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CHE 3161 Chemistry & Chemical Thermodynamics

Date: 26/5/2016 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) When two pure species are mixed at constant T and P to form a solution, the enthalpy of the
ideal solution can be represented by Hid = x1H1 + x2H2.
(4 marks)
TRUE. According to property change of mixing, ΔM = M – ∑xiMi, thus:
ΔH = H – ∑xiHi
ΔH = H – x1H1 – x2H2
H = ΔH + x1H1 + x2H2
But HE = ΔH
∴ H = HE + x1H1 + x2H2
Also, HE = H – Hid
∴ H = H – Hid + x1H1 + x2H2
∴ Hid = x1H1 + x2H2

Alternatively,
TRUE. According to property change of mixing, ΔM = M – ∑xiMi, thus:
ΔH = H – ∑xiHi
 ΔH = H – x1H1 – x2H2
H = ΔH + x1H1 + x2H2
But HE = ΔH
H= HE + x1H1 + x2H2
Equation above may be written for an ideal solution:
Hid= HE,id + x1H1 + x2H2
But, excess enthalpy is zero for an ideal solution, resulting HE,id = 0
∴ Hid = x1H1 + x2H2

b) Every equation that provides a relation among thermodynamic properties of a constant-

c) In a binary solution at constant T and P, the fugacity for a species i can be estimated by using
Lewis/Randall rule when the species i approaches purity.
(2 marks)
TRUE. When a species i approaches purity, the binary system displays an ideal-solution
behavior. According to Lewis/Randall rule, the fugacity of each species in an ideal solution is
proportional to its mole fraction, namely fˆi id = xi f i . Seeing that the system is at equilibrium,

fˆi l = fˆi v = fˆi id = xi f i .

d) When a reaction system reaches chemical equilibrium, the total entropy of the system is a
minimum.
(2 marks)
⎡∂ (nG) ⎤ ⎡∂ G t ⎤
∑υ µ i i = ⎢⎣ = ⎢ ⎥ =0
∂ε ⎥⎦T ,P ⎣ ∂ε ⎦T ,P
FALSE. The total Gibbs energy Gt is the minimum or i
when
a reaction system reaches chemical equilibrium.
(2) Assuming that a gas mixture, consisting of methane (1) and ethane (2), is forming an ideal

solution. Estimate fˆ1 and fˆ2 at T = 373.15K, P = 35 bar and y1 = 0.21. Provide your answers

in two decimal points.

Given:
Species Tc (K) Pc (bar) ω

Methane (1) 190.6 45.99 0.012

Ethane (2) 305.3 48.72 0.100

(10 marks)

Lewis/Randall rule applies to each species in an ideal solution at all conditions of temperature,

pressure and composition. Lewis/Randall rule gives an alternative form:

φˆiid = φi

Thus, φˆ1id = φ1; φˆ2id = φ2

P = PcPr, thus Pr = P/Pc T = TcTr, thus Tr = T/Tc

Pr,1 = 35/45.99 = 0.761035 Tr,1 = 373.15/190.6 = 1.957765

Pr,2 = 35/48.72 = 0.718391 Tr,2 = 373.15/305.3 = 1.222240

For low reduced pressure, the simplest form of the virial equation is valid to estimate φi:

⎡ Pr 0 ⎤
φi = exp⎢ ( B + ωB1 )⎥
⎣ Tr ⎦

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

0.422 0.172
B10 = 0.083 − = −0.061044 B11 = 0.139 − = 0.128764
1.9577651.6 1.9577654.2
 0.422 0.172
B 02 = 0.083 − = −0.223099 B12 = 0.139 − = 0.064959
1.2222401.6 1.2222404.2

⎡ 0.761035 ⎤
φˆ1id = φ1 = exp⎢ (−0.061044 + 0.012 × 0.128764)⎥ = 0.97714
⎣ 1.957765 ⎦

⎡ 0.718391 ⎤
φˆ2id = φ2 = exp⎢ (−0.223099 + 0.1 × 0.064959)⎥ = 0.88046
⎣1.222240 ⎦

Use fˆi = φˆi Pyi

fˆ1 = 0.97714 × 35 × 0.21 = 7.18 bar

fˆ2 = 0.88046 × 35 × (1 − 0.21) = 24.34 bar

(3) The volume change of mixing (cm3 mol-1) for the system ethanol(1)/methyl butyl ether(2) at
25oC is given by the equation:

ΔV = x1x2[-1.026 + 0.220(x1 - x2)]

Given that V1 = 58.63 cm3 mol-1 and V2 = 118.46 cm3 mol-1, determine the total volume of
mixture which is formed when 750 cm3 of pure species 1 is mixed with 1500 cm3 of species 2
at 25oC. Provide your answer in two decimal points.
(10 marks)
t t
V1 = n1V1 V2 = n2V2
n1 = 750/58.63 n2 = 1500/118.46
n1 = 12.7921 mol n2 = 12.6625 mol

x1 = n1/(n1 + n2)
x1 = 12.7921 / (12.7921 + 12.6625)
x1 = 0.5025
x2 = 1 – x1 = 1 – 0.5025 = 0.4975
Use property change of mixing, ΔM = M – ∑xiMi
For volume change of mixing in a binary system:
ΔV = V – x1V1 – x2V2
V = ΔV + x1V1 + x2V2
V = x1x2[-1.026 + 0.220(x1 - x2)] + x1V1 + x2V2
V = (0.5025)(0.4975)[-1.026 + 0.22(0.5025 – 0.4975)] + (0.5025)(58.63) + (0.4975)(118.46)
V = 88.1392 cm3 mol-1

Vt = nV
Vt = (12.7921 + 12.6625)(88.1392)
Vt = 2243.55 cm3