Solution thermodynamics: Theory

CHAPTER FOUR

4. THEORY OF SOLUTION THERMODYNAMICS

Chapter three treats the thermodynamic properties of constant-composition fluids. In this chapter
we are going to see the derivation of a fundamental property relation for homogeneous solutions
of variable composition.

In this chapter we will learn to answer the following questions.

How do we determine the thermodynamic properties of solution?

How do individual species behave in a solution?
What is chemical potential? And why it is important?
What is a fugacity and activity coefficient?

4.1. Fundamental Property Relation

For a closed system; Gibbs free energy is expressed in terms of temperature and pressure;

d(nG) = (nV)dP - (nS)dT ( 1)

Where: - n is the total number of moles of the system.

This equation may be applied to a single-phase fluid in a closed system where in no chemical
reactions occur. For such a system the composition is necessarily constant, and therefore

( nG )
=nV
P T ,n and [ ( nG )
T ]
P ,n
=nS (2)

Consider now the more general case of a single-phase, open system, material may pass into
and out of the system, and nG becomes a function of the numbers of moles of the chemicals
species present.
nG=g (T , P ,n 1 , n2 , . ni , ..)

The total differential of nG is:

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d ( nG )=
( nG )
P T ,n
dP+ [
( nG )
T ]
P ,n
dT +
i
[ ]
( nG )
ni P ,T ,n j
dni
( 3)

The derivative in the final term is important enough to be given its own symbol and name. Thus,
by definition the chemical potential of species i in the mixture is

i
= [ ]
( nG )
ni P ,T , n j

(4)

Substitute eqn. 2 and 4 into eqn. 3:

d ( nG )=( nV ) dP( nS ) dT + i dni

i (5)

Equation 5 is the fundamental property relation for single-phase fluid systems of constant or
variable mass and constant or variable composition, and is the foundation equation upon which
the structure of solution thermodynamics is built.
For special case of one mole n=1 and ni = xi

dG=VdPSdT + i dx i
i (6)

And G=G(T , P , x 1 , x 2 , . x i , ..)

The chemical potential of component i in a system is the change in the total Gibbs energy
upon the addition of a differential amount of that compound to the system at constant P, T
and all other nj.
Chemical potential is most relevant with mixtures. Matter flows spontaneously from a
region of high chemical potential to a region of low chemical potential.

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4.2. The Chemical Potential and Phase Equilibrium

Criteria for stability or equilibrium

Starting point; Closed system
2nd laws of thermodynamic;
For a change is exist between system and surrounding, if dS total 0 for a universe

total syst . surr.

dS =dS +dS 0

Qsurr
dS surr = But Q surr . =Q system . at Tsurr = Tsyst.
T surr

Q
dS
So, for the system T this gives Q TdS

Application of the first law provides:

dU =QW and Q=dU + PdV

dU + PdV TdS 0 (i)

The inequality applies to every incremental change of the system between non equilibrium
state, and it dictates the direction of change that leads toward equilibrium.
The equality holds for changes between equilibrium states (reversible processes).
Equation (i) is so general that application to practical problems is difficult; restricted
versions are much more useful. For example, by inspection:
Case 1: for processes that occur at constant S and V
( dU ) S ,V 0

Case 2: for processes that occur at constant U and V,

( dS )U ,V 0

Case 3: If a process is restricted to occur at constant T and P, then Eq. (i) may be written:

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 Solution thermodynamics: Theory

dU + PdV TdS 0

This eqn. is rewriting for constant T and P process as follows

[ d (U + PV TS) ]T ,P 0 But G = U + PV TS

So that [ dG ] T , P 0 (ii)
This is the most useful, because T and P, which are easily measured and controlled, are
more logical as constants than are other pairs of variables, such as U and V.

The equilibrium state of a closed system is that state for which the total Gibbs energy is a
minimum with respect to all possible changes at the given T and P.

