CHEM 1105 GAS EQUILIBRIA

1. Equilibrium Reactions - a Dynamic Equilibrium

Initial amounts: N2O4 = 0.10 mole NO2 = 0 mole

1.0 L container
NO2 = 0.12 mole
0.10

moles N2O4 = 0.04 mole

0
time

N2O4 2NO2
(a) In a 1.0 L container was placed 4.00 moles of NO(g) and the system was allowed to come to
equilibrium. At equilibrium, 1.82 moles of N2(g) were present. Calculate the moles of the other
gases at equilibrium. The equation is give below. (Ans. 1.82 moles O2; 0.36 mole NO)

2NO(g) k N2(g) + O2(g)

(b) In a 3.0 L container was placed 0.60 mole of NH3(g) and the system was allowed to come to
equilibrium. At equilibrium, 0.18 mole of H2(g) was present. Calculate the moles of the other
gases at equilibrium. The equation is give below. (Ans. 0.06 mole N2; 0.48 mole NH3)

k
k
2NH3(g) N2(g) + 3H2(g)
[see also Ebbing, 14.1 CO(g) + 3H2(g) CH4(g) + H2O(g)]

2. Equilibrium Constant
[NO2]2
At 100°C initial moles/L equilibrium moles/L
[N2O4]
Experiment 1 N2O4 0.10 0.04
0.36
NO2 0.00 0.12

Experiment 2 N2O4 0.00 0.014

0.37
NO2 0.10 0.072

Experiment 3 N2O4 0.10 0.070

0.37
NO2 0.10 0.16
([A] = moles A/L)
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Although the equilibrium concentrations of N2O4 and NO2 vary with their initial concentrations, the
ratio [NO2]2/[N2O4] is constant and is called the Equilibrium Constant, Kc. For a given equilibrium
system, Kc is independent of the initial concentrations, the volume and the total pressure but
depends on the temperature.

For the equation aA + bB k cC + dD, K = [A] [B]

c
[C]c [D]d
a b

[See also Ebbing, pp 601, 602 CO(g) + 3H (g) k CH (g) + H O(g)]

2 4 2

(a) Calculate Kc for 1(a). (Ans. 26)

(b) Calculate Kc for 1(b). (Ans. 1.7 x 10-4)

(c) Consider the equilibrium 2SO2(g) + O2(g) k

2SO3(g)
Into a 1.0 L container were placed 0.0080 mole SO2 and 0.0056 mole O2. At equilibrium, there
was 0.0040 mole of SO3. Calculate Kc. (Ans. 2.8 x 102)

(d) Consider the equilibrium 2NH3(g) + 4H2O(g) k

2NO2(g) + 7H2(g)
Into a 2.0 L container were placed 0.662 mole NH3, 0.122 mole H2O, 0.880 mole NO2 and
2.160 mole H2. When the system had reached equilibrium, there was 0.866 mole of H2O
present. Calculate the equilibrium concentrations of all of the gases and hence Kc.
(Ans. [NH3] = 0.517; [H2O] = 0.433; [NO2] = 0.254; [H2] = 0.429; Kc = 0.0184)

1
(1) Reaction reversed: Kreversed =
Kforward

(2) Reaction multiplied by n: Knew = (Kold)n

(3) Reaction 3 = Reaction 1 + Reaction 2: K3 = K1 x K2

3. Heterogeneous Equilibria
The concentration of pure liquids and solids are constant and hence do not appear in the expression

K
for Kc.
(a) Consider the equilibrium 3Fe(s) + 4H2O(g) Fe3O4(s) + 4H2(g)
In a 3.0 L container is placed 5.0 g of H2O and 3.0 g of Fe. At equilibrium, there was only 2.0
g of Fe present. Calculate Kc for the equilibrium. (Ans. 7.8 x 10-5)

k
4. Qualitative Significance of an Equilibrium Constant
(1) Kc is very small: At 25°C, Kc = 1 x 10-30 for N2(g) + O2(g) 2NO(g)
Very little NO present; negligible Forward Reaction, Backward Reaction goes to completion.
([NO] is so small that it cannot be measured; it must be calculated)

(2) Kc is very large: At 25°C, Kc = 1 x 1038 for 2Cl(g) Cl2(g) k

Very little Cl present; negligible Backward Reaction, Forward Reaction goes to completion.

