SOLUTION

THERMODYNAMICS: THEORY
FUNDAMENTAL PROPERTY RELATION
THE CHEMICAL POTENTIAL AND PHASE EQUILIBRIA
PARTIAL PROPERTIES
FUNDAMENTAL PROPERTY
RELATION
The first Tds relation or Gibbs equation:

d nU Td nS Pd nV (6.1)

Gibbs energy:
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 and combined with eq. (6.1):

d nH Td nS nV dP (6.4)
Combine eq. (6.3a) and (6.4) to yield:

d nG nV dP nS dT (6.6) 2
 Equation (6.6) relates the total Gibbs energy of any closed system to
temperature and pressure.
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
nV and nS (A)
P T ,n T 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 ni is the number of moles of species i.

3
 Total differential of nG is
nG nG nG
d nG dP dT dni (B)
P T ,n T P ,n i ni P ,T ,nj

The summation is over all species present, and subscript nj 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 (11.2)
Equation (11.2) is the fundamental property
irelation for single phase
fluid systems of variable mass and composition.

4
 For special case of one mole of solution, n = 1 and ni = xi:
dG VdP SdT i dxi
i
(11.3)
This equation relates molar Gibbs energy to T, P and {xi}.

G G P,T , x1 , x2 ,..., xi ,...

For special case of a constant composition solution:

dG VdP SdT (6.10)
Although the mole numbers ni of eq. (11.2) are independent variables,
the mole fractions xi in eq. (11.3) are not, because ixi = 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
5
 6

When the Gibbs energy is expressed as a function of its canonical

variables (T, P and {xi}), it plays the role of a generating function,
providing the means for calculation of all other thermodynamic
properties by simple mathematical operations (differentiation and
elementary algebra), and implicitly represents complete property
information.

6
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 dni

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.

7
d nG d nG nV nV dP nS nS dT i dni 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 dni 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,

dn dn 0
i
i i
i
i 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

dni dni and dn 0

i i i
8
 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. Above 0oC, the
chemical potential of ice is larger than water, so the ice melts. Below
0oC, the chemical potential of water is larger than ice, so the water
freezes. At 0oC, the water and ice are in equilibrium because their
chemical potential are the same.
9
 10

PARTIAL PROPERTIES
Partial molar property
Mi
of a species i in a solution is define as
_ nM
Mi (11.7)
ni P ,T ,nj
It is a measure of the response of total property nM to the addition
at constant T and P of a differential amount of species i to a finite
amount of solution.
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 , for example:

Pure species properties
M i M , for example:
i ViV,U
i , Ui i,, H
Hi i, ,SS i ,i Gi
i,G

Comparison of eq. (11.1) with eq. (11.7) written for the Gibbs
energy shows that the chemical potential and the partial molar
Gibbs energy are identical; i.e.,
nG
i (11.1) i G i (11.8)
ni P ,T ,nj 10
Example
When one mole of water is added to a large volume of water at
25C, the volume increases by 18cm3. The molar volume of pure
water would thus be reported as 18cm3 mol-1.
However, addition of one mole of water to a large volume of pure
ethanol results in an increase in volume of only 14cm3. The value
14cm3 is said to be the partial molar volume of water in ethanol.
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

11
 12

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 dP dT dni
P T ,n T P ,n i ni 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.

12
 Because ni = xin,
dni xi dn ndxi
Moreover,
d nM ndM Mdn
When dni and d(nM) are replaced in Eq. (11.9), it becomes
M M
ndM Mdn n dP n dT Mi xi dn ndxi
P T ,x T P ,x i

The terms containing n are collected and separated from those

containing dn to yield
M M

dM P
T ,x
dP T
P ,x
dT
i
M i dx i

n

M
i
x i M i dn 0

The left side of this equation can be zero if each term in brackets
be zero too. Therefore,
M M
(11.10)
dM dP dT M i dxi
P T ,x T P ,x i

13
 and
M xi M i (11.11)
i

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

nM ni M i (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 xi d Mi M i dxi
i i

Comparison of this equation with eq. (11.10), yields the Gibbs/Duhem

equation:
M M

P dP T dT xi d Mi 0 (11.13)
T ,x P ,x i

For changes at constant T and P,

x d M
i
i i 0 (11.14)
14
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 M i
approach the pure species property Mi.

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 M i M i
x i 0
15
 Equations for partial properties can be summarized as follows:
Definition:
_ nM
Mi
n (11.7)
i P ,T ,nj
which yields partial properties from total properties.
Summability:

M xi M i (11.11)
i

which yields total properties from partial properties.

Gibbs/Duhem:

M M
i i i P
x d M dP T dT
P ,x
(11.13)
T ,x

which shows that the partial properties of species making up

solution are not independent of one another.