At the equilibrium state differential variations can occur in the system at constant T and P
without producing any change in G. that is

( dG )T , P =0 (iii)

To apply this equation, one develops an expression for dG as a function of the mole number of
the species in the various phases, and sets it equal to zero.

Consider a closed system consisting of two phases in equilibrium. Within this closed
system, each individual phase is an open system, free to transfer mass to the other.

d ( nG ) =( nV ) dP( nS ) dT + i d ni
i
, T, P

, T, P d ( nG ) =( nV ) dP ( nS ) dT + i d ni
i

Where superscripts and identify the phases. The presumption here is that at equilibrium T and
P are uniform throughout the entire system.

The change in the total Gibbs energy of the two-phase system is the sum of these equations.
When each total-system property is expressed by an equation of the form,

nM =( nM ) + ( nM )

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 Solution thermodynamics: Theory

d ( nG )=( nV ) dP( n S ) dT + i d ni + i d n i
The sum is i i

Since the two-phase system is closed, eqn. (iii) holds true.

So that;
i d ni + i d ni =0
i i

The changes d ni and d ni result from mass transfer between the phases, and mass

conservation requires:

N ni +ni , dN = 0 = d ni
+ d ni

d ni = d ni

Therefore,
( i i ) d ni =0
i

Since the d ni : are independent and arbitrary, the only way the left side of this equation can in

general be zero is for each term in parentheses separately to be zero. Hence,

i =i (I = 1, 2, 3 N)

i =i = i = i

Where N is the number of species present in the system

Thus, multiple phases at the same T and P are in equilibrium when the chemical potential
of each species is the same in all phases.

Criteria for equilibrium for open system;

T =T =T =T

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 Solution thermodynamics: Theory

P =P =P =P

i =i= i = i

4.3. Partial Properties

The three kinds of properties used in solution thermodynamics are distinguished by the following
symbolism:
M = the properties of solution (H, S, V, U, G)
i i
M i= Partial properties ( H i , Si , V i , U , G ) of species i in the

solution
Mi = Pure species properties (Vi, Ui, Hi, Si, Gi)

The definition of the chemical potential brings to light an important concept relative to solution
thermodynamics... the partial property.

i= ( nG )
i = G ( ni ) P ,T , n j

We can extend the principle of chemical potential to any other thermodynamic properties; all
extensive thermodynamic properties of the individual components in a mixture can be described
with partial properties.

M
[
i ( nM )
ni ]P ,T . nJ
(7)

Where M is any system property (e.g., H, S, V, G, U )

This is called PARTIAL PROPERTY or RESPONSE FUNCTION, which represents the

change in the total property, nM, due to the addition of a small (differential) amount of (moles
of) species i, at constant T & P, to the solution. This provides the means for calculation of partial
properties from solution-property data.

i= ( nG )
i = G ( ni )
P ,T , n j

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 Solution thermodynamics: Theory

This implies that the chemical potential and partial molar Gibbs energy are identical.

4.3.1. Equations relating molar and partial molar properties

nM =M (T , P , n1 , n2 , . ni , ..)

The total differential of n M is

d (nM )=
( nM )
+
P T ,n T [
( nM )
] P,n
+
i
[ ( nM )
ni ] P ,T ,n j
dni

(8)

Since the first two partials are at constant n, we can remove n from the derivative, and we will
write the last partial in the simpler form

d (nM )=n
M
dP+n
P T ,x
M
T [ ] P, x
dT + M
i dni
i

(9)

ni=x i n so d ni =x i dn+ nd x i
But (10)

When dni is replaced by this expression, and d (nM) is replaced by the identity,
d (nM) = ndM + Mdn (11)
Combining 9, 10 and 11 gives:
x

M i ( i dn+nd xi )
(12)
ndM + Mdn=n
M
dP+n
P T,x
M
T [ ] P, x
dT +
i

The terms containing n are collected and separated from those containing dn to yield.

