B18PA/B18AP: Semester 1, Week 10 Heriot-Watt University, EPS

School of
Engineering &
Physical Sciences

Model answer
B18PA1 Tutorial and B18AP Workshop

Semester 1, Week 10
Chemical equilibrium and partial molar volumes
Dr N Hendrik Nahler

2015/16

1 Concepts
a) Le Chatelier’s principle
The exothermic reaction ◦(g)
•(g) reaches the following equilibrium:

Indicate and justify which of the following cases (boxes A – E) is met by the descriptions
below. Hint: You need to count the number of molecules of each type for the ’Equilib-
rium’ state of the system and in each of the boxes A - E. The relative arrangement of
molecules in each box is irrelevant.

i) Some of molecule • is added to the ’Equilibrium’ system. Which of the boxes above
best represents the new equilibrium position? Justify your answer.

We need to judge the change to the equilibrium system and compare this
to boxes A – E. Therefore, we first count the composition of all the boxes.
• ◦
Equilibrium 6 4
A 11 4
B 5 5
C 6 4
D 9 6
E 9 4

Copyright
c Dr N Hendrik Nahler, 2015/16 1

©HERIOT-WATT UNIVERSITY B18AP April 2016 v3

 In this case D is the correct answer. The equilibrium is

• 6
= = 1.5
◦ 4
The only box fulfilling this condition

• 9
= = 1.5
◦ 6
is box D.

ii) The temperature of the ’Equilibrium’ system is increased. Which of the boxes above
best represents the new equilibrium position? Justify your answer.

B is the correct answer. In an exothermic reaction, an increase in temperature

will decrease the equilibrium constant, i.e. shift to reactants. Box B is the only
one where the equilibrium constant is smaller than in the initial box. It is also,
apart from Box C, the only one where the total number of molecules is 10.

iii) The pressure of the ’Equilibrium’ system is increased. Which of the boxes above
best represents the new equilibrium position? Justify your answer.

C is the correct box. According to LeChatelier’s principle, an increase in pres-

sure favours the side with fewer gas-phase molecules. However, in this reaction,
the stochiometric factors in the reaction are the same for reactants and products.
Therefore, the equilibrium constant Kp is independent of pressure. A change in
pressure has no effect on the equilibrium of this reaction.

2 Phase diagrams
Draw a generic phase diagram (pressure vs. temperature), similar to the one shown in the
lecture, and label it appropriately. Then draw the pathways corresponding to the following
processes on your phase diagram:

a) You have some tea left in your thermos flask. Through a rubber stopper you insert a
test tube into the flask. After filling the test tube with liquid nitrogen you cannot hear
any tea slushing around in the bottle when you shake it.

b) A pure liquid in equilibrium with its vapour pressure is contained in a transparent cylinder
and piston assembly. You can see the interface between the liquid and vapour. By slightly
increasing the temperature the interface disappears.

©HERIOT-WATT UNIVERSITY B18AP April 2016 v3

 liquid
a
b

Pressure
critical
point
solid

triple
point
vapour

Temperature

3 Chemical equilibrium
a) Consider the following reaction at room temperature (T = 298.15 K):

N2 O4 (g) 2NO2 (C 1)

i) Use the data from the appendix of Elements of Physical Chemistry, Atkins & de
Paula to calculate ∆r G−◦ and Kp for this reaction.

∆r G = 2 · ∆f G(NO2 ) − ∆f G(N2 O4 )
= 2 · 51.31 kJ·mol−1 − 96.89 kJ·mol−1 = 4.73 kJ·mol−1
!
4730 kJ·mol−1
 
∆r G
Kp = exp − = exp − = 0.148
RT 8.314 J·K−1 ·mol−1

ii) Both gases are contained in a reaction vessel at pressures pN2 O4 = 650 mbar and
pNO2 = 350 mbar respectively. Calculate the reaction quotient and judge if this
system is at equilibrium using your result above.

p2NO 0.352
2
Q= = = 0.188
pN2 O4 0.65

Note: pressures are always given in respect to the standard pressure p−◦ = 1 bar.
As Q 6= Kp , the system is not in equilibrium.

©HERIOT-WATT UNIVERSITY B18AP April 2016 v3

iii) If the system is not at equilibrium, i.e. Q 6= Kp , must it move toward reactants or
products to reach equilibrium?

As Q > Kp , the reaction will move to form more reactants to establish equilib-
rium.

iv) Calculate Kc for reaction C 1.

