1

Topic 2: Solution Thermodynamics: Theory and Application

 2

OVERVIEW
 The purpose of this chapter is to express the theoretical foundation
for applications of thermodynamics to gas mixtures and liquid
solutions.
 Separation processes of multicomponent gases and liquids in
chemical, petroleum and pharmaceutical industries commonly
undergo composition changes, transfer of species from one phase
to another and chemical reaction. Thus compositions become
essential variables, along with temperature and pressure.
 This chapter introduce new property, i.e. chemical potential which
facilitate treatment of phase and chemical reaction equilibria;
partial properties which are properties of individual species as they
exist in solution; and fugacity which provide treatment for real gas
mixtures through mathematical formulation.
 Another solution properties known as excess properties, is the
deviation from ideal solution property.
 3

Topic 2: Solution Thermodynamics:

Theory and Application

WEEK 5:
- FUNDAMENTAL PROPERTY RELATION
- THE CHEMICAL POTENTIAL AND PHASE EQUILIBRIA
- PARTIAL PROPERTIES
 4

Course Learning Outcomes

At the end of this chapter, the student should be able to:
 Understand the fundamental properties relation, fugacity of pure
species and species in solution.
 Analyse and apply the concepts of solution thermodynamics and
various models for the excess Gibbs
• Describe thermodynamic terms such as partial and residual
properties, fugacity and fugacity coefficient in chemical engineering
• Differentiate the difference between pure, partial, and solution
properties.
• Estimate the fugacity and fugacity coefficient for given pure (ideal or
real), and mixture species at specified conditions and approaches
 5

FUNDAMENTAL PROPERTY RELATION

 The most important property relation is that of Gibbs free energy change.
G  H − TS (6.3)
 Multiplied by n and differentiated eq. (6.3):
d ( nG ) = d ( nH ) − Td ( nS ) − ( nS ) dT (6.3a)
 Enthalpy: H  U + PV (2.11)

 Multiplied by n, differentiated, d ( nH ) = d ( nU ) + Pd ( nV ) + ( nV ) dP (2.11a)

 The first Tds relation or Gibbs equation:

d ( nU ) = Td ( nS ) − Pd ( nV ) (6.1)
 Substitute eq. (6.1) into (2.11a) to yield:
d ( nH ) = Td ( nS ) + ( nV ) dP (6.4)
 Substitute eq. (6.4) into (6.3a) to yield:
d ( nG ) = ( nV ) dP − ( nS ) dT (6.6)

 Equation (6.6) relates the total Gibbs energy of any closed system to
temperature and pressure.
 6

d ( nG ) = ( nV ) dP − ( nS ) dT (6.6)
 An appropriate application is to a single phase fluid in a closed
system wherein no chemical reactions occur. For such a system
the composition is necessarily constant, and therefore

  ( nG )    ( nG ) 
 P  = nV and  T  = −nS (A)
  T ,n   P ,n

The subscript n indicates that the numbers of moles of all chemical

species are held constant.
 For 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 chemical species present, and still
a function of T and P.
nG = g ( P , T , n1, n2 ,..., ni ,... )
where n i is the number of moles of species i.
 7

Total differential of nG is

  ( nG )    ( nG )   nG 
d ( nG ) = 
 P  dP +  T  dT +   n  dni (B)
  T ,n   P ,n i  i  P ,T ,nj

The summation is over all species present, and subscript n j indicates

that all mole numbers except the ith are held constant.
 The derivative in the final term is called the chemical potential of
species i in the mixture. It is define as

  ( nG ) 
i    (11.1)
  ni  P ,T ,nj
 With this definition and with the first two partial derivatives [eqn. (A)]
replaced by (nV) and –(nS), the preceding equation [eqn. (B)]
becomes
d ( nG ) = ( nV ) dP − ( nS ) dT + i dni 
i
(11.2)

 Equation (11.2) is the fundamental property relation for single phase

fluid systems of variable mass and composition.
 8

 For special case of one mole of solution, n = 1 and ni = xi:

dG = VdP − SdT +  i dx i (11.3)
i

 This equation relates molar Gibbs energy to T, P and {xi}.