[ dM
M
dP
P T ,x
M
T [ ] P ,x
dT M
] [
i d x i n+ M x i M
i
i dn=0
i ]
(13)

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 Solution thermodynamics: Theory

The only way that the left side of this equation can then, in general, be zero is for each term in
brackets to be zero. Therefore,

dM =
M
dP+
P T ,x [ ]
M
T P ,x
dT + M
i
i d xi

(14)
M = x i M
i
And i

(15)
n M = ni M
i
Or i

(16)
Equations (15) and (16) on the other hand are new and vital. Known as surnmability relations,
they allow calculation of mixture properties from partial properties,
Since Eqn. (15) is a general expression for M, differentiation yields a general expression for dM:
dM = x i d M
i + M
i d xi
i i

(17)

Competition with eqn. (14) yield another general equation for dM, yields the Gibbs/Duhem
equation.

M
dP+
P T,x
M
T[ ] P, x
dT xi d M
i
i =0

(18)
For special case of constant T and P
x i d M i=0
i

(19)
4.3.2. Partial Properties in Binary Solutions

Equations for partial properties can always be derived from an equation for the solution property
as a function of composition by direct application of Eq. (14). For binary systems, however, an

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 Solution thermodynamics: Theory

alternative procedure may be more convenient. Written for a binary solution, the summability
relation, Eq. (i), becomes:

1 + x2 M
M =x 1 M 2

(A)

1+ M
dM =x 1 d M 1 d x 1+ x 2 d M
2+ M
2 d x2
Whence, (B)

When M is known as a function of Xl at constant T and P, the appropriate form of the

Gibbs/Duhem equation

x i d M i=0
i

For binary solutions;

1+ x 2 d M
x1 d M 2=0

(C)

Since X1 + X2 = 1, it follows that dX1 = -dX2. Eliminating dx2 in favor of dx1 in Eq. (B) and
combining the result with Eq. (C) gives

1 d x 1 M
dM = M 2 d x1

dM 2
= M1 M
d x1 (D)

Elimination first of M2 and then of M1 from Eqn. (A) and (D) yields

1=M + x2 dM
M
d x1

(E)

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 Solution thermodynamics: Theory

2=M x 1 dM
M
d x1

(F)

Thus for binary systems, the partial properties are readily calculated directly from an expression
for the solution property as a function of composition at constant T and P. when the composition
of each species is known, which can be illustrated graphically as follows.

Lets consider a plot between M (M can be either H, S, or V, or etc. any system property) and
X1.

Figure 4.1: A Plot between M (any thermodynamic property) and x1

The slope of the line I1I2 can be calculated as follows

dM M I 2 M I 2
= =
dX 1 X 10 X1

dM I 1I 2
And = =I 1I 2
dX 1 10

Rearranging

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 Solution thermodynamics: Theory

dM
I 2 =M X 1
dX 1

(G)

dM
I 1 =M +(1 X 1)
dX 1

(H)

I1 1
M
When we compare eqn. G and H with eqn. E and F; is the same as that of and

I2 2
M
is the same as that of (M and N) . Thus the tangent intercepts give directly the

values of the two partial properties.

The plot below shows how to find the partial properties under infinite dilution conditions. Plot
the property of the mixture as a function of composition (green line).

2
M
The tangent line drawn at X1 = 0 (pure species 2), = M2, and at the opposite intercept,

1
M 1
M
= . Similar comments apply to the tangent drawn at X 1 (pure species 1). In this

2 2
case M 1 = M1 and M = M .

