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CHE 3161 Chemistry & Chemical Thermodynamics

Test 3 Questions

Date: 30/03/2013 Total Marks: 25 marks

The exam is a closed book test. Use R = 8.314 J mol-1K-1 = 8.314 m3Pa mol-1K-1.

1) Read carefully and determine whether the following statements are true or false and
indicate your thermodynamic reasoning. If you claim that a statement is false, you may
state that it violates a law of thermodynamics, or you may employ a physical counter-
example or any plausible reason. You may wish to amend any false statement with a
clarifying phrase that makes the statement true. If you claim that a statement is true,
please indicate your thermodynamic reasoning.

(a) The relationship between chemical potential and fugacity of species i in solution could be
written as:

∧
µ i − µ iig f
= ln i (2 marks)
RT yi P

True.
We know that:
µ iig = Γi (T ) + RT ln yi P (1)
∧
µ i = Γi (T ) + RT ln f i (2)

∧
(2) – (1): µ i − µ iig = RT (ln f i − ln yi P)
∧
µ i − µ iig f
∴ = ln i
RT yi P

(b) At sufficiently low pressures, the fugacity coefficient could be estimated by using:

ln φ ≈ Z – 1 (2 marks)

True.
For a pressure low enough that Z and ln φ are given approximately by:
BP BP
Z = 1+ (1) ln φ = (2)
RT RT
(2) – (1): ln φ – Z = –1
 ∴ ln φ ≈ Z – 1

(c) If a mixture of chemical species is in chemical equilibrium, any reaction that occurs at constant
temperature and pressure is leading to a decrease in the total Gibbs energy of the system.
(2 marks)

False. If a mixture of chemical species is in chemical equilibrium, the total Gibbs energy Gt
is constant at its minimum value. At this equilibrium state, (dGt)T,P = 0.

2) For a particular binary liquid solution at constant T and P, the molar enthalpies of
mixtures are represented by the equation:

H = x1(a1 + b1x1) + x2(a2 + b2x2)

where H is in J mol-1 and both ai and bi are constants.

a) Find expressions for the partial molar enthalpies of species 1 and 2 at T and P
as functions of x1.
b) Then, using both expressions obtained in 2(a), determine the partial molar
enthalpies of species 1 and 2 at infinite dilution.
(12 marks)

Solution:

a)
H = x1(a1 + b1x1) + x2(a2 + b2x2)
H = a1x1 + b1x12 + (1 – x1) [a2 + b2(1 – x1)]
H = a1x1 + b1x12 + (1 – x1) (a2 + b2 – b2x1)
H = a1x1 + b1x12 + a2 + b2 – b2x1 – a2x1 – b2x1 + b2x12
H = b1x12 + b2x12 + a1x1 – 2b2x1 – a2x1 + a2 + b2
dH
∴ = 2b1 x1 + 2b2 x1 + a1 − 2b2 − a2
dx1
dM
Use M 1 = M + x2
dx1
H1 = b1x12 + b2x12 + a1x1 – 2b2x1 – a2x1 + a2 + b2 + (1 – x1)(2b1x1 + 2b2x1 + a1 – 2b2 – a2)
H1 = (b1 + b2 – 2b1 – 2b2) x12 + (a1 – 2b2 – a2 + 2b1 + 2b2 – a1 + 2b2 + a2) x1 + (a2 + b2 +
a1 – 2b2 – a2)
H1 =(– b1 – b2) x12 +(2b1 + 2b2) x1 + (a1 – b2)
 dM
Use M 2 = M − x1
dx1
H 2 = b1x12 + b2x12 + a1x1 – 2b2x1 – a2x1 + a2 + b2 – x1(2b1x1 + 2b2x1 + a1 – 2b2 – a2)
H 2 =(b1 + b2 – 2b1 – 2b2) x12 + (a1 – 2b2 – a2 – a1 + 2b2 + a2) x1 + (a2 + b2)
H 2 = (– b1 – b2) x12 + (a2 + b2)

b)
At infinite dilution for species 1, x1 = 0, thus

H1∞ = (−b1 − b2 )(0)2 + (2b1 + 2b2 )(0) + (a1 − b2 )

H1∞ = (a1 − b2 ) J mol −1

At infinite dilution for species 2, x2 = 0 or x1 = 1, thus

H 2∞ = (−b1 − b2 )(1) 2 + (a2 + b2 )

H 2∞ = (a2 − b1 ) J mol −1

3) A single P-x1 data point of x1 = 0.389 is available for a binary system at T = 35oC and P
= 108.6 kPa. For this system, P1sat = 120.2 kPa and P2sat = 73.9 kPa. Assume that the
excess Gibbs energy, GE obeys the following model:

GE = A(x1x2) RT

Determine constant A by using approriate equations.

(7 marks)

Solution:

For the given model of excess Gibbs energy, we know that the activity coefficients are given by
the Redlich/Kister expansion:

ln γ 1 = Ax22 ln γ 2 = Ax12

Use Modified Raoult’s Law to determine constant A:

yi P = xiγ i Pi sat
P = ∑ xiγ i Pi sat
i

P = x1γ 1P1sat + x2γ 2 P2sat

P = x1 exp[ A(1 − x1 ) 2 ]P1sat + (1 − x1 ) exp[ Ax12 ]P2sat
{ } { }
108.6 = 0.389 × exp[ A × (1 − 0.389) 2 ] × 120.2 + (1 − 0.389) × exp[ A × 0.3892 ] × 73.9

The only unknown value in this equation is A, which can be solved to give:

A = 0.622