(3) Kc is neither large nor small:

Both "reactants" (LHS) and "products" (RHS) present in significant amounts. These are the
reactions we are considering.
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k
5. Using Kc to Predict the Direction of Reaction for a System not at Equilibrium
Consider the equilibrium 2SO2(g) + O2(g) 2SO3(g) at a temperature at which Kc = 280.
In a 3.0 L container were placed 1.0 mole SO3, 0.20 mole SO2 and 0.90 mole O2. Is the system at
equilibrium, will the reaction go to the right (form more SO3) or will the reaction go to the left
(form more SO2 and O2) to attain equilibrium? To answer the question, one must compare the
reaction quotient, Qc, with Kc. The expression for Qc has the same form as that for Kc except that the
concentrations are not necessarily the equilibrium concentrations.
2
[SO3]2i  1.0
 3.0
= = 83 ([A]i = moles/L at a particular instant)
[SO2]2i [O2] i 2 0.90
 0.20  
 3.0   3.0 
Qc is less than Kc; hence the reaction will go to the right (more SO3 will form) until Qc = Kc (i.e.,
equilibrium is attained). Obviously, if Qc > Kc, the reaction will go to the left (to produce more
"reactants" and less "products").

(a) Consider the equilibrium 2NO(g) k N2(g) + O2(g) at a temperature at which Kc = 26.
In a 2.0 L container were placed 0.20 mole NO, 1.0 mole O2 and 1.4 mole N2. Will the
reaction go to the left (more NO produced) or to the right (more O2 and N2 produced) as the
system attains equilibrium? (Ans. To the left, since Qc = 35)
(See also Example 14.5, Exercise 14.8 and Problems 14.47 and 14.48)

6. Using Kc to Calculate Equilibrium Concentrations

In the trivial case, the value of Kc and all but one of the equilibrium concentrations are given and the
unknown equilibrium concentration is to be found.

(a) For the equilibrium H2(g) + I2(g) K2HI(g), Kc = 55. Decomposing HI at 55°C gave [HI] at
equilibrium = 0.50 M. Calculate [H2] and [I2] at equilibrium. (Ans. [H2] = [I2] = 0.067 M)
(See also Example 14.6, Exercise 14.9 and Problems 14.51 and 14.52)

More commonly, Kc and the starting amount (or concentration) for one or more of the substances is

K
given and all the equilibrium amounts (or concentrations) are to be calculated. (See Example 14.7)
(b) Consider the equilibrium 2HI(g) H2(g) + I2(g) at the same temperature as the equilibrium
in 6(a). In a 1.0 L container is placed 0.80 mole of HI. Calculate the moles of each substance at
equilibrium. (Ans. 0.63 mole HI, 0.084 mole I2 and 0.084 mole H2)
(See also Exercise 14.10 and Problems 14.53 and 14.54)

(c) To the equilibrium system in 6(b) [i.e., with the molar amounts given in the answer to 6(b)] is
added 0.060 mole H2 and 0.060 mole of I2. Calculate the moles of each substance when
equilibrium has been re-established. (Ans. 0.72 mole HI, 0.097 mole I2 and 0.097 mole H2)

The problems in Example 14.7 and in 6(b) and 6(c) were easily solved since they involved perfect
squares. If perfect squares are not present, a quadratic (or higher order) equation will have to be
solved (See Example 14.8). Because this takes too much time or is too difficult, if such a problem is
given only setting up the expression for Kc will be required.

(d) Consider the system 2NH3(g) k N2(g) + 3H2(g) (Kc = 1.8 x 104)
Into a 4.0 L container was placed 0.80 mole of NH3. What are the equilibrium concentrations?
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7. Effect of Changing the Conditions of an Equilibrium System (Le Chatelier’s Principle).