Figure 4.1: Infinite dilution values of partial properties

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4.3.3. Relation among partial properties

i
i=G d ( nG )=( nV ) dP( nS ) dT + i dni
We know that and i

d ( nG )=( nV ) dP( nS ) dT + G
i dni
i (20)

Application of the criterion of exactness gives: the Maxwell relation,

V
=
T P ,n
S
P [ ] T,n

(21)

Plus two additional relations:

i i

G
=
P T,n ni [
( nV )
] P ,T ,n j

G
=
T P ,n [ ]
(nS )
ni P ,T ,n j

Gi
=V i (22)
P T,x

Gi
=S i (23)
T P ,x

These equations allow calculation of the effect of temperature and pressure on the partial Gibbs
energy (or chemical potential).

Every equation that provides a linear relation among thermodynamic properties of a

constant-composition solution has as its counterpart an equation connecting the
corresponding partial properties of each species in the solution.
H=U + PV nH=nU + P(nV )

Differentiation with respect to ni at constant T , P, and nj yields:

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[ (nH )
ni ] [
P ,T ,n j
=
(nU )
n i ]
P ,T , n j
+P
[ (nV )
ni ]
P , T , nj
i=U i + P V i
H

In a constant-composition solution, G i is a function of P and T, and therefore:

Gi i
G
i=
dG dP+ i=V i dPS i dT
dT ( 2223 ) d G
P T,x T P , x

These examples illustrate the parallelism that exists between equations for a constant-
composition solution and the corresponding equations for the partial properties of the species in
solution.

4.4. Ideal-Gas Mixtures

If n moles of a mixture of ideal gases contain in a container with a volume of Vt at the

temperature of T, the total pressure of the container can be calculated using the following
equation:
nRT
P= t
V

and if ni moles of species i contain in the same container, the partial pressure of species i (Pi) at
the same temperature, T, is as follows:

ni RT
P i= t
V

ni RT
Pi Vt n
= = i = yi
P nRT n
t
V

P i= y i P

Partial volume of species i (ideal gas) can be written in the form of equation as follows:

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( RTP )
( )
ig
n RT n RT
ig
V =
i
nV
ni ( )
T ,P ,n j
ni T , P , nj
( )
P ni T , P ,n j
=
P

Since n=ni + n j but n is constant, we obtain

j

( n i+ n j ) ( n j )
n
( )
ni T ,P, nj
(
=
ni ) ( ) (
T , P , nj
=
ni
ni T ,P ,n j
+
ni )
T , P ,n j
=1

Thus,

RT
V igi = =V igi =V ig
P

(24)

This illustrates that, in the case of an ideal-gas mixture

V igi =V igi

The above relation can also be extended to other thermodynamic properties:

A partial molar property of a constituent species in an ideal-gas mixture is equal to the

corresponding molar property of the species as a pure ideal gas at the same temperature,
but at a pressure equal to its partial pressure in the mixture.

This can be written in the form of equation as follows:

igi ( T , P )=M igi ( T , P i )

M (25)

For Enthalpy:
igi ( T , P )=H igi ( T , Pi )
H

However, we have known that an enthalpy of an ideal gas is independent of P.

Hence,

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 Solution thermodynamics: Theory
igi ( T , P )=H igi ( T , Pi )=H igi ( T , P )
H

This means that,

igi =H igi
H

(26)

Apply the summability relation

yi M

M i

To enthalpy, yields;

ig i = y i H i
H = y i H
ig ig

H ig y i H igi =0

This indicates that, for an ideal-gas solution, the summation of an enthalpy of each pure
species is equal to the enthalpy of the solution (Enthalpy of mixing is zero).

For Entropy:

Since entropy of an ideal gas depends on both T & P. when T is constant, we obtain
dT 0 dP dP
dS igi =C P R =R =R dlnP
T P P

Integrating the above equation from P = Pi to P = P yields;

ig ig P P ig ig
S i ( T , P ) S i ( T , Pi ) =R dln = =R ln y i S i ( T , Pi ) =S i ( T , P ) R ln y i
Pi y i P

Sigi ( T , P )=S igi ( T , P ) R ln y i S igi =S igi R ln yi

(27)

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 Solution thermodynamics: Theory
ig
where S i is the pure-species value at the mixture T and P.

