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Test 3 Solution 2012 PDF

The document contains the instructions and questions for a closed book chemistry test. Question 1 asks students to determine if several statements about thermodynamics are true or false, providing reasoning. Question 2 asks students to determine expressions for partial molar enthalpies and numerical values using the enthalpy equation for a binary liquid system.

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Manishaa Varatha Raju
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195 views3 pages

Test 3 Solution 2012 PDF

The document contains the instructions and questions for a closed book chemistry test. Question 1 asks students to determine if several statements about thermodynamics are true or false, providing reasoning. Question 2 asks students to determine expressions for partial molar enthalpies and numerical values using the enthalpy equation for a binary liquid system.

Uploaded by

Manishaa Varatha Raju
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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NO Examination Papers Are To Be Removed From The Room.

CHE 3161 Chemistry & Chemical Thermodynamics


Test 3 Questions

Date: 24/05/2012 Total Marks: 25 marks

The exam is a closed book test.

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:

H iig = H ig (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 H iig = H iig ) and not its solution property. Hig
could be found using summability relation, in which case H ig = ∑ y i H iig = ∑ y i H iig .
i i

(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 − Giig ,
thus Gi R = µ i − µ iig .

(c) According to Lewis/Randall rule, the fugacity of each species in an ideal solution is
proportional to its mole fraction in liquid phase either at low or high pressure. (2 marks)

True. Lewis/Randall rule applies to each species in an ideal solution at all conditions of
temperature, pressure and composition. The proportionality constant is the fugacity of pure
species i in the same physical state as the solution and at the same temperature and pressure.
(d) For a pure species coexisting liquid and vapor phases are in equilibrium, the corresponding
fugacity coefficients φi could be expressed as:
φiv = φil = 1 (2 marks)

False. When the system is in equilibrium, φ iv = φil . However, φ iv = φil = 1 is only applicable
when the vapor phase (in equilibrium) is an ideal gas because φ iv = 1 .

(e) For a system initially contains n1 moles CH4 and n2 moles H2O and undergoing the
following reaction with ε as a reaction coordinate,

CH4 + H2O  CO + 3H2 ,

the mole fractions of H2 could be expressed as:


(n + n 2 ) + 3ε
yH2 = 1 (2 marks)
n1 + n 2 + 2ε

ni0 + vi ε 3ε
False. Using yi = , the mole fraction of H2 should be y H 2 = , in which
n0 + vε n1 + n 2 + 2ε
case v = ∑vi = -1-1+1+3 = 2, n0 = ∑nio = n1 + n2 and nio for H2 should be 0.

2) 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-1.

Determine:

− −
a) expressions for H 1 and H 2 . (7 marks)

Given H = 400x1 + 600x2 + x1x2(40x1 + 20x2) and x2 = 1 – x1

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


H = 400 x1 + 600 − 600 x1 + ( x1 − x12 )(20 + 20 x1 )
H = 400 x1 + 600 − 600 x1 + (20 x1 − 20 x13 )
H = −20 x13 − 180 x1 + 600
dH
∴ = −60 x12 − 180
dx1

dM
Use M 1 = M + x2
dx1
H1 = (−20 x13 − 180 x1 + 600) + (1 − x1 )(−60 x12 − 180)
H1 = 40 x13 − 60 x12 + 420

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

b) numerical values for the pure-species enthalpies H1 and H2, using the expressions you
have determined from 2a. (4 marks)

H1 = H1 when x1 = 1
H1 = 40(1) 3 − 60(1) 2 + 420
H1 = 400 J mol −1

H 2 = H 2 when x2 = 1 or x1 = 0
H 2 = 40(0) 3 + 600
H 2 = 600 J mol −1

− ∞ − ∞
c) numerical values for the partial enthalpies at infinite dilution H 1 and H 2 . , using the
expressions you have determined from 2a. (4 marks)

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

H 2∞ = H 2 when x2 = 0 or x1 = 1
H 2∞ = 40(1) 3 + 600
H 2∞ = 640 J mol −1

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