CHEMICAL EQUILIBRIUM

Most chemical reactions seem to have gone to completion, that is, all the reactants appear to have been converted
to products. Sometimes, however, reactants can come together and form products and products can come together to re-
form reactants. This is called Chemical Equilibria. An irreversible reaction is one that reaches completion.

Reversible Reactions
 A reaction where there are two opposing processes occurring simultaneously and does not go to completion and
thus attain chemical equilibria. ∆G=0
 Experiments show that complete conversion of reactants to products does not really occur in most chemical
reactions
 When all apparent chemical change has ceased, there are usually significant amounts of the reactants and
products present in the reaction mixture. This is because as soon as enough products are produced, they begin to
react with each other to reform the reactants
 Just as the reactants interact to form the products in the forward direction, the products also interact to form back
the reactants, in the opposite/reverse direction
 The forward and reverse reactions do not stop once equilibrium has been achieved. The reactants and products
continue to react since the rates of forward and backward reactions are equal, the net concentrations of the
reactants and products do not change.
Law of Mass Action
 For the rate determining step in a reaction, the rate of the reaction is proportional to the products of the
concentrations of the reactants, each raised to the power of its coefficient in the balanced equation.
 Cato Goldberg and Peter Waage
 aA +bB ⇌ cC + dD
K= [C]c[D]d
[A]a[B]b

 The exponents are respective coefficients in the balanced equations.

 The equilibrium constant (K) has no unit.

Equilibrium Constant (K)

 ratio of product to reactants
 it is not the absolute value of moles that is the important quantity, but rather the concentration (M)  Kc (Equilibrium
Constant for Concentration)
 Since the partial pressure of a gas is a measure of its concentration, for reactions in which all the reactants and
products are gases, the equilibrium constant expression may be expressed in terms of partial pressures instead of
molar concentrations  Kp (Equilibrium Constant for Partial Pressures)
 The value of K is not changed by catalysts. It varies with temperature, so it should always be stated.
 Sample
Homogenous Equilibrium Heterogenous Equilibrium
CO(g)+2H2(g)⇌CH3OH(g) 2NaHCO3(s)⇌Na2CO3(s)+H2O(g)+CO2(g)
Kp= [CH3OH]
[CO][H2]2 Kp= [H2O] [CO2]

N2(g)+3H2(g)⇌2NH3(g) C(s)+O2(g)⇌CO2(g)
Kp= [NH3]2 Kp= [CO2]
[N2] [H2]3 [O2]
 Kc= 1
[C]

Reactant (left) ⇌Product (Right)

Magnitude of K Position of Equilibrium

K>1 Equilibrium favors the products. (forward reaction)
Equilibrium lies to the right.
K<1 Equilibrium favors the reactants. (Backward Reaction)
Equilibrium lies to the left.
K=1 Both the reactants and the products are present at equilibrium.

Sample Problems
 Calculate K for the reaction between the general reactants A2 and B2. A2+ B2 ⇌ 2AB The equilibrium concentrations
are as follows: [A2]= 0.25 M; [B] = 0.25 M and [AB]= 0.5 M. K=4, favors the products, to the right
 Calculate K for the reaction of N2 and H2 to form NH3, with the given balanced equation and the following equilibrium
concentrations: [N2] = 0.12 M; [H2] = 0.36 M; [NH3] = 1.1M.
N2(g) + 3 H2(g) ⇌ 2 NH3(g) K=216, favors the products, to the right

Le Chatelier’s Principle
 If a chemical system at equilibrium is disturbed or stressed, the system will react in
the direction that counteracts the disturbance or relieves the stress
 Henri Le Chatelier

Source of Stress Effect on Equilibrium

Concentration Adding Reactant Equilibrium favors the products.
Removing reactant Equilibrium favors the reactants.
Adding product Equilibrium favors the reactants.
Removing product Equilibrium favors the products.
Temperature Increasing Endothermic Equilibrium favors the products.
temperature Reaction
Exothermic Equilibrium favors the reactants.
Reaction
Decreasing Endothermic Equilibrium favors the reactants.
temperature Reaction
Exothermic Equilibrium favors the products.
Reaction
Pressure Increasing pressure Equilibrium favors the side that has fewer
moles.
Decreasing pressure Equilibrium favors the side that has more
moles.
Volume This quantity is inversely proportional to pressure, therefore, use the rules for
pressure.
Catalysts No effect
Sample Problems
In which direction is the equilibrium shifted with each of the following concentration changes for the reaction that follows:
2SO2(g) + O2(g) ⇌ 2SO3(g) ΔH=-22kJ (exothermic)
1. Increase of concentration in SO2 right
2. Increase of concentration in SO3 left
3. Decrease of concentration in O2 left
4. Decrease of concentration in SO3 right
5. Increase in temperature left
6. Decrease in temperature right

Activity 9.
1. Write the expression for Kc and Kp for the following reactions. Indicate whether the equilibrium is homogenous or
heterogenous.
a. 3O2(g) ⇌ 2O3(g)
b. Bi2S3(s) ⇌ 2 Bi3+(aq) + 3S2-(aq)
2. Write the chemical equation for an equilibrium system that would give the expression for K.
Kp= [CO2] [H2O]2
[CH4][O2]2

3. For the reaction, C6H6 (g) + 3H2 (g) ⇌ C6H12 (g) + heat, determine the direction of equilibrium as a result of the following
changes.
a. Increasing the concentration of H2
b. Decreasing the concentration of C6H6
c. Removal of C6H12
d. Increasing the temperature
e. Decreasing the pressure by increasing the volume of the container
4. For the following reaction: 6CO2(g) + 6H2O(l) ⇌ C6H12O6(s) + 6O2 (g), determine the direction of the shifts under the
following conditions.
a. Decreasing the temperature
b. Increasing pCO2
c. Increasing the total pressure
d. Adding a catalyst
5. Consider the exothermic reaction: C2H4(g) + Cl2(g) ⇌C2H4Cl(g). What effect does each of the following changes have
on the direction of equilibrium?
a. Increase C2H4
b. Decrease Cl2
c. Decrease C2H4Cl
d. Decrease pressure
e. Increase temperature
f. Decrease temperature
6. Calculate the equilibrium constant for each reaction using the balanced chemical equations and the concentrations
of the substances at equilibrium.
a. CO(g) + H20(g) ⇌ CO2(g) + H2(g) ΔH=2816 kJ
[CO] = 0.0236 M [H20] = 0.00240 M
[CO2] = 0.0164 M [H2] = 0.0164 M
b. 2 NO2(g) ⇌ N2O4(g)
[NO2] = 0.0760 M [N2O4] = 1.26 M