2.

Solving Equilibrium Problems

• Two basic flavors of chemical equilibrium problems

1. Equilibrium quantities are given (concentrations or partial

pressures) and we solve for Kc. This is easy plug and chug.

2. Kc and initial quantities are given and we solve for the

equilibrium concentrations.

In either case we can use a book-keeping technique

Initial, Change Equilibrium Method
Using ICE Book-keeping
1. Alway write a balanced chemical equation.
2. Make an organized table with a balanced equation at the top
followed by a row of initial concentrations of reactants and
products, another row of changes in concentrations of reactants
and products and a final row of equilibrium concentrations.
3. Use as the unknown variable x for one substance and use the
stoichiometry to determine relative concentrations of other
reactants and products. Think, before choosing the x-variable.
6. Substitute the equilibrium concentrations into the equilibrium
expression from the balanced equation.
7. Solve the equation for x
8. Answer the questions, remember significant figures.
Determining equilibrium concentrations from Kc

PROBLEM:

In a study concerning the conversion of methane to other

fuels, a chemical engineer mixes gaseous CH4 and H2O in a
0.32 L flask at 1200 K. At equilibrium, the flask contains 0.26
mol of CO, 0.091 mol of H2, and 0.041 mol of CH4. What is
the [H2O] at equilibrium? A Handbook states that Kc = 0.26
for this reaction is:

CH4(g) + H2O(g) CO(g) + 3H2(g)

PLAN: Use the balanced equation to write the Kc expression, and then
substitute values for each component.

SOLUTION: [CO][H2 ]3
Kc =
[CH4 ][H2 O]

concentration (M) CH4(g) + H2O(g) CO(g) + 3H2(g)

initial ? ? ? ?
change ? ? ? ?
equilibrium 0.041 mol/0.32 L ? 0.26mol 0.091 mol
0.32 L 0.32 L
= 0.13 M
= 0.81 M = 0.28 M

[CO]eq[H2]eq3 (0.81)(0.28]3
[H2O]eq = = = 0.53 M
[CH4]eq Kc (0.13)(0.26]
Calculating Kc from concentration data
PROBLEM: In a study of hydrogen halide decomposition, a researcher
fills an evacuated 2.00 L flask with 0.200 mol of HI gas and
allows the reaction to proceed at 453oC. At equilibrium, it
is found that the concentration of [HI] = 0.078 M. What is
the equilibrium constant Kc?

2HI(g) H2(g) + I2(g)

PLAN:

Find the molar concentration of the starting material (in this

case [HI] and then use algebra and the balanced chemical
equation to determine the amount of reactants and
products at equilibrium.
SOLUTION: 2HI(g) H2(g) + I2(g)

0.200 mol
[HI] = = 0.100 M
[H2] [I2] 2.00 L
Kc =
[HI]2
concentration (M) 2HI(g) H2(g) + I2(g)

initial 0.100 0 0
change -2x x x
equilibrium 0.100 - 2x x x

The problem said that: [HI]eq = 0.078 M

[HI]eq = 0.078 M = 0.100 - 2x ; x = 0.011 M

[H2] [I2] = [0.011][0.011]

Kc = = 0.020 = Kc
[HI]2 [0.078]2
Determining equilibrium concentrations from initial
concentrations and Kc

PROBLEM:

Fuel engineers use the extent of the change from CO and H2O to
CO2 and H2 to regulate the proportions of synthetic fuel mixtures. If
0.250 mol of CO and 0.250 mol of H2O are placed in a 125 mL flask
at 900K, what is the composition of the mixture at equilibrium? At
900K, Kc is 1.56 for this reaction.

CO(g) + H2O(g) CO2(g) + H2(g)

PLAN: 1)Balance equation, 2)write equilibrium expression, 3)

set up ICE table, 4)find the concentrations of all species
at initial conditions or equilibrium in the problem 5)use
algebra to determine equilibrium concentrations and then
substitute into a Kc expression.
SOLUTION: Initial concentrations must be calculated as M, we have
from the data given [CO] = [H2O] = 0.250/0.125L = 2.00M.

concentration CO(g) + H2O(g) CO2(g) + H2(g)

_________________________________________________
initial 2.00 2.00 0 0
change -x -x x x
equilibrium 2.00 -x 2.00 -x x x

[CO2 ][H2 ] x2 x2
Kc = = = = 1.56
[CO][H2 O] (2.00 − x)(2.00 − x) (2.00 − x)2

x √
= 1.56 = ±1.25 (the negative result is ignored)
2.00 − x
2.00 - x = 0.89 M
x = 1.25(2.00 − x) = 2.50 − 1.25x
[CO] = [H2O] = 0.89 M
2.25x = 2.50
x = 1.11M [CO2] = [H2] = 1.11 M
 A wee-bit tougher ICE problem

At 1280˚C the equilibrium constant (Kc) for the reaction

Br2 (g) 2Br (g)
is 1.1 x 10-3. If the initial concentrations are [Br2] =
0.063 M and [Br] = 0.012 M, calculate the
concentrations of these species at equilibrium.
1. Write Balanced Equation Br2 (g) 2Br (g)
[Br]2
2. Write Equilibrium Expression Kc =
[Br2]
3. Set Up ICE Table
Br2 (g) 2Br (g)
Let x
be the
Initial (M) [0.063] [0.012] change
Change (M) -x +2x in
concent
Equilibrium (M) 0.063 - x 0.012 + 2x
ration
of Br2
[Br]2 (0.012 + 2x)2
Kc = = Kc = = 1.1 x 10-3
[Br2] 0.063 - x
Solve for x using quadratic equation
 (0.012 + 2x)2
Kc = = 1.1 x 10-3
0.063 - x
4x2 + 0.048x + 0.000144 = 0.0000693 – 0.0011x
4x2 + 0.0491x + 0.0000747 = 0
-b ± !b2 – 4ac
x=
2a
ax2 + bx + c =0
x = -0.0105 x = -0.00178

