Le Chteliers principle, states that if an external stress

is applied to a system at equilibrium, the system adjusts in such a way that the stress
is partially offset as the system reaches a new equilibrium position. The word stress
here means a change in concentration, pressure, volume, or temperature that removes
the system from the equilibrium state. We will use Le Chteliers principle to assess
the effects of such changes.
At 720C, the equilibrium constant Kc for the reaction
N2(g) 1 3H2(g) 2NH3(g)
is 2.37 3 1023. In a certain experiment, the equilibrium concentrations are [N2] 5 0.683 M,
[H2] 5 8.80 M, and [NH3] 5 1.05 M. Suppose some NH3 is added to the mixture so that its
concentration is increased to 3.65 M. (a) Use Le Chteliers principle to predict the shift in
direction of the net reaction to reach a new equilibrium. (b) Confi rm your prediction by
calculating the reaction quotient Qc and comparing its value with Kc.
Strategy (a) What is the stress applied to the system? How does the system adjust to
offset the stress? (b) At the instant when some NH 3 is added, the system is no longer at
equilibrium. How do we calculate the Qc for the reaction at this point? How does a
comparison of Qc with Kc tell us the direction of the net reaction to reach equilibrium.
Solution (a) The stress applied to the system is the addition of NH 3. To offset this
stress, some NH3 reacts to produce N2 and H2 until a new equilibrium is established.
The net reaction therefore shifts from right to left; that is,
N2(g) 1 3H2(g) 2NH3(g)
(b) At the instant when some of the NH3 is added, the system is no longer at
equilibrium. The reaction quotient is given by
Qc 5
[NH3]20
[N2]0[H2]30
5
(3.65)2
(0.683) (8.80)3
5 2.86 3 1022
Because this value is greater than 2.37 3 1023, the net reaction shifts from right to
left until Qc equals Kc.

14.16 Consider the following equilibrium process at

700C:
2H2(g) 1 S2(g) 2H2S(g)
Analysis shows that there are 2.50 moles of H2, 1.35 3
1025 mole of S2, and 8.70 moles of H2S present in a
12.0-L fl ask. Calculate the equilibrium constant Kc
for the reaction.
14.18 The equilibrium constant KP for the reaction
2SO3(g) 2SO2(g) 1 O2(g)
is 1.8 3 1025 at 350C. What is Kc for this reaction?
14.20 A reaction vessel contains NH3, N2, and H2 at equilibrium
at a certain temperature. The equilibrium
concentrations are [NH3] 5 0.25 M, [N2] 5 0.11 M,
and [H2] 5 1.91 M. Calculate the equilibrium constant
Kc for the synthesis of ammonia if the reaction
is represented as
(a) N2(g) 1 3H2(g) 2NH3(g)
(b) 12
N2(g) 1 32
H2(g) NH3(g)
14.22 At equilibrium, the pressure of the reacting mixture
CaCO3(s) CaO(s) 1 CO2(g)
is 0.105 atm at 350C. Calculate KP and Kc for this
reaction.
14.24 Ammonium carbamate, NH4CO2NH2, decomposes
as follows:
NH4CO2NH2(s) 2NH3(g) 1 CO2(g)
Starting with only the solid, it is found that at 40C
the total gas pressure (NH3 and CO2) is 0.363 atm.
Calculate the equilibrium constant KP.
14.26 Pure phosgene gas (COCl2), 3.00 3 1022 mol, was
placed in a 1.50-L container. It was heated to 800 K,
and at equilibrium the pressure of CO was found to
be 0.497 atm. Calculate the equilibrium constant KP
for the reaction
CO(g) 1 Cl2(g) COCl2(g)

14.28 A 2.50-mole quantity of NOCl was initially in a

1.50-L reaction chamber at 400C. After equilibrium
was established, it was found that 28.0 percent of the
NOCl had dissociated:
2NOCl(g) 2NO(g) 1 Cl2(g)
Calculate the equilibrium constant Kc for the reaction.
14.30 The following equilibrium constants have been determined
for oxalic acid at 25C:
H2C2O4(aq) H1(aq) 1 HC2O4
2(aq)
K.c 5 6.5 3 1022
HC2O4
2(aq) H1(aq) 1 C2O4 22(aq)
Kc 5 6.1 3 1025
Calculate the equilibrium constant for the following
reaction at the same temperature:
H2C2O4(aq) 2H1(aq) 1 C2O4 22(aq)
14.32 At a certain temperature the following reactions have
the constants shown:
S(s) 1 O2(g) SO2(g) K.c 5 4.2 3 1052
2S(s) 1 3O2(g) 2SO3(g) Kc 5 9.8 3 10128
Calculate the equilibrium constant Kc for the following
reaction at that temperature:
2SO2(g) 1 O2(g) 2SO3(g)
The Relationship Between Chemical Kinetics
and Chemical Equilibrium
Review Questions
14.34 Explain why reactions with large equilibrium constants,
such as the formation of rust (Fe2O3), may
have very slow rates.
Problems
14.36 Consider the following reaction, which takes place
in a single elementary step:
2A B
k1
k1
1 A2B
If the equilibrium constant Kc is 12.6 at a certain
temperature and if kr 5 5.1 3 1022 s21, calculate the
value of kf.

What Does the Equilibrium Constant Tell Us?

