Thermodynamics Asst. Professor A. N.

Al-Mosawi
2nd Course /Lecture 20
5 3rd Year/Chem. Eng.

Partial Molar Property

Partial Properties
Let M represent any extensive property (U, H, S, G, V, etc….), then the general
equation for partial molar property:

………………eq. (1)
Where: i is the partial molar property of species i in a solution, and (−) is overbar.
M is the molar solution property
Mi is the molar property of pure species

So that:
 (nV )    (nU )   (nH )    (nS ) 
Vi    Ui    Hi    Si   
 ni  P , T , n j  ni  P , T , n j  ni  P , T , n j  ni  P , T , n j

The definition leads to partial molar property depend on temperature, pressure, and
composition of liquid solution, where:
i is the partial molar volume
V is the molar volume of solution
Vi is the molar volume of pure species
also:
i is the partial molar enthalpy
H is the molar enthalpy of solution
Hi is the molar enthalpy of pure species
Comparison of Eq. (1) with the partial molar Gibbs energy shows that the chemical
potential and the partial molar Gibbs energy are identical:
  (nG ) 
i  G i    ………………eq. (2)
 ni  P , T , n j
Thermodynamics Asst. Professor A. N. Al-Mosawi
5
2nd Course /Lecture 20 3rd Year/Chem. Eng.

The partial molar properties are related to the corresponding total and molar
thermodynamic quantities as the total property:
Mt = n1 1 + n2 2 +……. = Σ ni i ………………eq. (3)
Where: Mt is the total property and equal nM ; M is the molar property of solution.
So, nM = Σ ni i ………………eq. (4)
By dividing on n:
M = Σ xi i ………………eq. (5)
Where: xi = ni/n; mole fraction of species i
For example: Vt = nV = Σ ni i → V = Σ xi i

Partial Properties in Binary Solutions

For binary systems, however, an alternative procedure may be more convenient.
Written for a binary solution eq. (5), becomes:

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

Gibbs/Duhem equation:

Since x1+x2=1, it follows that dx1=−dx2 and combining the result with (c) gives:

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

………………eq. (6)

………………eq. (7)
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.
Thermodynamics Asst. Professor A. N. Al-Mosawi
5
2nd Course /Lecture 20 3rd Year/Chem. Eng.

Example Describe a graphical interpretation of eqs. (6) and (7).

The following figure shows a representative plot of M vs. xl for a binary system.

Values of the derivative dM/dx1, are given

by the slopes of lines drawn tangent to the
curve of M vs. x1. One such line drawn
tangent at a particular value of x1 as shown
in the figure. Its intercepts with the
boundaries of the figure at x1=1 and x1= 0
are labeled I1 and I2. As is evident from the
figure, two equivalent expressions can be
written for the slope of this line:

Solving the first equation for I2 and the second for I1 (with elimination of I2) gives:

Comparison of these expressions with Eqs. (5) and (6) shows that:

Thus the i values for the two components of a binary solution mixture are equal to
the M-intercepts of the tangent drawn to the M vs. x1 curve at given composition.
Infinite Dilution of Solution
Intercepts of course shift as the point of tangency moves along the curve, and limiting
values are indicated by the constructions as shown in the following figure, where:
∞
1 is the partial molar property of species 1 when it is present in solution at infinite
dilution x1→0
∞
2 is the partial molar property of species 2 when it is present in solution at infinite
dilution x1→1
Thermodynamics Asst. Professor A. N. Al-Mosawi
2nd Course /Lecture 20
5 3rd Year/Chem. Eng.

1. The tangent drawn at x1=0 (pure

species 2) gives 2 = M2, and the
∞
opposite intercept gives 1 = 1 the
partial property of species 1 when it is
present at infinite dilution x1= 0.
2. Similar comments apply to the
tangent drawn at x1=1 (pure species 1).
∞
In this case 1 = M1 and 2 = 2 ,
since it is species 2 that is present at
infinite dilution (x1 =1, and x2 = 0).

Example 11.2, p.325

The need arises in a laboratory for 2000 cm3 of an antifreeze solution consisting of a
30 mole percent solution of methanol in water. What volumes of pure methanol and
of pure water at 25°C must be mixed to form the 2000 cm3of antifreeze also at 25°C?
Partial molar volumes for methanol and water in a 30 mole percent methanol solution
at 25°C are:
Methanol (l): 1 =38.632 cm3mol-1
Water (2): 2 =17.765 cm3mol-1
For the pure species at 25°C:
Methanol (1): V1 = 40.727 cm3 mol-1
Water (2): V2 = 18.068 cm3 mol-1
Solution: Apply of eq. (5) gives:
Thermodynamics Asst. Professor A. N. Al-Mosawi
5
2nd Course /Lecture 20 3rd Year/Chem. Eng.

Note that the simple sum of the initial volumes gives a total of 2070 cm 3, a volume
more than 3 % larger than that of the solution formed.

Example 13.2, p.426

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 + x1x2(40x1 + 20x2)
Where H is in J/mol. Determine expressions for 1 and 2 as functions of the
numerical values for the pure-species enthalpies H1 and H2 , and numerical for the
∞ ∞
partial enthalpies at infinite dilution 1 and 2 .
Solution:
Elimination of x2 in the given equation for H in term of x1 yields

Substitution for H and dH/dx1 into eq. (6) gives:

Replacing x2 by 1− x1 and simplifying, then:

eq. (A)
Similarly, substitution for H and dH/dx1 into by eq. (7) gives:
Thermodynamics Asst. Professor A. N. Al-Mosawi
2nd Course /Lecture 20
5 3rd Year/Chem. Eng.

eq. (B)
For pure species values:
at x1=1, x2=0 substitution into eq. (A) gives:
H1= 400 Jmol-1
at x1=0, x2=1 substitution into eq. (B) gives:
H2= 600 Jmol-1
Infinite dilution values:
at x1=0, substitution into eq. (A) gives:
∞
1 = 420 Jmol-1
at x1=1, substitution into eq. (B) gives:
∞
2 = 640 Jmol-1

The Gibbs-Duhem equation

For thermodynamic property M we may write:

………….. eq(a)
The total differential of nM is then:

…………. eq(b)
As the first two partial derivatives on the right are evaluated at constant n, so:

……….. eq(c)
Where: subscript x denotes differentiation at constant composition.
Since ni= xi n

Substitution the above relation into equation (c) gives:

Thermodynamics Asst. Professor A. N. Al-Mosawi
5
2nd Course /Lecture 20 3rd Year/Chem. Eng.

……….. eq(d)
Separating n and dn:

……….. eq(e)
The only way that the left-hand side of this equation can then, in general, be zero is
for both quantities enclosed by brackets to be zero, therefore:
1st term =0, so that ……….. eq(f)

2nd term=0, so that ……….. eq(g)

Differentiation of eq. (g) ……….. eq(h)

Comparison of eqs. (f) and (h), gives:
……….. eq(i)

For constant T and P, thus:

……………eq. (8)
For binary system:

Summary