∆νgas = νgas (prod.) − νgas (react.) = 2 − 1 = 1

−∆νgas
298.15 K −1
  
T
Kc = Kp = 0.148 = 5.97 × 10−3
12.027 K 12.027 K

v) Calculate the equilibrium constant, Kp for the reaction:

1
NO2 (g) N O (C 2)
2 2 4
using your result from i).
1/2
p2NO pN
−1/2
2 O4
Kp (i) = pN O
2
while Kp (v) = pNO = Kp (i) = 2.60.
2 4 2

vi) Use the data from the appendix of Elements of Physical Chemistry, Atkins & de
Paula to calculate at which temperature the mixture in ii) following reaction C 1
would be in equilibrium, i.e. Kp = Q. Temperature dependence of chemical equi-
libria is described by the van’t Hoff equation.

• Solve van’t Hoff equation

∆r H −◦
 
1 1
ln K2 − ln K1 = −
R T1 T2

• With T1 = 298.15 K, K1 = 0.148 and K2 = 0.188, we need to solve for T2 .

• Which yields
 −1
1 R K2
T2 = − −
◦
ln
T1 ∆r H K1

• We need to calculate ∆r H −◦ according to Hess law using the reference data:

∆r H −◦ = 2·∆f H(NO2 )−∆f H(N2 O4 ) = 2·33.18 kJ·mol−1 −9.16 kJ·mol−1 =
57.2 kJ·mol−1
• It follows
!−1
1 8.314 J·K−1 ·mol−1 0.188
T2 = − ln = 301.3 K
298.15 K 57 200 J·mol−1 0.148

©HERIOT-WATT UNIVERSITY B18AP April 2016 v3

 b) Consider the gas-phase reaction 2 A + B 3 C + 2 D at a pressure of 1 bar. At
the beginning, there are 1.0 mol of A, 3.0 mol of B, 0 mol of C, and 2.0 mol of D. At
equilibrium, there are 1.2 mol of C.
i) Calculate the mole fractions of all reactants and products at equilibrium following
the stochiometry of the reaction.

A B C D Total
Amount at start / mol 1.0 3.0 0 2.0 6.0
Amount at equilibrium /mol 0.2 2.6 1.2 2.8 6.8
Mole fractions 0.029 0.38 0.18 0.41 0.999
The disappearance (A and B) and formation (C and D) of molecules follows
the stochiometry of the reaction. Each molecule of B forms three molecules
of C. So, if 1.2 mol of C are formed, then 0.4 mol of B will have been used to
result in 2.6 mol of B at equilibrium. The same concept is applied for A and D
(formation).
The mole fraction of each substance is the number of moles of that substance
divided by the total number of moles (reactants and products). Do not use
excessive significant figures.

ii) Define the equilibrium constant, Kp , for this reaction in respect of the mole fractions
and the total pressure, ptot . Remember that each partial pressure is defined as
pA = xA × ptot .

p3C · p2D x3C · x2D 2

Kp = = p
p2A · pB x2A · xB tot

iii) Calculate the equilibrium constant, Kp , for this reaction.

Kp = 3.1
Use the numbers for the mole fractions from the table above in the expression
for Kp . According to the question text, the total pressure is 1 bar which is the
same as the standard pressure, p−◦ .

4 Mixtures
a) You mix 50 ml of water with 50 ml of ethanol at room temperature. Use the data provided
in the lecture handout to estimate the volume of the solution to 2 s.f.

To calculate the volume of the mixture we use V = nH2 O VH2 O + nEtOH VEtOH . We
can read the partial molar volumes of H2 O and EtOH off the graph provided in the
lecture handout. However, we first need to calculate the number of moles of water

©HERIOT-WATT UNIVERSITY B18AP April 2016 v3

and ethanol in the mixture based on the given initial volumes, the densities and
molar masses.
mA V (A)ρA
nA = =
MA MA
Note that V (A) is the volume of component A before mixing and ρA is the density
of A.

H2 O EtOH
V (A) / cm3 50 50
ρA / g·cm−3 0.998 0.789
MA / g·mol−1 18.02 46.07
nA / mol 2.77 0.856
xA 0.764 0.236
VA / cm3 ·mol−1 17.8 55.4

V = 2.77 mol · 17.8 cm3 ·mol−1 + 0.856 mol · 55.4 cm3 ·mol−1
= 97 cm3

You can see that the mixture has a considerably lower volume than the sum of its
two components.

©HERIOT-WATT UNIVERSITY B18AP April 2016 v3