G = G ( P , T , x1, x2 ,..., x i ,... )

 For special case of a constant composition solution:

dG = VdP − SdT (6.10)
 Although the mole numbers n i of eq. (11.2) are independent
variables, the mole fractions xi in eq. (11.3) are not, because i xi = 1.
Eq. (11.3) does imply
 G   G 
V =  (11.4) S = −   (11.5)
 P T , x  T  P ,x

 Other solution properties come from definitions; e.g., the enthalpy,

from H = G + TS. Thus, by eq. (11.5),
G 
H = G − T  
 T P , x
 9

THE CHEMICAL POTENTIAL AND PHASE

EQUILIBRIA
 For a closed system consisting of two phases in equilibrium, each
individual phase is open to the other, and mass transfer between
phases may occur. Equation (11.2) applies separately to each
phase:

d ( nG ) = ( nV ) dP − ( nS ) dT +  i dni
  

d ( nG ) = ( nV ) dP − ( nS ) dT +  i dni
  

where superscripts  and  identify the phases.

 The presumption here is that equilibrium implies uniformity of T and P
throughout the entire system.
 The change in the total Gibbs energy of the two phase system is the
sum of these equations.
d ( nG ) + d ( nG ) = ( nV ) + ( nV )  dP − ( nS ) + ( nS )  dT +  i dni +  i dni
     

i i
 10

d ( nG ) + d ( nG ) = ( nV ) + ( nV )  dP − ( nS ) + ( nS )  dT +  i dni +  i dni

     

i i

 When each total system property is expressed by an equation of

the form,
 
nM = ( nM) + ( nM)
the sum is
d ( nG ) = ( nV ) dP − ( nS ) dT +  i dni +  i dni
i i
 Because the two phase system is closed, eq. (6.6) is also valid.
Comparison of the two equations shows that at equilibrium,

 i i  i i =0

i

dn
+  
dn
i

d ( nG ) = ( nV ) dP − ( nS ) dT (6.6)

 The changes dni and dni result from mass transfer between the
phases; mass conservation therefore requires

dni = −dni and  ( i


−  
i)dn
=0 i
 11

 Quantities dni are independent; therefore the only way the left side
of the second equation can in general be zero is for each term in
parentheses separately to be zero. Hence,
i = i ( i = 1,2,..., N )
where N is the number of species present in the system.
 For multiple phases ( phases):
i = i = ... = i ( i = 1,2,..., N ) (11.6)

Multiple phases at the same T and P are in equilibrium when the

chemical potential of each species is the same in all phases.

A chemical species is transported from a phase of

larger potential to a phase of lower potential.
 Example: A glass of liquid water with ice cubes in it. When the
chemical potential of ice is larger than water, the ice melts. When
chemical potential of water is larger than ice, the water freezes.
Water and ice are in equilibrium when their chemical potential are
the same.
 12

PARTIAL PROPERTIES
 A species exhibits its pure property when no other species exist
with it, i.e. pure component exhibits pure properties.
 Species exhibits its partial property when it co-exists with other
species in a mixture or solution.
−
 Partial molar property Mi of a species i in a solution is define as
_   ( nM ) 
Mi    (11.7)
 ni  P ,T ,nj
 It is the change of total property nM to the addition of a
differential amount of species i to a finite amount of solution at
constant T and P.
 Three kinds of properties used in solution thermodynamics are
distinguished by the following symbolism:
 Solution properties M, for example: V,− U, −H, S, −
G− −
−
 Partial properties Mi , for example: Vi , U i , Hi , Si , G i
 Pure species properties M i , for example: Vi , Ui , Hi , Si , Gi
 13

Example
When one mole of water is added to a large volume of water at
25ºC, the volume increases by 18 cm 3.
However, addition of one mole of water to a large volume of
pure ethanol results in an increase in volume of only 14 cm 3.

In general, the partial molar volume of a substance i in a mixture

is the change in volume per mole of i added to the mixture.
_   ( nV ) 
Vi   
 ni  P ,T ,nj

* The increase in volume is different due to intermolecular forces

between molecules, size and shape of molecules are different in
mixture rather than pure species.
 14

EQUATIONS RELATING MOLAR AND

PARTIAL MOLAR PROPERTIES
 Total thermodynamic properties of a homogeneous phase are functions
of T, P, and the numbers of moles of the individual species which
comprise the phase. Thus, for property M:
nM =  (T , P , n1, n2 ,..., ni ,... )
 The total differential of nM is

  ( nM )    ( nM)    ( nM ) 
d ( nM ) = 
 P  T ,n
 dP +  
 T  P ,n
dT +  
i  ni
 dni
 P ,T ,nj
where subscript n indicates that all mole numbers are held constant, and
subscript nj that all mole numbers except ni are held constant.
 Because the first two partial derivatives on the right are evaluated at
constant n and because the partial derivative of the last term is given by
eq. (11.7), this equation has the simpler form:
  ( M)    ( M)  −
d ( nM) = n   dP + n   dT +  Mi dni (11.9)
 P T , x  T P , x i

where subscript x denotes differentiation at constant composition.