igi =H igi T Sigi + RT ln y i

G

igi =Gigi + RT ln y i
igi =G

(28)

H ig = y i H igi
i

(29)
ig ig
S = y i S i R y i ln y i
i i

(30)

G ig = y i G igi + RT y i ln y i
i i

(31)

ig ig 1
S y i S i =R y i ln
From (30) i i yi

The left side is the entropy change of mixing for ideal gases. Since 1 / y i > 1, this quantity is
always positive, in agreement with the second law. The mixing process is inherently irreversible.
An alternative expression for the chemical potential is:
RT
dG igi =V igi dP= dP=RT dlnP
P (Const T)

Integration gives:
ig
Gi = i ( T ) + RT lnP (32)

Where i ( T ) , the integration constant at constant T ,is a function of temperature only.

Equation (28) may therefore be written:

igi = i ( T ) + RT ln y i P

(33)
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Application of the summability relation gives:

G ig= y i i ( T ) + RT y i ln y i P
i i

(34)

These equations, remarkable in their simplicity, provide a full description of ideal-gas behavior.

4.5. Fugacity and Fugacity Coefficient: Pure species

i
We have seen that the chemical potential provides the fundamental criterion for phase

equilibria. This is true as well for chemical-reaction equilibria. However, it exhibits

i
characteristics which discourage its use. The Gibbs energy, and hence , is defined in

relation to the internal energy and entropy, both primitive quantities for which absolute values

i
are unknown. As a result, absolute values for do not exist.

i
For an ideal-gas mixture approaches negative infinity when either P or yi approaches zero.

The origin of the fugacity concept resides in Eq. (32), valid only for pure species i in the ideal-
gas state. For a real fluid, we write an analogous equation:
Gi= i ( T )+ RT ln f i (35)

fi
P replaced by the fugacity of pure species i with units of pressure.

Subtraction of Eq. (32) from Eq. (35), both written for the same T and P, gives:

fi
GiGigi =RT ln (36)
P

GiGigi =GiR then

GRi =RTln i

(37)

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fi
When =i (38)
P

It is called fugacity coefficient.

The definition of fugacity is completed by setting the ideal-gas-state fugacity of pure species i
equal to its pressure:
f igi =P

(39)
R
i=1
Thus for the special case of an ideal gas Gi =0 , ,

GRi
i
The identification of ln with RT gives

P
dP
ln i= ( Z i1 ) (Cont T)
0 P

(40)
Fugacity coefficients (and therefore fugacities) for pure gases are evaluated by this equation from
P V T data or from a volume-explicit equation of state. Example from the two term Virial
equation of state.
B ii
Z i1= P
RT

Because the second virial coefficient Bii is a function of temperature only for a pure species,
substitution into Eq. (40) gives:
Bii P
ln i=
RT 0
dP (Cont T)

B ii P
Whence ln i=
RT

(41)

4.6. Vapor liquid equilibrium (VLE) for pure Species

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Equation (35), which defines the fugacity of pure species i, may be written for species i as a
saturated vapor:
Gvi = i ( T )+ RT ln f iv (42a)

and for species i as a saturated liquid at the same temperature:

l l
Gi= i ( T )+ RT ln f i (42b)

f vi
Gvi Gli =RT ln
By difference, f li

v l
At equilibrium Gi Gi =0 then,

f iv =f li=f sat
i (43)
sat
Where f i indicates the value for either saturated liquid or saturated vapor.

For a pure species coexisting liquid and vapor phases are in equilibrium when they have
the same temperature, pressure, and fugacity.

An alternative formulation is based on the corresponding fugacity coefficients:

f isat
sat
i =
Psat
i

(44)
v l sat
Whence i =i = i (45)

This equation, expressing equality of fugacity coefficients, is an equally valid criterion of vapor
liquid equilibrium for pure species.