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 17

PARTIAL PROPERTIES IN BINARY

SOLUTIONS
For binary solution, the summability relation, eq.(11.11) becomes

M x1 M 1 x 2 M 2 (A)

Differentiation of eq. (A) becomes

dM x1 d M1 M1 dx1 x2d M 2 M 2 dx2 (B)

When M is known as a function of x1 at constant T and P, the

appropriate form of the Gibbs/Duhem equation is eq. (11.14),
expressed as
x1 d M 1 x 2 d M 2 0 (C)
Because x1 + x2 = 1, dx1 + dx2 = 0 dx1 = - dx2. Substitute eq. (C)
into eq. (B) to eliminate dx2 gives
dM
M1 M 2 (D)
dx1
17
 18

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

x1 and x2:
x1 1 x 2 x 2 1 x1

M 1 x2 M 1 x2 M 2 M x1 M 1 1 x1 M 2

M M 1 x2 M 1 x2 M 2 M x1 M 1 M 2 x1 M 2




M M 1 x2 M 1 M 2 and M x1 M 1 M 2 M 2

In combination with eq. (D) becomes

dM
M 1 M x2 (11.15)
dx1

dM
M 2 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.
18
 Eq. (C), the Gibbs/Duhem equation, may be written in derivative
forms:

d M1 d M2
x1 x2 0 (E)
dx1 dx1

dM1 x2 dM2
(F)
dx1 x1 dx1

dM2 x dM1
1 (G)
dx1 x2 dx1

When M 1 and M2 are plotted vs. x1, the slopes must be of
opposite sign.

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 Moreover,



d M1 Provided lim d M
lim 0 2
is finite
x1 1 dx
1
x1 1 dx
1


Similarly,



d M2 Provided lim d M
lim 0 1
is finite
x2 1 dx
1
x2 1 dx
1



Thus, plot of M 1 and M2 vs. x1 become horizontal as each
species approaches purity.

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EXAMPLE 11.2
Describe a graphical interpretation of eqs. (11.15) and (11.16).

Solution: Figure 11.1 (a) shows a representative 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 I 2 dM
and I1 I 2
dx1 x1 dx1
The first equation is solved for I2; it combines
with the second to give I1.
dM dM
I 2 M x1 and I 1 M 1 x1
dx1 dx1
Comparison of these expression with eqs.
(11.16) and (11.15) show that

I1 M 1 and I2 M 2
The tangent intercepts give directly the values of
the two partial properties. 21
 The limiting values are indicated by Fig.
11.1 (b).
For the tangent line drawn at x1 = 0

(pure species 2), M 2 M 2
and at the opposite intercept,

M1 M1
For the tangent linedrawn at x1 = 1
(pure species 1), M 1 M 1 and at the
opposite intercept,


M 2 M 2

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EXAMPLE 11.3
The need arises in a laboratory for 2000 cm3 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 cm3 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 cm 3 mol -1 V1 40.727 cm 3 mol-1

Water 2 : V2 17.765 cm 3 mol-1 V2 18.068 cm3 mol-1

23
 24

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 xi Vi
i
V x1 V1 x2 V2
0.3 38.632 0.7 17.765
24.025 cm3 mol-1
Because the required total volume of solution is Vt = 2000 cm3, 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:

ni xi n n1 0.3 83.246 24.974 mol

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
24

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

curve for V becomes
V1 and V2 2
horizontal at x1= 0 or x2 = 1.

The curves for V1 and V2
appear to be horizontal at both
ends.

For the tangent line drawn at x1 = 0 (pure species 2), V2 V2 and at the opposite

intercept, V V
1 1

For the tangent line drawn at x1 = 1 (pure species 1), V1 V1 and at the opposite

intercept,
V2 V2 25
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 400x1 600x2 x1 x2 40x1 20x2

where H is in Jmol-1. Determine expressions for H1 and H 2 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 H1 and H2

26
 27

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
H 1 H x2
dx1

Then, H1 600 180 x1 20 x1 180 x2 60 x1 x2
3 2

Replace x2 by 1 x1 and simplify:

H1 420 60 x12 40 x13 (B)

By eq. (11.16),

dH
H 2 H x1 600 180 x1 20 x13 180 x1 60 x13
dx1
or
H 2 600 40 x13 (C)
27
 28

A numerical value for H1 results by substitution of x1 = 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 x1 = 0.

The result is H2 = 600 J mol-1.


The infinite dilution H and H2 are found from eq. (B) and (C)
1
when x1 = 0 in eq. (B) and x1 = 1 in eq. (C). The results are:
- -

H = 420 Jmol and H2 = 640 Jmol -1
1
-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.

28
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
T P (6.16)
P ,n T ,n 29
 30
Plus the two additional equations:

Gi nV Gi nS
P ni P ,T ,n T ni P ,T ,n j
T ,n j P ,n

where subscript n indicates constancy of all ni, and subscript nj

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:

Gi V (11.18) (11.19)

Gi

S
P i
T i
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.
30
 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)
H i U i P Vi HU+PV

In a constant-composition solution, Gisi a function of P and T, and
therefore:


Gi dP Gi
d Gi dT
P T
T , x P ,x
By eqs. (11.18) and (11.19),
Similar to eq. (6.10)
d Gi 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
31
properties of the species in solution.
REFERENCES
Smith, J.M.,Van Ness, H.C., and Abbott, M.M. 2005. Introduction to
Chemical Engineering Thermodynamics. Seventh Edition. Mc Graw-Hill.
http://www.chem1.com/acad/webtext/thermeq/TE4.html
http://mpdc.mae.cornell.edu/Courses/ENGRD221/LECTURES/lec2
6.pdf
http://science.csustan.edu/perona/4012/partmolvolsalt_lab2010.pdf

32
PREPARED BY:
MDM. NORASMAH MOHAMMED MANSHOR
FACULTY OF CHEMICAL ENGINEERING,
UiTM SHAH ALAM.
norasmah@salam.uitm.edu.my
03-55436333/019-2368303