 15

 Because n i = xi n,
dni = x i dn + ndx i
Moreover,
d ( nM)  ndM + Mdn


 When dn i and d(nM) are replaced in Eq. (11.9), it becomes

 M   M  −
ndM + Mdn = n   dP + n   dT +  Mi ( x i dn + ndx i )
 P T , x  T P , x i

 The terms containing n are collected and separated from those

containing dn to yield
  M   M  −   − 
dM −   dP −   dT −  Mi dx i  n +  M −  x i Mi  dn = 0
  P T , x  T P , x i   i 
 The left side of this equation can be zero if each term in brackets be
zero too. Therefore,

 M   M  − −
M =  x i Mi
dM =   dP +   dT +  Mi dx i (11.10) (11.11)
 P T , x  T P , x i i
 16

 Multiplication of eq.(11.11) by n yields the alternative expression:

−
nM =  ni Mi (11.12)
i

 Equations (11.11) and (11.12) are known as summability relations,

they allow calculation of mixture properties from partial properties.
 Differentiate eq. (11.11) yields:
− −
dM =  x i d Mi +  Mi dx i
i i

 Comparison of this equation with eq. (11.10), yields the

Gibbs/Duhem equation:

 M  dP +  M  dT − x d M− = 0
 
 P T , x
 
 T P , x
i i i (11.13)

 For changes at constant T and P,

−
xdM
i
i i =0 (11.14)
 17

A RATIONALE FOR PARTIAL PROPERTIES

 Partial properties have all characteristics of properties of individual
species as they exist in solution. Thus, they may be assigned as
property values to the individual species.
 Partial properties, like solution properties, are functions of
composition.
−
 In the limit as a solution becomes pure in species i, both M and Mi
approach the pure species property M i .
−
lim M = lim Mi = Mi
xi →1 xi →1

 For a species that approaches its infinite dilution limit, i.e., the values
as its mole fraction approaches zero, no general statements can be
made. Values come from experiment or from models of solution
behavior. By definition,
− −

lim Mi  M i
x i →0
 18

 Equations for partial properties can be summarized as follows:

 Definition:
_   ( nM ) 
Mi    (11.7)
  ni  P ,T ,nj
which yields partial properties from total properties.
 Summability:
−
M =  x i Mi (11.11)
i

which yields total properties from partial properties.

 Gibbs/Duhem:
−
 M  dP +  M  dT
i i i  P T ,x  T P ,x
x d M = (11.13)

which shows that the partial properties of species making up

solution are not independent of one another.
 19

PARTIAL PROPERTIES IN BINARY

SOLUTIONS
 For binary solution, the summability relation, eq.(11.11) becomes
− −
M = x1 M1 + x 2 M2 (A)

 Differentiation of eq. (A) becomes

− − − −
dM = x1d M1 + M1 dx1 + x 2 d M2 + M2 dx 2 (B)

 When M is known as a function of x 1 at constant T and P, the

appropriate form of the Gibbs/Duhem equation is eq. (11.14),
expressed as
− −
x1d M1 + x 2 d M2 = 0 (C)

 Because x1 + x2 = 1, dx1 + dx2 = 0 → dx1 = - dx2. Substitute eq. (C) into

eq. (B) to eliminate dx 2 gives
dM − −
= M1 − M2 (D)
dx1
 20

 Two equivalent forms of eq. (A) result from elimination separately of

x1 and x2:
x1 = 1− x 2 x 2 = 1− x1
− − − −
M = (1− x 2 ) M1 + x 2 M2 M = x1 M1+ (1− x1 ) M2
− − − − − −
M = M1 − x 2 M1 + x 2 M2 M = x1 M1+ M2 − x1 M2
−
(
M = M1 − x 2 M1 − M2
− −
) and ( − −
M = x1 M1 − M2 + M2 ) −