The most important, and common, reason to change the conditions of an equiluibrium system is to
increase the amount of a desired product. The conditions whose change can affect the equilibrium
composition and hence increase the amount of a desired product are concentration (by adding or
removing any of the gaseous components of the equilibrium system), volume (resulting in a change
of pressure ) and temperature. Le Chatelier’s Principle can be used to predict how the equilibrium
composition will change on changing any of the conditions above. This principle states that when a
system in chemical equilibrium is disturbed by changing concentration, pressure or temperature, the
equilibrium composition changes in a way that tends to offset, or counteract, the change in the
condition(s). In considering changes in concentration and pressure, the equilibrium expression can
also be used.

(1) Changes in Concentration

Increasing a concentration by adding more substance is easy. Decreasing a concentration by
removing a substance is more difficult. Examples are cooling to remove H2O, adding acid to
remove NH3 and NaOH to remove CO2.

(2) Changes in Volume (≡ ≡ Change in Pressure)

When the pressure is increased by decreasing the volume, the system shifts so as to decrease
the number of moles of gas (i.e., in the direction of fewer gas molecules).
Conversely, when the pressure is decreased by increasing the volume, the system shifts so as to
increase the number of moles of gas (i.e., in the direction of more gas molecules).
It follows that if there are the same number of gas molecules on each side of the equation, such
a system is not affected by changes in volume (and hence changes in pressure). Also,
equilibrium systems are not affected by changes in pressure caused by adding an inert
gas (a gas that cannot react with any of the equilibrium components).

Consider the equilibrium N2(g) + 3H2(g)

2
k
2NH3(g)
n
 NH3 n 2 x V2
[NH3]2 V  NH3 (n = moles
Kc = 3 = 3
= 3 V = volume in L)
[N2] [H2] n n x n
 N2  n H2 N2 H2
 V  V 
If V is decreased (P is increased) the numerator will get smaller and hence Qc ≠ Kc. The
system will then shift to make more NH3 by the reaction of N2 with H2 until Qc = Kc (the
system is shifting to the right (in the direction of fewer gas molecules).
For equilibria with the same number of gas molecules on each side, V will not appear in the Kc
expression using moles and hence changing volume will not affect such equilibria.

(3) Changes in Temperature

Increase in temperature favours the endothermic reaction.
Decrease in temperature favours the exothermic reaction.
If the forward reaction is endothermic, Kc increases as T increases.
If the forward reaction is exothermic, Kc decreases as T increases.

Consider the equilibrium: N2O4(g) k 2NO2(g); ∆H = +58.2 kJ

If the temperature is increased, the system will counteract this by trying to get rid of the heat
supplied. To do this, the system will shift to the right (i.e., the forward reaction will proceed
since it is endothermic and will absorb heat).
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3 (a) Consider the equilibrium 3Fe(s) + 4H2O(g) KFe3O4(s) + 4H2(g)

In a 3.0 L container is placed 5.0 g of H2O and 3.0 g of Fe. At equilibrium, there was only 2.0
g of Fe present. Calculate Kc for the equilibrium. (Ans. 7.8 x 10-5)

3.0 L 3Fe(s) + 4H2O(g) K Fe3O4(s) + 4H2(g)

Start: 3.0 g 5.0 g 0 0

0.278 mol

Change: -1.0 g
-0.0179 mol -0.0239 mol +0.0239 mol

Equilibrium: 2.0 g 0.278 mol +0.0239 mol

-0.0239 mol
= 0.254 mol
Moles/L 0.0847 mol/L 0.00797 mol/L

Kc = 0.007974/0.08474 = 7.8 x 10-5

3 (b) Consider the equilibrium C(s) + CO2(g) K

2CO(g).
When this system is at equilibrium in a 2.0 L container at 700°C, there are 0.10 mol CO,
0.20 mol CO2 and 4.8 g C. When cooled to 600°C, an additional 0.48 g of C forms. Calculate
Kc at 700°C and at 600°C. (Ans. 2.5 x 10-2; 8.3 x 10-4)