Solutions to Practice questions (Chapter 6)

Q1. Use LeChateliers principle to predict the sense of the shift in equilibrium for the system
2NO
2
N
2
O
4

when it is cooled to -75C and use the vant Hoff equation to confirm your prediction with a quantitative
calculation of K at -75C, given H = -13.67 kcal/mol (-57.2kJ/mol) and K=6.97 at 25 C.
Solution
Cooling an exothermic reaction causes it to produce more heat by running forward hence more
dimerization will occur, as observed.
Ln(K
2
/K
1
) = +[13.670 cal/mol/1.9872 cal/Kmol)](1/198K -1/298K)
=11.6
K2 = (1.16 X 10
5
) (6.97) = 8.06 X 10
5
This large value of K implies nearly complete reaction.

Q2. The system 2NO
2
N
2
O
4
is brought to equilibrium at a total pressure of 1.00 atm at 25C. K=6.97
at 25 C. What are the partial pressures of NO
2
and N
2
O
4


Solution
Let P
0
is the initial pressure of NO2
2NO2 N2O4 Total pressure
Initial P
0
0 P
0
Change -2x x
Equilbm P
0
-2x x p
0
-x

P
0
-x = 1 atm
P
0
=1-x
K=x/(1-x)
2

x may vary from 0-1
The resulting quadratic equation has a solution of x=0.686, 1.457.
Only 0.686 is acceptable, yielding
P
N2O4
= 0.686 atm and P
NO2
= 0.314 atm. Position of equilibrium lies to the right as expected.

Q3. Assuming the rapid attainment of equilibrium, which of the following conditions would be most
favourable for the production of ethanol from the reaction of ethylene with steam
CH2=CH2(g) + H2O(g) CH3CH2OH(g)
a. P=5 atm, T=600K
b. P=50 atm, T=400K
c. P=50 atm, T=600K
d. P=5 atm, T=400K

Q4. For the synthesis of ammonia at 500C, the equilibrium constant is 6.0 X 10
-2
Predict the direction in
which the system will shift to reach equilibrium in each of the following cases.
a. [NH
3
]
0
= 1.0 X 10
-3
M; [N
2
]
0
= 1.0X10
-5
M; [H
2
]
0
= 2.0X10
-3
M
b. [NH
3
]
0
= 2.0 X 10
-4
M; [N
2
]
0
= 1.5X10
-5
M; [H
2
]
0
= 3.54X10
-1
M
c. [NH
3
]
0
= 1.0 X 10
-4
M; [N
2
]
0
= 5.0 M; [H
2
]
0
= 1.0X10
-2
M


Solution:
a. Q = 1.3 X 10
7
Q>K The system shift to the left.
b. Q = 6.01 X 10
-2
Q=K No shift will occur in the system.
c. Q = 2.0 X 10
-3
Q<K The system shift to the right.

Q5. Assume that the reaction for the formation of gaseous hydrogen fluoride from hydrogen and
fluorine has an equilibrium constant of 1.15 X 10
2
at a certain temperature. In a particular experiment at
this temperature 3.0000 moles of each component was added to a 1.500-liter flask. Calculate the
equilibrium concentration of all species.


Solution:
H2(g) + F2(g) 2HF(g)

We first calculate the initial concentration
[HF]
0
= [H
2
]
0
= [F
2
]
0
= 3.000 mol/1.5 L = 2.000 M

Q = 1.000, Q<K , system must shift to right.
Use ICE method:

H2(g) F2(g) 2HI(g)
Initial 2.000 2.000 2.000
Change -x -x 2x
Equilibrium 2.000-x 2.000-x 2.000+2x
K=1.15X 10
2
= (2.000+2x)
2
/(2.000-x)
2

X=1.528
[H
2
]=[F
2
]=0.472 M
[HF] = 5.056 M


Q6 .At 327C, the equilibrium concentrations are [CH3OH]=0.15 M, [CO]=0.24 M and [H2] = 1.1 M for
the reaction
CH3OH
(g)
CO
(g)
+ 2H
2(g)

Calculate K
p
at this temperature.

K
c
= 0.24 X (1.1)
2
/0.15
=1.936
Kp = K
c
(RT)
n

=1.936 (0.08205 x 600)
2

=4.69 x 10
3