Review Questions
14.38 Outline the steps for calculating the concentrations
of reacting species in an equilibrium reaction.
14.40 For the synthesis of ammonia
N2(g) 1 3H2(g) 2NH3(g)
the equilibrium constant Kc at 375C is 1.2. Starting
with [H2]0 5 0.76 M, [N2]0 5 0.60 M, and [NH3]0 5
0.48 M, which gases will have increased in concentration
and which will have decreased in concentration
when the mixture comes to equilibrium?
14.41 For the reaction
H2(g) 1 CO2(g) H2O(g) 1 CO(g)
at 700C, Kc 5 0.534. Calculate the number

14.1 Kc 5
[NO2]4[O2]
[N2O5]2 ; KP 5
P4
NO2PO2
P2
N2O5

14.2 2.2 3 102

14.3 347 atm 14.4 1.2
14.5 Kc 5
[Ni(CO)4]
[CO]4 ; KP 5
PNi(CO)4
P4
CO

14.6 KP 5 0.0702; Kc 5 6.68 3 1025

14.7 (a) Ka 5
[O3]2
[O2]3 (b) Kb 5
[O3]2
3

[O2]
; Ka 5 K3b
14.8 From right to left. 14.9 [HI] 5 0.031 M, [H2] 5 4.3 3
1023 M, [I2] 5 4.3 3 1023 M 14.10 [Br2] 5 0.065 M,
[Br] 5 8.4 3 1023 M 14.11 QP 5 4.0 3 105; the net
reaction will shift from right to left. 14.12 Left to right.
14.13 The equilibrium will shift from (a) left to right,
(b) left to right, and (c) right to left. (d) A catalyst has no
effect on the equilibrium.

14.14 (a) A 1 C AC. (b) A 1 D AD. 14.16 1.08 3 107. 14.18 3.5 3 1027. 14.20 (a) 0.082. (b)
0.29. 14.22 0.105; 2.05 3 1023. 14.24 7.09 3 1023. 14.26 3.3. 14.28 3.53 3 1022. 14.30 4.0 3
1026. 14.32 5.6 3 1023. 14.36 0.64/M2 ? s. 14.40 [NH3] will increase and [N2] and [H2] will
decrease. 14.42 NO: 0.50 atm; NO2: 0.020 atm. 14.44 [I] 5 8.58 3 1024 M; [I2] 5 0.0194 M.
14.46 (a) 0.52. (b) [CO2] 5 0.48 M, [H2] 5 0.020 M, [CO] 5 0.075 M, [H2O] 5 0.065 M. 14.48

[H2] 5 [CO2] 5 0.05 M, [H2O] 5 [CO] 5 0.11 M. 14.54 (a) Shift position of equilibrium to the
right. (b) No effect. (c) No effect. 14.56 (a) No effect. (b) No effect. (c) Shift the position of
equilibrium to the left. (d) No effect. (e) To the left. 14.58 (a) To the right. (b) To the left. (c) To
the right. (d) To the left. (e) No effect. 14.60 No change. 14.62 (a) More CO2 will form. (b) No
change. (c) No change. (d) Some CO2 will combine with CaO to form CaCO3. (e) Some CO2
will react with NaOH so equilibrium will shift to the right. (f) HCl reacts with CaCO3 to
produce CO2. Equilibrium will shift to the left. (g) Equilibrium will shift to the right. 14.64 (a)
NO: 0.24 atm; Cl2: 0.12 atm. (b) 0.017. 14.66 (a) No effect. (b) More CO2 and H2O will form.
14.68 (a) 8 3 10244. (b) The reaction has a very large activation energy. 14.70 (a) 1.7. (b) A: 0.69
atm, B: 0.81 atm. 14.72 1.5 3 105. 14.74 H2: 0.28 atm, Cl2: 0.049 atm, HCl: 1.67 atm. 14.76 5.0
3101 atm. 14.78 3.84 3 1022. 14.80 3.13. 14.82 N2: 0.860 atm; H2: 0.366 atm; NH3: 4.40 3
1023 atm. 14.84 (a) 1.16. (b) 53.7%. 14.86 (a) 0.49 atm. (b) 0.23. (c) 0.037. (d) Greater than
0.037 mol. 14.88 [H2] 5 0.070 M, [I2] 5 0.182 M, [HI] 5 0.825 M. 14.90 (c). 14.92 (a) 4.2 3
1024. (b) 0.83. (c) 1.1. (d) In (b): 2.3 3103; in (c): 0.021. 14.94 0.0231; 9.60 3 1024. 14.96 NO2:
1.2 atm; N2O4: 0.12 atm. KP 5 12. 14.98 (a) The equilibrium will shift to the right. (b) To the
right. (c) No change. (d) No change. (e) No change. (f ) To the left. 14.100 NO2: 0.100 atm;
N2O4: 0.09 atm. 14.102 (a) 1.03 atm. (b) 0.39 atm. (c) 1.67 atm. (d) 0.620.
14.104 22 mg/m3. Yes. 14.106 Temporary dynamic equilibrium between the melting ice cubes
and the freezing of the water between the ice cubes. 14.108 [NH3] 5 0.042 M, [N2] 5 0.086 M,
[H2] 5 0.26 M. 14.110 1.3 atm. 14.112 2115 kJ/mol. 14.114 SO2: 2.71 atm; Cl2: 2.71 atm;
SO2Cl2: 3.58 atm. 14.116 4.0. 14.118 (a) The plot curves toward higher pressure at low values of
1/V. (b) The plot curves toward higher volume as T increases.