ID: Name:

ChemS 360: Advanced Physical Chemistry I

Exercise 2 (September 26, 2022)
Problem 1
Use the data in the following table to determine at what temperature a 0.20−mol ∙ k g−1
solution of the analgesic codeine, C18H21NO3, in benzene will freeze.

Problem 2

For the reaction N 2 ( g ) +3 H 2 (g)⇌ 2 N H 3 ( g) at 400 K, the equilibrium constant (K) is 41. Find
the value of K for each of the following reactions at the same temperature:

(a) 2 N H 3 ( g ) ⇌ N 2 ( g ) +3 H 2 (g)
(b) 0.5 N 2 ( g ) +1.5 H 2 ( g ) ⇌ N H 3 (g)
(c) 2 N 2 ( g )+6 H 2(g)⇌ 4 N H 3 ( g)

Problem 3
Calculate the standard reaction Gibbs free energy for the following cell reactions:
−¿ (aq )¿
3+¿ (aq ) +I ¿

(a) 2 C e 4 +¿ ( aq)+3 I , Ecell °=+ 1.08V .

3
−¿→ 2C e ¿
¿
+¿ (aq )¿
2−¿ ( aq) +14 H ¿

, Ecell °=−1.29V .
2+¿ ( aq )+C r O ¿

(b) 6 F e3+ ¿ (aq )+2 C r 3+ ¿ ( aq )+ 7 H2 O →6 Fe

2 7
¿
¿
Problem 4

A sealed container was filled with 0.300 mol H2(g), 0.400 mol I2(g), and 0.200 mol HI(g) at 870 K
and total pressure 1.00 bar. Calculate the amounts of the components in the mixture at
equilibrium given that K=870 for the reaction H 2 ( g )+ I 2 ( g)⇌ 2 HI (g).

Problem 5
The enthalpy of vaporization of a certain liquid is found to be 14.4 kJ mol -1 at 180 K, its boiling
point. The molar volumes of the liquid and the vapor at the boiling point are 115 cm 3 mol-1 and
14.5 dm3 mol-1, respectively.
(a) Estimate dp/dT from the Clapeyron equation.
(b) Calculate the percentage error if the Clausius-Clapeyron equation is used instead.

Problem 6
The excess Gibbs energy of solutions of methylcyclohexane (MCH) and tetrahydrofuran (THF) at
303.15 K was found to fit the expression:

G E=RTx ( 1−x ) ( 0.4857−0.1077 ( 2 x−1 ) +0.0191 ( 2 x −1 )2 )

where x is the mole fraction of MCH. Calculate the Gibbs energy of mixing when a mixture of
1.00 mol of MCH and 3.00 mol of THF is prepared.
Problem 7
The figures below show the experimentally determined phase diagrams for the nearly ideal
solution of hexane and heptane:

(a) Label the regions of the diagrams as to which phases present.

(b) For a solution containing 1 mol each of hexane and heptane, estimate the vapor
pressure at 70 ℃ when vaporization on reduction of the external pressure just begins.
(c) What is the vapor pressure of the solution at 70 ℃ when just one drop of liquid
remains?
(d) Estimate from the figures the mole fraction of hexane in the liquid and vapor phases
from the conditions of part (b).
(e) What are the mole fractions for the conditions of part (c)?
(f) At 80 ℃ and 760 torr, what are the percentages of substance in the liquid and vapor
phases when z Heptane =0.40?
Problem 8
Molecular bromine is 24.0 percent dissociated at 1600 K and 1.00 bar in the equilibrium
B r 2 (g)⇌ 2 Br (g). Calculate:

(a) K
(b) Δ r G°
(c) K at 2000 ℃, given that Δ r H ∘=+112 kJ mol−1

Problem 9
A galvanic cell is constructed that carries out the reaction:
3+¿ ¿
2+ ¿ ( aq ) →Pb ( s) +2 C r ¿

P b2+ ¿ (aq )+2 C r ¿

If the initial concentration of P b2+ ¿(aq )¿ is 0.15 M, that of C r 2+¿(aq)¿ is 0.20 M, and that of
3 +¿(aq)¿
Cr is 0.0030 M, calculate the initial voltage generated by the cell at 25 ℃ .

Half-Reaction o
E [V ]
−¿ →Pb (s )¿

P b2+ ¿+ 2e ¿
-0.1263
2+¿ ¿

-0.424
−¿→C r ¿
3 +¿+e ¿
Cr

Problem 10
For toluene, the solid-liquid coexistence curve is given by:
p/ ¯¿ p 3 / +1000×
¯ ( 5.60+11.727 x ) x

where x=T /T 3 −1 and the triple point pressure and temperature are p3=0.4362 μbar and
T 3=178.15 K . The liquid-vapor curve is given by:

ln ⁡¿
where y=T /T c =T /(593.95 K ).

(a) Estimate the standard melting point (T m) of toluene.

(b) Estimate the standard boiling point (T b) of toluene. [This question requires a numerical
solver. If a numerical solver is not available, skip this part and use T b=383.7 K in the
next question.]
 (c) Compute the standard enthalpy of vaporization of toluene, give that the molar volumes
of the liquid and vapor at the normal boiling point are 0.12 L/mol and 30.3 L/mol,
respectively.
Problem 11

The total enthalpy of mixing of n A moles of component A and n B moles of component B at a

temperature (T) and a pressure (P) is measured to be:
2 n A n B RT
Δ H mix=
n A +n B

The excess entropy of mixing is zero for this liquid mixture. Obtain the activity coefficients of
the two components, γ A and γ B , given that n A =1.00 mol , n B=2.00 mol , T =300 K , and P=1 ¯¿.

Problem 12
(a) Draw two T-xy diagrams for a binary solution with (i) a maximum boiling azeotrope, and
(ii) a minimum boiling azeotrope.
(b) Suppose two solvents form an azeotrope at 75 ℃. Compute the azeotropic pressure and
composition of the mixture given that the solution can be modeled by the Margules
equations with the following coefficients and properties:
ξ=0.458
sat
P1 ( 75 ℃ )=105.1 kPa
sat
P2 ( 75 ℃ )=79.4 kPa

Problem 13
Using the definition of fugacity:

RT ln ( ff° )=G ( T , P )−G ° (T , P °)

where f ° , G °, and P ° denote arbitrary references. Let f ° =P ° =1 ¯¿, G °=0, and T =300 K in
this problem.

(a) Calculate the fugacity of C O2 at 20 bar and at 50 bar. Assume C O2 is an ideal gas.
(b) Calculate the fugacity of C O2 at 20 bar and at 50 bar. Assume C O2 follows the following
equation of state:
RT
P=
V −b
 1 RTc
3
−5 m
where b= =4.28 ×10 .
8 Pc mol