAuteu) -Gauo+Xsi Gsiew) -Si

(E.10.13)

=XnuGAueu) Gu+ uGu Xau

Combining Eq. (E.l10.13) with Eq. (E.10.12),

Since Cp of solid and

G XAuGu u) +Xs
are assumed as the same, from
i S) (E.10.14)

liquid Eq. (10.52),

s)- G'a) =- =- n2 (T, -636) (E.10.15)

For Au,
T
Tm 1336 K, AH =12,760 Jmol
For Si,

Tm 1683 K, AH=50,630 J mol

the values
Substituting in
Eqs. (E.10.15) and (E.10.14), we get

AG, = 0.814 x 12,760o

- = -11300J
11300J
mof".

1336
(636 1336) + 0.186 x 50,630 (636-1683)
(636 1683)
1683
 and Equilibria amongst Phasos of
Variable
Potential
Chemical
Compositions 177
177

al Free Energy vs.

Composition
Diagrams
10.4
Solubility in Solid and Liquid Phases
Complete
10.4.1 the hase diagram schematically. An
shows example is
iron-nickel
(a) ltine points of purc A and purc B, system.
10.5a) are melting respectivcely. AtT =T. nure
Figune and 7Tm(B) B is solid.
iA) but pure
the
the frece energy diagrams
ts at To. It 1s to be
hquid. presents noted that, in
s
10.5(b) soutiOn in tne reality.
Figure er liquid or solid Cntire
composition range. Hence. hoth
ei

do not
have and partly real at T To. Since the stablest states of A
c
artly hypothetical and

olid, respectively, GX() and Gg(s) have been arbitrarily taken

B are liquid a and

alues at metastable states. Hence, they correspond to
and
Gs) states A and
of A and B, f
B, and the values can be calculated by employing
hypothetical

Eqs. (10.47) and

tandard is the
common tangent.
1052): ef
ef
and show activity vs. composition relations for B and A,
10.52): 10.
and 10.5(d)
10.5(¢) respectively
Figures
corresponding to have liquid A and B have standard
Curves
liquidsolution states.
at 1o to those of solid solutions have solid standard states.
curves corresponding
whereas

s04.2 Eutectic Phase Diagram with Finite Solid Solubilities

FEaures 10.6a) and are the schematic phase diagrams. The terminal solid solutions
10.7(a)

and B. Figures 10.6(b)

and 10.6(c) present free energy vs. composition and activity
= =
at T T1. Figures l0.7(b) and 10.7(c) are those at T T3. Curves
position diagrams

in both Figs. 10.6(b) and 10.7(b) for the liquid solution have liquid standard states (real or

hypothetical,
as the case may be). Curves for aand B solid solutions, respectively. have
solid
B as standard states. The activity vs. composition curves have employed the real (i.e.
A and

stablest)
standard states for each component.

10.4.3 Phase Diagram with an Intermediate Phase

at
Figure 10.8(a) shows the nature of free-energy composition curves temperature T1
phase; a and yare
the
phase diagram with an
intermediate
rigure 10.8(6) is a schematic of a
wO Lerminal solid solutions. In addition, a high-melting intermediate
solid phase ß is present.

0.5 in a Phase in Binary System

10.5
Solubility of Solute
of the same in the
to the concentration
Sol ty of a component
with another phase at equilibrium.
in a solution refers
In this section,
this will be illustrated

e CXISting
simple binary system A-D:
and

guantitative relations derived using B at T T2 are Xg = (sat)

and XG (sat)
E'g. The solubilities of component
10.7(a).
 and Metallurgical Thermodynamics
178 Textbook
of Materials

B
A

Liquid

(a)

+ve at Ti

(b)

-ve
L
tLI

aA

ag

(c)

at
B
X activity
solid
Fig. 10.6 (a) Phase diagram, (b) free energy-compositiondia ninal

composition diagram
at T = Ti, for a binary eutectic
system w
solubilities (schematic).
 amongst Phases
of Variable
ihria
Equilibria
Compositions 179
and
Polential
Por B
hemical

Liquid

(a)

T2

+Ve

a
AG
(b)

-ve

-a+pJp

aA
aB

(C)

(a)
Fig
Phase diagram, (b) free energy-composition
at T for a=
diagram at
eutectic system
T
= T2, and (c) activity-
with terminal solid
composition diagram T2, binary
solubilities
(schematic).
 of Materials and Metallurgical Themodynamics
180 Textbook

Inter- y Primary
La Primary
mediate
solid
solid solution
solution phase
(
Liquid
solution
(a)
(L)

T
B+L +L (b)
B+L

1.0
0.5
0

(schematic),
for (b) binary phase
diagram at temperature
Ti

Fig. 10.8 (a) AG-composition

an intermediate phase.
diagram with

Since at these compositions

aand Bphases are co-existing

in aand phases, respectively. we have

to Eq. (10.19),
at equilibrium,according (10.53)

latXg (sat)]
=4s [at Xg(sat)]
is smal.
since its concentration

B Law in a-phase Law in -phas.

