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CHE 3161 Chemistry & Chemical Thermodynamics

Solutions of Test 3

Date: 29/5/2014 Total Marks: 30 marks

The exam is a closed book test.

Let R = 8.314 J mol-1K-1 = 83.14 cm3bar 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) It is correct to represent excess Gibbs energy as GE = Σ xiµi – Gid .
(3 marks)
TRUE
ME = M – Mid
Summability relations: M = ∑ xi M i

Thus, M E = ∑ xi M i − M id

G E = ∑ xi Gi − G id
but µ i ≡ Gi

∴ G E = ∑ xi µi − G id

b) According to Lewis/Randall rule, the fugacity of each species in an ideal solution is

proportional to its mole fraction at the same T and P.
(2 marks)
TRUE
 Lewis/Randall rule is given as fˆi id = xi f i , in which case the proportionality constant is the
fugacity of pure species i in the same physical state as the solution with similar T and P.

c) If a mixture of chemical species is not in chemical equilibrium, any reaction that occurs at
constant T and P must lead to a decrease in the total Gibbs energy of the system.
(2 marks)
TRUE
The total Gibbs energy of a system at constant T and P must decrease until the condition for
equilibrium is reach when Gt attains its minimum value. At this equilibrium state, its
differential is zero or (dGt)T,P = 0.

(2) The molar entropy (J mol-1 K-1) of a binary liquid system of species 1 and 2 at constant T

and P is given by the equation S = 120x1 + 70x2 + (15x1 + 8x2) x1x2. Determine expressions as

functions of x1 for the partial molar entropy of species 1, S1 and species 2, S 2 .

(8 marks)

S = 120x1 + 70x2 + (15x1 + 8x2) x1x2

But x1 + x2 = 1
∴x2 = 1 – x1
S = 120 x1 + 70(1 – x1) + [15x1 + 8(1 – x1)] x1(1 – x1)
Reagreement and simplification of equation will lead to:
S = -7x13 – x12 + 58x1 + 70
dS
= −21x12 − 2 x1 + 58
dx1

dS
Using Eq. (11.15), S1 = S + x2
dx1
 S1 = −7 x13 − x12 + 58 x1 + 70 + (1 − x1 )(−21x12 − 2 x1 + 58)
Reagreement and simplification of equation will lead to:
S1 = 14 x13 − 20 x12 − 2 x1 + 128

dS
Using Eq. (11.16), S 2 = S − x1
dx1

S 2 = −7 x13 − x12 + 58 x1 + 70 − x1 (−21x12 − 2 x1 + 58)

Reagreement and simplification of equation will lead to:
S 2 = 14 x13 + x12 + 70

(3) Consider the following set of vapor-liquid equilibrium (VLE) data for system of species
1 and species 2 at 120 oC as shown in Table 1:

Table 1: VLE data for species 1 and species 2 at 120 oC

P/kPa x1 y1 ln γ1 ln γ2 GE/RT GE/x1x2RT
53.4 0.000 0.000
61.1 0.200 0.305
70.6 0.400 0.560
88.4 0.700 0.839
109.2 1.000 1.000
   
a) Complete all the missing entries in Table 1.  
(10 marks)
⎛ y P ⎞
Use modified Raoult’s Law or ln γ i = ln⎜⎜ sati ⎟⎟ to calculate ln γ1 and ln γ2, in which P2sat
⎝ Pi xi ⎠
= 53.4 kPa and P1sat = 109.2 kPa.
 GE
Use Eq. (12.6) or = x1 ln γ 1 + x2 ln γ 2 to calculate GE/RT
RT
The missing entries are tabulated as shown:
P/kPa x1 y1 ln γ1 ln γ2 GE/RT GE/x1x2RT
53.4 0.000 0.000 0 0
61.1 0.200 0.305 -0.159 -0.006 -0.0365 -0.228
70.6 0.400 0.560 -0.100 -0.031 -0.0584 -0.243
88.4 0.700 0.839 -0.030 -0.118 -0.0566 -0.270
109.2 1.000 1.000 0 0

b) A student found that the activity coefficients of species 1 and species 2 follow
Redlich/Kister expansion, namely
GE
= Ax1 x2
RT
  where A is a constant. Using the data calculated in Table 1, determine the expressions
of both ln γ1 and ln γ2.
(5 marks)
  According to Redlich/Kister expansion,
GE
  = A , whereby ln γ 1 = Ax22 ; ln γ 2 = Ax12  
x1 x2 RT
   
  Thus, A is the average values of GE/x1x2RT which are calculated in (3a).
(−0.228) + (−0.243) + (−0.270) − 0.741
A= = = −0.247
3 3

The expressions of both ln γ1 and ln γ2 are given as:

ln γ 1 = −0.247 x22
ln γ 2 = −0.247 x12