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CHE 3161 Chemistry & Chemical Thermodynamics

Test 3 Solutions

Date: 21/05/2018 Total Marks: 30 marks

The exam is a closed book test.

Use 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) For an ideal gas mixture, the following statement is a consequence of Gibbs Theorem:
"#
!" = ! "# (2 marks)
False. The enthalpy of an ideal gas is independent of pressure, thus the partial molar
#$ #$
enthalpy is equal to pure-species enthalpy (or "# = "# ) and not its solution property.
"#
Uig could be found using summability relation, in which case ! "# = " %" !" .

b) The relationship between partial residual Gibbs energy and chemical potential could be
written as:
Gi R = µ i - µ iig (2 marks)
True. The chemical potential and the partial molar Gibbs energy are identical, i.e.
µ i = Gi . Seeing that the residual Gibbs energy could be written as Gi R = Gi - Gi ig ,
thus Gi R = µ i - µ iig .

c) Henry’s Law applies to a species as it approaches purity in a binary solution.

(2 marks)
FALSE. Henry’s Law applies to a species as it approaches infinite dilution in a binary
solution, while the Lewis/Randall rule applies to a species as it approaches purity (ideal
solution).
d) For a pure species coexisting liquid and vapor phases are in equilibrium, the
corresponding liquid fugacity coefficients !"# = 1 if the vapor phase is an ideal gas.
 (2 marks)
True. When the system is in equilibrium, f iv = f il . For an ideal gas, fiv = 1. Therefore, !"#
= 1.

e) It is correct to represent excess Gibbs energy as GE = Σ xiµi – Gid . (2 marks)

TRUE
ME = M – Mid
Summability relations: M = å xi M i

Thus, M E = å xi M i - M id

G E = å xi Gi - G id

but µ i º Gi

\ G E = å xi µi - G id

(2) In a binary liquid system of species 1 and 2 at fixed T and P, the expressions for partial
molar internal energy of species 1 and 2 are given as:

U1 = 420 - 60 x12 + 40 x13 U 2 = 600 + 40 x13

where U i is in J mol-1.

a) Determine the numerical values for U1 and U2. (4 marks)

When x1 = 1, then U1 = U1

U1 = 420 – 60(1)2 + 40(1)3

U1 = 400 J mol-1

When x2 = 1 or x1 = 1 – x2 = 0, then U 2 = U 2

U2 = 600 + 40(0)3
 U2 = 600 J mol-1

- ¥ - ¥
b) Determine the numerical values for U 1 and U 2 . (4 marks)

When x1 = 0, then U1 = U1¥

2 3
U 1¥ = 420 – 60(0) + 40(0)
-1
U 1¥ = 420 J mol

When x2 = 0 or x1 = 1 – x2 = 1, then U 2 = U 2¥

3
U 2¥ = 600 + 40(1)
-1
U 2¥ = 640 J mol

c) Determine the expression for U as a function of x1. Then, using the expression of U to
find the numerical value for U if x2 = 0.4. (5 marks)

Use summability relation to determine expression for U:

M = å xi M i
i

U = å xiU i
i

U = x1U1 + x2U 2
U = x1 (420 - 60 x12 + 40 x13 ) + (1 - x1 )(600 + 40 x13 )
U = 420 x1 - 60 x13 + 40 x14 + 600 + 40 x13 - 600 x1 - 40 x14

U = -20 x13 - 180x1 + 600

If x2 = 0.4, then x1 = 1 – 0.4 = 0.6

U = – 20(0.6)3 – 180(0.6) + 600

U = 487.68 J mol-1
(3) For a gas mixture of species(1)/species(2), estimate fˆ1 , fˆ1 and G1R at T = 423 K, P = 30 bar
and y2 = 0.65 if this mixture is an ideal solution. The characteristic properties of species(1)
are Tc = 282.3 K, Pc = 50.4 bar and w = 0.087. (12 marks)

If the gas mixture is an ideal solution, then Lewis/Randall rule can be applied as shown:

fˆiid = fi , where

fˆ1id = f1

For species(1):

Tr = 423/282.3 = 1.498

Pr = 30/50.4 = 0.595

With low Pr, virial equation is valid:

é Pr 0 ù
f = expê ( B + wB1 )ú
ë Tr û

Also,

0.422 0.172
B 0 = 0.083 - B1 = 0.139 -
Tr1.6 Tr4.2

0.422 0.172
B 0 = 0.083 - = -0.1381 B1 = 0.139 - = 0.1075
1.4981.6 1.4984.2

é 0.595 ù
f1 = expê (-0.1381 + 0.087 ´ 0.1075)ú
ë 1.498 û

f1 = fˆ1 = 0.9501

For a gas mixture, fugacity coefficient is given as:

fˆi
fˆi =
yi P
 fˆ1
fˆ1 =
y1 P
fˆ1 = 0.9501(1 - 0.65)(30)
fˆ = 9.976 bar
1

Gi R = RT ln fˆi

G1R = RT ln fˆ1
G1R = 8.314 ´ 423 ´ ln 0.9501
G1R = -180.02 Jmol -1