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CHE 3161 Chemistry & Chemical Thermodynamics

Test 3

Date: 27/5/2015 Total Marks: 50 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) During vapor and liquid equilibrium (VLE), modified Raoult’s law ( yi P = xiγ i Pi sat ) could be

fˆi
derived using the definition of activity coefficient, which is given as γ i ≡ .
fˆ id
i

(6 marks)

TRUE.
According to Lewis/Randall rule, fˆi id = xi f i

fˆi fˆi
Thus, γ i ≡ = (1)
fˆi id xi f i

Also, fˆi = yi Pφˆi (2)

At low pressure, the vapor phase may be assumed as an ideal gas, thus φˆi = 1

Also, f i = Pi sat (3) , if the liquid and vapor phases are in equilibrium at low pressure
 Use Equations (2) and (3) into Equation (1):

fˆi y Pφˆ
γi = = i sati
xi f i xi Pi
At VLE with low pressure,
yi P
γi =
xi Pi sat
yi P = xiγ i Pi sat

b) According to Gibbs’s theorem, any partial molar property of a constituent species in an ideal-
gas mixture is equal to the corresponding molar property of the species as a pure ideal gas at
the mixture temperature but at a pressure equal to its partial pressure in the mixture.
(4 marks)

FALSE
In an ideal-gas mixture system, Gibbs’s theorem could be represented by the equation:
M iig (T , P) = M iig (T , pi )

However, the above equation (or statement) is not valid to the molar volume ( M iig ≠ Vi ig )

because Vi ig = Vi ig = V ig .

(2) The molar volume V (cm3 mol-1) of a binary liquid system of species 1 and 2 at constant T

and P is given by the equation of V = 400x1 + 600x2 + (40x1 + 20x2)x1x2.

a) Find expressions (as functions of x1) for the partial molar volume of species 1, V1 and species

2, V2 .

(6 marks)
 Given V = 400x1 + 600x2 + (40x1 + 20x2)x1x2 and x2 = 1 – x1

V = 400 x1 + 600(1 − x1 ) + x1 (1 − x1 )[40 x1 + 20(1 − x1 )]

V = 400 x1 + 600 − 600 x1 + ( x1 − x12 )(20 + 20 x1 )
V = 400 x1 + 600 − 600 x1 + (20 x1 − 20 x13 )
V = −20 x13 − 180 x1 + 600 (*)

dV
∴ = −60 x12 − 180
dx1

dM
Use M 1 = M + x2
dx1
V1 = (−20 x13 − 180 x1 + 600) + (1 − x1 )(−60 x12 − 180)
V1 = 40 x13 − 60 x12 + 420

dM
Use M 2 = M − x1
dx1
V2 = (−20 x13 − 180 x1 + 600) − x1 (−60 x12 − 180)
V2 = 40 x13 + 600

b) Show that the expressions of V1 and V2 satisfy summability relation.

(4 marks)

M = ∑ xi M i

V = ∑ xiVi = x1V1 + x2V2

V = x1 (40 x13 − 60 x12 + 420) + (1 − x1 )(40 x13 + 600)

V = 40 x14 − 60 x13 + 420 x1 + 40 x13 + 600 − 40 x14 − 600 x1
V = −20 x13 − 180 x1 + 600 ( same as Eq.*)
∴V = 400 x1 + 600 x2 + (40 x1 + 20 x2 ) x1 x2
 c) Determine the numerical values for the partial molar volumes at infinite dilution V1 ∞ and V2∞ .