4.7. Fugacity and fugacity coefficient: species in solutions

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The definition of the fugacity of a species in solution is parallel to the definition of the pure
species fugacity. For species i in a mixture of real gases or in a solution of liquids, the equation
analogous to Eq. (33), the ideal-gas expression, is:
i= i ( T )+ RT ln f^ i (46)

^
Where f i is the fugacity of species i in solution, replacing the partial pressure yi P.

^ ^ ^
For equilibrium f i =f i = ..=f i (i=1, 2, N) (47)

Thus, multiple phases at the same T and P are in equilibrium when the fugacity of each
constituent species is the same in all phases.

This criterion of equilibrium is the one usually applied by chemical engineers in the solution of
phase-equilibrium problems.
For the specific case of multicomponent vapor/liquid equilibrium, Eq. (47) becomes:
f^ i v =f^ il (i = 1, 2, N)

(48)
The definition of a residual property is
M R =M M ig nM R =nM nM ig

Differentiation with respect to ni at constant T, P, and nj gives:

[ (n M R )
ni ] [
P , T ,n j
=
(n M )
ni ] [
P , T , nj

( n M ig )
ni ]
P , T , nj

Ri = M
M i M
igi

(49)
an equation which defines the partial residual Gibbs energy.
Ri =G
G i G
igi

(50)
Subtracting (33) from (46) gives

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f^ i
iigi =RT ln
yi P

i
i G
This result combined with Eq. (50) and the identity gives:

Ri =RT ln ^ i
G

(51)
^f
^ i=
i
Where by definition yi P

(52)
^ i the fugacity coefJicient of species isolution .

yi xi
- For liquids can be replaced by .
R ^ ig
- For an ideal gas, Gi is necessarily zero; therefore i =1 , and

f^ iig = yi P

(53)
Thus the fugacity of species i in an ideal-gas mixture is equal to its partial pressure.

4.8. The ideal solution

An ideal solution is a model which serves as a standard to which real-solution behavior can be
compared.
igi =Gigi + RT ln yi
G (28)

Eqn. (28) is useful model for ideal gas mixture and analogously for ideal solution we can write
the equation as follows.
idi =Gi + RT ln x i
G (54)

Where superscript id denotes an ideal-solution property

Gi, the Gibbs energy of pure species i as it actually exists at the mixture T and P and in the same
physical state (real gas, liquid, or solid) as the mixture.

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The partial entropy results from differentiation with respect to temperature at constant pressure
and composition and then combination with Eq. (23) written for an ideal solution:
id
( ) ( )
S idi = Gi
T P, x
=
Gi
T P
R ln xi

By ( G T ) =S
i

P
i whence

S idi =Si R ln xi

(55)
Similarly, as a result of Eq. (22),
iid

( ) ( )
V idi =
G
P T,x
=
Gi
P T

V idi =V i

(56)
idi =G
H idi +T S idi
Since , substitution by Eqns. (54) and (55)

idi =Gi +RT ln x i+ S iR ln x i

H

idi =H i
H
Or

(57)
By summability relation
Eqns. (54) through (57)
id
G = x i Gi+ RT x i ln xi
i i

(58)
S id = x i S iR x i ln x i
i i

(59)

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V id = x i V i
i

(60)
H id = x i H i
i

(61)

4.9. The Lewis/Randall rule

A simple equation for the fugacity of a species in an ideal solution follows from Eq. (54). Written
for the special case of species i in an ideal solution, Eq. (46) becomes:
id
i =G idi = i ( T ) + RT ln f^ iid

i (T )
When this equation and Eq. (35) are combined with Eq. (54), is eliminated, and the

resulting expression reduces to:

f^ i =xi f i
id

(62)

This equation, known as the Lewis/Randall rule, applies to each species in an ideal solution at all
conditions of temperature, pressure, and composition.