Br2 (g) 2Br (g)

Two solutions
Initial (M) [0.063] [0.012]
Change (M) -x +2x
Equilibrium (M) 0.063 - x 0.012 + 2x

At equilibrium, [Br] = 0.012 + 2x = -0.009 M and 0.00844 M

At equilibrium, [Br2] = 0.062 – x = 0.06378 M
PROBLEM: Phosgene is a potent chemical warfare agent that is now
outlawed by international agreement. It decomposes by
the reaction,

COCl2(g) CO(g) + Cl2(g) Kc = 8.3 x 10-4 (at 360 oC)

Calculate [CO], [Cl2], and [COCl2] at equilibrium when the initial

amount of phosgene gas is 0.100 mol in a 10.0 L flask.

Given information in the problem

[COCl2] = 0.100 mol/10.0 L = 0.0100 M

Kc = 8.3 x 10-4 (at 360 oC)

 COCl2(g) CO(g) + Cl2(g)
[CO] [Cl2]
Kc = 8.3 x 10-4 =
[COCl2]

COCl2(g) CO(g) + Cl2(g)

Initial (M) 0.010 0.0 0.0

Change (M) -x +x +x
Equilibrium (M) 0.010 - x x x

(x) (x)
Kc = 8.3 x 10-4 =
(0.010 - x)
 (x) (x)
(continued) Kc = 8.3 x 10-4 =
(0.010 - x)
Kc = 8.3 x 10-4 (0.010 - x) = x2

Kc = 8.3 x 10-6 - 8.3 x 10-4 x = x2

Kc = x2 + 8.3 x 10-4 x - 8.3 x 10-6 = 0

a=1 ax2 + bx + c =0
b = 8.3 x 10-4
c = - 8.3 x 10-6
-b ± !b2 – 4ac
x=
2a

Solving for x yields x = 2.5 x 10-3 M and 0.0100 - x = 7.5 x 10-3 M.

[CO] + [Cl2] [COCl2]

 (x) (x)
(continued) Kc = 8.3 x 10-4 =
(0.010 - x)
Kc = 8.3 x 10-4 (0.010 - x) = x2
Kc = 8.3 x 10-6 - 8.3 x 10-4 x = x2
Kc = x2 + 8.3 x 10-4 x - 8.3 x 10-6 = 0

ax2 + bx + c =0 a = 1
! b = 8.3 x 10 -4
-b ± b – 4ac
2
x=
2a c = - 8.3 x 10-6
4 a c = 4 x 1 x - 8.3 x 10-6
b2 = (8.3 x 10-4)2 = 6.89 X 10-7
c = - 8.3 x 10-6 -3 M
Solving for x yields x = 2.5 x 10
c = - 8.3 x 10-6 -3
and 0.0100 - x = 7.5 x 10 M.
Predicting reaction direction and calculating equilibrium
concentrations
The research and development unit of a chemical company is
studying the reaction of CH4 and H2S, two components of natural gas.

CH4(g) + 2H2S(g) CS2(g) + 4H2(g)

In one experiment, 1.00 mol of CH4, 1.00 mol of CS2, 2.00 mol of
H2S and 2.00 mol of H2 are mixed in a 250 mL vessel at 960 oC.
At this temperature, Kc = 0.036.
(a) In which direction will the reaction proceed to reach
equilibrium?
(b) If [CH4] = 5.56 M at equilibrium, what are the equilibrium
concentrations of the other three substances?
PLAN: Find the initial molar concentrations of all components and use these to
calculate Qc. Compare Qc to Kc, determine in which direction the reaction
will progress, and draw up expressions for the equilibrium concentrations.
SOLUTION:

[CH4]initial = 1.00 mol/0.25 L = 4.00 M

[CS2]initial = 1.00 mol/0.25 L = 4.00 M
[H2S]initial = 2.00 mol/0.25 L = 8.00 M
[H2]initial = 2.00 mol/0.25 L = 8.00 M

[CS2][H2]4 =
[4.0][8.0]4
Qc = = 64.0
[CH4][H2 S]2 [4.0][8.0]2

Qc of 64 is >> than Kc = 0.036

The reaction will progress to the left.

CH4(g) + 2H2S(g) CS2(g) + 4H2(g)

SOLUTION:

concentrations CH4(g) + 2H2S(g) CS2(g) + 4H2(g)

______________________________________________________
initial 4.00 8.00 4.00 8.00

change +x + 2x -x - 4x

equilibrium 4.00 + x 8.00 + 2x 4.00 - x 8.00 - 4x

At equilibrium [CH4] = 5.56 M, so 5.56 = 4.00 + x; thus,

x = 1.56 M

[H2S] = 8.00 + 2x = 11.12 M

Therefore:
[H2] = 8.00 - 4x = 1.76 M

[CS2] = 4.00 - x = 2.44 M