(4 marks)

V1 ∞ = V1 when x1 = 0
V1 ∞ = 40(0)3 − 60(0) 2 + 420
V1 ∞ = 420 cm 3 mol −1

V2∞ = V2 when x2 = 0 or x1 = 1
V2∞ = 40(1)3 + 600
V2∞ = 640 cm 3 mol −1

(3) Consider the following set of vapor-liquid equilibrium (VLE) for system of chloroform(1)
and 1,4-dioxane(2) at 50 oC as shown in Table 1

Table 1: VLE data for chloroform(1) and 1,4-dioxane(2) at 50 oC

P/kPa x1 y1 ln γ1 ln γ2 GE/RT
15.79 0.000 0.000 - 0.000 0.000
18.15 0.1248 0.2383 -0.694 0.000 -0.086
24.95 0.3615 0.6184 -0.486 -0.057 -0.212
42.10 0.6718 0.9137 -0.192 -0.355 -0.245
69.36 1.000 1.000 0.000 - 0.000
   
a) Complete all the missing entries (in 3 decimal points) in Table 1.  
(Note: Using only one set of data, say at P = 24.95 kPa, show clearly how you obtain ln γ1,
ln γ2 and GE/RT. Table 1 with the answers should be redrawn in your answer scripts)  
(15 marks)

Table 1 shows that:

P1sat = 69.36 kPa  

P2sat = 15.79 kPa  

 Use  modified Raoult’s law ( yi P = xiγ i Pi sat ) to determine ln γ1 and ln γ2:

yi P = xiγ i Pi sat

y1 P = x1γ 1 P1sat
⎛ y P ⎞
ln γ 1 = ln⎜⎜ 1 sat ⎟⎟
⎝ x1 P1 ⎠
For example, at P = 24.95 kPa, x1 = 0.3615 and y1 = 0.6184,
⎛ 0.6184 × 24.95 ⎞
ln γ 1 = ln⎜ ⎟ = −0.486  
⎝ 0.3615 × 69.36 ⎠
Similarly,
y2 P = x2γ 2 P2sat
⎛ y P ⎞ ⎛ (1 − y1 ) P ⎞ ⎛ (1 − 0.6184) × 24.95 ⎞
ln γ 2 = ln⎜⎜ 2 sat ⎟⎟ = ln⎜⎜ ⎟ = ln⎜⎜
sat ⎟
⎟⎟ = −0.057
⎝ x2 P2 ⎠ ⎝ (1 − x1 ) P2 ⎠ ⎝ (1 − 0.3615) × 15.79 ⎠

GE
Use = x1 ln γ 1 + x2 ln γ 2
RT
At P = 24.95 kPa, x1 = 0.3615
GE
= x1 ln γ 1 + x2 ln γ 2 = x1 ln γ 1 + (1 − x1 ) ln γ 2
RT  
GE
= 0.3615(−0.486) + (1 − 0.3615)(−0.057) = −0.212
RT
 
 
b) Jimmy found that the activity coefficients of chloroform(1) and 1,4-dioxane(2) follow
Margules equations, in which case A12 = -0.72 and A21 = -1.27. Determine the total
pressure P and vapor-phase mole fractions yi if x1 = 0.475. Give the answers in 2 decimal
points.
(11 marks)

According to Margules equations,

ln γ 1 = x22 [ A12 + 2( A21 − A12 ) x1 ]
ln γ 2 = x12 [ A21 + 2( A12 − A21 ) x2 ]
If A12 = -0.72 and A21 = -1.27, then
ln γ 1 = x22 [−0.72 + 2{−1.27 − (−0.72)}x1 ]
ln γ 1 = x22 [−0.72 − 1.1x1 ]

ln γ 2 = x12 [−1.27 + 2{−0.72 − (−1.27)}x2 ]

ln γ 2 = x12 [−1.27 + 1.1x2 ]

Determine γ1 and γ2 at x1 = 0.475 and x2 = 1 – 0.475 = 0.525

ln γ 1 = 0.5252 [−0.72 − 1.1(0.475)]
γ 1 = 0.71002

ln γ 2 = 0.4752 [−1.27 + 1.1(0.525)]

γ 2 = 0.85535

According to modified Raoult’s law,

P = ∑ xiγ i Pi sat = x1γ 1P1sat + x2γ 2 P2sat
i

P = 0.475(0.71002)(69.36) + 0.525(0.85535)(15.79) = 30.48296

P = 30.48 kPa

yi P = xiγ i Pi sat
Also, x1γ 1P1sat
y1 =
P
(0.475)(0.71002)(69036)
y1 =
30.48296
y1 = 0.77
y2 = 1 – y1 = 0.23