 In combination with eq. (D) becomes

− dM
M1 = M + x 2 (11.15)
dx1
− dM
M2 = M − x1 (11.16)
dx1
 Thus for binary systems, the partial properties are calculated directly
from an expression for the solution property as a function of
composition at constant T and P.
 21

 Eq. (C), the Gibbs/Duhem equation, may be written in derivative

forms:
− −
d M1 d M2
x1 + x2 =0 (E)
dx1 dx1

− −
dM1 x dM2
=− 2 (F)
dx1 x1 dx1

− −
dM2 x1 dM1
=− (G)
dx1 x 2 dx1
− −
 When M1 and M2 are plotted vs. x 1, the slopes must be of opposite
sign.
 22

 Moreover,
− −
d M1  d M2 
lim =0  Provided lim is finite 
x1 →1 dx  x1 →1 dx 
1
 1

Similarly,
− −
d M2  d M1 
lim =0  Provided lim is finite 
x2 →1 dx  x 2 →1 dx1 
1
 
− −
Thus, plot of M1 and M2 vs. x 1 become horizontal as each species
approaches purity.
 23

EXAMPLE 11.2
Describe a graphical interpretation of eqs. (11.15) and (11.16).
 Figure 11.1 (a) shows a representative
Solution: plot of M vs. x1 for a binary system.
 The tangent line shown extend across the
figure, intersecting the edges (at x1 = 1
and x1 = 0) at points label I1 and I2.
 Two equivalent expressions can be
written for the slope of this tangent line:
dM M − I2 dM
= and = I1 − I2
dx1 x1 dx1
 The first equation is solved for I 2; it
combines with the second to give I 1.
dM dM
I2 = M − x1 and I1 = M + (1− x1 )
dx1 dx1
 Comparison of these expression with eqs.
(11.16) and (11.15) show that
− −
I1 = M1 and I2 = M2
 The tangent intercepts give directly the
23
values of the two partial properties.
 24

 The limiting values are indicated

by Fig. 11.1 (b).
 For the tangent line drawn
−
at x 1
= 0 (pure species 2), M2 = M2
and at the opposite intercept,
− −

M1 = M 1

 For the tangent line drawn

−
at x 1
= 1 (pure species 1), M1 = M1
and at the opposite intercept,
− −

M2 = M 2

24
 25

EXAMPLE 11.3
The need arises in a laboratory for 2000 cm 3 of an antifreeze
solution consisting of 30 mole % methanol in water. What volumes
of pure methanol and of pure water at 25oC (298.15K) must be
mixed to form the 2000 cm 3 of antifreeze, also at 25oC (298.15K)?
Partial molar volumes for methanol and water in a 30 mole %
methanol solution and their pure species molar volumes, both at
25oC (298.15K), are
−
Methanol (1) : V1 = 38.632 cm3 mol-1 V1 = 40.727 cm3 mol-1
−
Water ( 2 ) : V2 = 17.765 cm3 mol-1 V2 = 18.068 cm3 mol-1
 26
Solution:
Equation (11.11) is written for the molar volume of the binary
antifreeze solution, and known values are substituted for the mole
fractions and partial volumes:
−
− −
V =  x i Vi V = x1 V1 + x 2 V2
i
= ( 0.3)( 38.632 ) + ( 0.7 )(17.765 )
= 24.025 cm3 mol-1
Because the required total volume of solution is Vt = 2000 cm 3, the
total number of moles required is
Vt 2000
n= = = 83.246 mol
V 24.025
Of this, 30% is methanol, and 70% is water:
n1 = ( 0.3)( 83.246 ) = 24.974 mol
ni = x i n
n2 = ( 0.7 )( 83.246 ) = 58.272 mol
The total volume of each pure species is Vit = niVi; thus,
V1t = ( 24.974 )( 40.727 ) = 1017 cm3
V2t = ( 58.272 )(18.068 ) = 1053 cm3
 27

− −
 Values of V1, V2 and V for the
binary solution
methanol(1)/water(2) at
25oC (298.15K) are plotted in
Fig. 11.2 as functions of x1.
 The line drawn tangent to
the V vs x1 curve at x1 = 0.3
illustrates the graphical
procedure
− −
by which values
of V1 and V2 may be
obtained. −
 The curve V1 becomes
− − horizontal at − x1 = 1 and the
V1 and V2
curve for V2 becomes
horizontal at x1= −
0 or x−2 = 1.
 The curves for V1 and V2
appear to be horizontal at
both ends.
−
For the tangent line drawn
−
at− x 1 = 0 (pure species 2), V2 = V2 and at
the opposite intercept, V1 = V1 −
For the tangent line drawn
−
at− x 1 = 1 (pure species 1), V1 = V1 and at
the opposite intercept, V2 = V2
 28