Division of both sides of Eq. (62) by Px i and substitution of ^ iid for ^f iid /x i P [Eq. (52)] and

i for f i /P
of [Eq. (38)] gives an alternative form:

^ iid= i

(63)

Thus the fugacity coefficient of species i in an ideal solution is equal to the fugacity coefficient
of pure species i in the same physical state as the solution and at the same T and P. Since Raoult's
law is based on the assumption of ideal-solution behavior for the liquid phase, the same systems
that obey Raoult's law form ideal solutions.

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4.10. The excess properties

Liquid solutions are often more easily dealt with through properties that measure their
departures, not from ideal-gas behavior, but from ideal-solution behavior.
The definition for excess property is:
M E =M M id

(64)

For example
GE =GGid H E =HH id S E =SS id etc
E E E
G =H T S

(65)
Indeed, excess properties have a simple relation to residual properties,
M E M R =(M id M ig)

Since an ideal-gas mixture is an ideal solution of ideal gases, Eqs. (58) through (61) become

expressions for Mig when Mi is replaced by M igi for example, Eq. (58) becomes:

ig ig
G = x i Gi + RT x i ln x i
i i

The two sets of equations, for Mid and Mig, therefore provide a general relation for the difference:

M id M ig = x i M i x i M igi = xi M Ri
i i i

Where in the summation terms with logarithms have canceled. This leads immediately to the
result:
M E =M R x i M Ri
i

(66)

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 Solution thermodynamics: Theory

Note that excess properties have no meaning for pure species, whereas residual properties exist
for pure species as well as for mixtures.
The partial-property relation analogous to Eq. (49) is:

Ei = M
M i M
idi

(67)

Ei
M
Where is a partial excess property.

The fundamental excess-property relation is derived in exactly the same way as the fundamental
residual-property relation and leads to analogous results.
E E E iE
G
d( )
nG
RT
=
nV
RT
dT
nH
RT
2
dT +
i RT
dn i

(68)
This is the fundamental excess-property relation.

4.11. The excess Gibbs energy and the activity coefficient

The excess Gibbs energy is of particular interest. Equation (46) may be written:

i= i ( T )+ RT ln f^ i
G

In accord with Eq. (62) for an ideal solution, this becomes:

idi = i ( T )+ RT ln x i f i
G

f^ i
idi =RT ln
i G
G
By difference xi f i

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 Solution thermodynamics: Theory
Ei
G
The left side of this equation is the partial excess Gibbs energy the dimensionless ratio

^f i
i
x i f i ,appearing on the right is the activity coefficient of species i in solution, symbol .

Thus, by definition,
^f
i
i=
xi f i

(69)

Ei =RT ln i
G
Whence,
(70)

An alternative form of Eq. (68) follows by introduction of the activity coefficient through Eq.

nG E nV E nH E
(70): d ( )
RT
=
RT
dT
RT 2
dT + ln i dni
i

(71)
The generality of these equations precludes their direct practical application. Rather, use is made
of restricted forms, which are written by inspection:

V
RT
E
= [ ]
(
GE
RT
P
)

T,x

(72)

HE
RT
=T [ ]
(
GE
RT
T
)

P, x

(73)

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 Solution thermodynamics: Theory

[ ]
nG E
( )
RT
ln i=
ni P ,T , n j

(74)
Activity coefficients are found from vapor/liquid equilibrium data, and v E and HE values come
from mixing experiments.
The partial property analogs of Eqs. (72) and (73) are:
V Ei
[ ]
ln i
P T,x
=
RT

(75)

Ei
[ ]
ln i
T P, x
=
H
RT 2

(76)

These equations allow calculation of the effect of pressure and temperature on the activity
coefficient.
The following forms of the summability and Gibbs/Duhem equations result from the fact that

ln i GE
is a partial property with respect to RT :

GE
= xi ln i
RT i

(77)

x i dln i=0(Const T , P) (78)

i

These equations find important applications in phase-equilibrium thermodynamics.

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