Let us assume that obeys Henry's B will obey Raoult's
in section 9.5.1,
based on the discussion
Therefore,
Hence,
= +RT InaslatX5 (sat)]
latXg (sat))
+RT In I Xg (sat0
(10.54)

+ RT In +RT In [Xg(sat)]

=% +RT In aflatXg(sat)]
latX (sat)]
(10.55)

+RT In
(Xg (sat)]
 hases of Variable 181
amongst Compositions
and Equilibria
Po
Chemvical

(l we get
and (10.55),
54) and
(10,54)
tq8.
In |XH(sa)|+ In (10.56)
Fouating In X(sat)=

= (sat)
Xg (sat)
(10.57)

in p-phase, as shown in Fig. 10.9. Then

there is
no solid solubility
anw that
that
now
Suppose
= l. Hence,
Ng(sat)

x (sat)
=- (10.58)

TB)

L
TmA)
L+ B
a+L
-.
T
Metastable extensions

a+B

B
A Xg Xg (sat)

equation
for B
illustrating
derivation ofsolubility
Hypothetical binary phase diagram extensions.
show metastable
in
phase; dashed lines

Let us
a in aphase, and
let ag be the activity ofB at Xg. Then,
compositionXp
(10.59)

ag YiB X (sat)

]
From
Eq. (10.25),
(10.60)

=RT =
In ag RT|InXy-X5
(sat)
 182 Textbook of Maternials and Metallurgical Thermodynamics

At fixed composition Xp. on the basis of Gibbs-Hclmholtz cquation i.e. Eqs.

Eqs. (c
(6.28),
and their applications molar propertics [Eqs. (9.31), (9.33)J

=
to partial (6.29)

- =i=- d In Xg (sat)]

d(1/T) (10.61)

Again. from Eq. (10.60).

d (4-yT
d(1/T)
= -R dX In (sat
d(1/T)
(10.62)

Combining Eqs. (10.61) and (10.62), and integrating

x (sat) =A exp|
RT (10.63)

where A is a constant.

Equation (10.63) thus provides a quantitative relation between B

solubility of in aenhs
hase
with temperature. Figure 10.9 metastable of curves
showsthe extensions by dashed lne
It should be noted that the solubility vs. temperature relation would be governed by

Eq. (10.62)even in the metastable state.

EXAMPLE 10.8 Melting point of lithium is 453 K. Solubility of iron in

liquid Li is

minimum at melting point of Li, and increases increasing Given

with temperature. that

solubilities
of Fe in Li Xpe (sat)] are 4.36 x 10 at 1473 K and 4.97 x 10 at 673K.
determine the minimum solubility.

Solution From Eq. (10.63),

XFe(sat)
=A exp (E.10.16)

where
H
= partial heat of mixing of Fe in liquid Li. Hence,

In
[Xpe(sat)] =In A - He (E.10.17)
RT
Puting in the values of Xpe (sat) at 1473 K and 673 K in Eq. (E.10.17), we obtaim

-7.738 = In A - H
Rx 1473
(E.10.18)

-12.212= In
ARRxx 673
673
(E.10.19)

of
the values
Solving the above equations, In A =-3.97, H =46143 J mol". Putting
ng

the above equations, Xfe (sat) at 453 K = 9 x 10 J mol'

K]
[Note: A may be =-40.65
considered as equal to exp (Sm/R) which gives Spe
 and Equilibria amongst Phases of Variable Comnoeit.
Equilibr 183
Potentialand
Chemical Phases
of Metastable
olubility
Solubility
olubilities
of B in aphase in mectastable
cxtensions are larger than
10.5.1 solubi 1hc schematic
that
f the bounding curves.
of
9
0.9
10
shows
regions at a temperature abo
frcc-cnergy
bove the cutectoid
composition
stable rbon system temperature is
Figune in the iron-carbon cenite is the stable phase at the Fe-end. For
the
the carbon, graphite
those for
gram is
the metastable
state. This means that
the chemical potential of
and cementit in graphite. As Fig. 0.10 shows, this leads to a
than that higher
stable is higher
equilibrium with cementite as compared to that in
ishe nentite
in cemen. in austenite
in

carbon of carbon
of Experimentalphase diagram data have confirmed this.
solubility with graphite.
uilibrium
equilt
Chemical of carbon
potential

for metastable equilibrium of

austenite and cementite
+ve
Cementitee
Graphite
Pure iron

G" Austenitee
Ac

Solubility of
Solubility
-ve of graphite cementite

C
Fe
Xc austenite
of carbon in
Fe-C system explaining why
solubility
of
Fig. 10.10 Schematicdiagram as compared to that for graphite.
with cementite
is higher at equilibrium

EL

10.6 Summary a
i in
of a
component
(u,)
are several definitions of chemical
potential
here definition
in chemical and metallurgical
the commonly employed
SOIution. However, free energy,
as follows:
is in terms of Gibbs
nermodynamics

G Jp,T,nm, 2, except nj
O
molar free energy ofcomponent
i
(G)
same as the partial
way, 4; becomes the