EXAMPLE 11.4
The enthalpy of a binary liquid system of species 1 and 2 at fixed T
and P is represented by the equation

H = 400 x1 + 600 x2 + x1x2 ( 40 x1 + 20 x 2 )

− −
where H is in Jmol-1. Determine expressions for H1 and H2 as a
functions of x1, numerical values for the pure species enthalpies H1
and H2, and
−
numerical
−
values for the partial enthalpies at infinite
dilution H  and H 
1 2
 29

Solution:
Replace x2 by 1 – x1 in the given equation for H and simplify:
H = 600 −180 x1 − 20 x13 (A)
dH
= −180 − 60 x12
dx1
By equation (11.15),
− dH
H1 = H + x 2
dx1
−
Then, H1 = 600 −180 x1 − 20 x1 −180 x 2 − 60 x1 x 2
3 2

Replace x2 by 1 – x1 and simplify:

−
H1 = 420 − 60 x12 + 40 x13 (B)

By eq. (11.16), − dH
H2 = H − x1 = 600 −180 x1 − 20 x13 +180 x1 + 60 x13
dx1
− (C)
or H2 = 600 + 40 x13
 30

A numerical value for H1 results by substitution of x 1 = 1 in either eq

(A) or (B). Both eqn. yield H1 = 400 J mol-1.

H2 is found from either eq. (A) or (C) when x 1 = 0.

The result is H2 = 600 J mol-1.
− −
 
The infinite dilution H and H
1 2 are
found from eq. (B) and (C) when
x1 = 0 in eq. (B) and x1 = 1 in eq. (C). The results are:
- -

H = 420 Jmol
1
-1
and H2 = 640 Jmol-1

Exercise: Show that the partial properties as given by eqs. (B) and
(C) combine by summability to give eq. (A), and conform to all
requirements of the Gibbs/Duhem equation.
 31

RELATIONS AMONG PARTIAL PROPERTIES

 By eq. (11.8), −
i  G i (11.8)
and eq. (11.2) may be written as

d ( nG ) = ( nV ) dP − ( nS ) dT +  i dni (11.2)
i

−
d ( nG ) = ( nV ) dP − ( nS ) dT +  G i dni (11.17)
i

 Application of the criterion of exactness, eq. (6.12),

dz = Mdx + Ndy  M   N 
  =  (6.12)
 y x  x y

yields the Maxwell relation,

 V  = −  S 
    (6.16)
 T P ,n  P T ,n
 32

 Plus the two additional equations:

  G−    G−    ( nS ) 
 =  ( )
  nV 
 i  i  = − 
 P  ni  P ,T ,n  T   n
 T ,n  j   P ,n  i  P ,T ,n j

where subscript n indicates constancy of all n i , and subscript n j

indicates that all mole numbers except the ith are held constant.
 In view of eq. (11.7), the last two equations are most simply
expressed:
  G−  − (11.18)   G−  − (11.19)
 i  = Vi  i  = − Si
 P   T 
 T , x  P , x
 These equations allow calculation of the effects of P and T on the
partial Gibbs energy (or chemical potential). They are partial
property analogs of eqs. (11.4) and (11.5).
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.
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 An example is based on the equation that defines enthalpy:

H = U + PV
 For n moles,
nH = nU + P ( nV )
 Differentiation with respect to ni at constant T, P, and nj yields
  ( nH )    ( nU )    ( nV ) 
  =  +P 
  ni  P ,T ,n j   ni  P ,T ,n j  ni  P ,T ,n j
 By eq. (11.7) this becomes Similar to eq. (2.11)
− − −
Hi = U i + P Vi H≡U+PV
−
 In a constant-composition solution, G i is a function of P and T, and
therefore:
−   G−    G− 
d Gi =  i  dP +  i  dT
 P   T 
 T , x  P , x
 By eqs. (11.18) and (11.19), Similar to eq. (6.10)
− − −
d G i = Vi dP − Si dT dG=VdP-SdT
 These examples illustrate the parallelism that exists between equations
for a constant-composition solution and the corresponding equations for
partial properties of the species in solution.