Lecture 4: Chemical Equilibrium

Objectives:
• Define chemical equilibrium and calculate equilibrium constant.
• Define and discuss Le Châtelier's Principle.
• Solve a variety of chemical equilibrium problems.

Lecture Notes:
A chemical reaction can achieve a state in which the forward and reverse processes are occurring at the same rate.
This condition is called chemical equilibrium, and it results in the formation of an equilibrium mixture of the
reactants and products of the reaction. The composition of an equilibrium mixture does not change with time if
temperature is held constant. An example of this is the conversion of N2O4, a colorless substance that dissociates
to form brown NO2.
A frozen N2O4 sample is nearly colorless. On warming, the N2O4
becomes a gas and partially dissociates to form brown NO2(g).
Colors stop changing, equilibrium reached: rate of reaction N2O4(g)
→ NO2(g) = rate of reaction 2 NO2(g) → N2O4(g). The equilibrium
mixture results because the reaction is reversible: N2O4 can form
NO2, and NO2 can form N2O4. Dynamic equilibrium is represented by
writing the equation for the reaction with two half arrows pointing in
opposite directions:
N2O4(g) ⇌ 2 NO2(g)
colorless brown
We can write the decomposition of N2O4 the forward reaction and the formation of N2O4 the reverse reaction and
their individual rate laws as:
Forward reaction: N2O4(g) → 2 NO2(g) Ratef = kf [N2O4]
Reverse reaction: 2 NO2(g) → N2O4(g) Rater = kr [NO2]2
At equilibrium, the rate at which NO2 forms in the forward reaction equals the rate at which N2O4 forms in the
reverse reaction:
kf [N2O4] = kr [NO2]2
Rearranging this equation gives:
[NO2 ]2 kf
= = a constant
[N2 O4 ] kr
Remember always:
• At equilibrium, the concentrations of reactants and products no longer change with time.
• For equilibrium to occur, neither reactants nor products can escape from the system.
• At equilibrium, a particular ratio of concentration terms equals a constant.

An equilibrium that is used throughout this chapter is the reaction N2(g) + 3 H2(g) ⇌ 2 NH3(g). This reaction is the
basis of the Haber process for the production of ammonia. The relationship between the concentrations of the
reactants and products of a system at equilibrium is given by the law of mass action. For an equilibrium equation of
the form a A + b B ⇌ d D + e E, the equilibrium constant expression is written as
[D]d [E]e
Kc = a b
[A] [B]
where Kc is a dimensionless constant called the equilibrium constant. When the equilibrium system of interest
consists of gases, it is often convenient to express the concentrations of reactants and products in terms of gas
pressures:
(PD )d (PE )e
Kp =
(PA )a (PB )b
Kc and Kp are related by the expression Kp = Kc (RT)∆n. To do this conversion properly, use
R = 0.08206 L-atm/mol-K and temperature in kelvins.
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→ Worked Examples:
Write the equilibrium-constant expression of the Haber process.
Solution: The Haber process has a reaction N2(g) + 3 H2(g) ⇌ 2 NH3(g). Using the equilibrium constant expression
formula
[D]d [E]e products
Kc = a b
[A] [B] reactants
we can assume that:
1. The numerator of the equilibrium-constant expression is the product of the concentrations of all substances on
the product side of the equilibrium equation, each raised to a power equal to its coefficient in the balanced
equation.
2. The denominator is similarly derived from the reactant side of the equilibrium equation.
Therefore, the equilibrium-constant expression for the Haber process is:
[NH3 ]2
Kc =
[N2 ][H2 ]3

→ Exercises:
Write the equilibrium-constant expression for the following reaction.
• 2 O3(g) ⇌ 3 O2(g)
• 2 NO(g) + Cl2(g) ⇌ 2 NOCl(g)
• Ag+(aq) + 2 NH3(aq) ⇌ Ag(NH3)2+(aq)
[SO ]2
3
Write the reaction for the equilibrium-constant expression: Kc = [O ][SO ]2
.
2 2

The value of the equilibrium constant changes with temperature. A large value of Kc indicates that the equilibrium
mixture contains more products than reactants and therefore lies toward the product side of the equation. A small
value for the equilibrium constant means that the equilibrium mixture contains less products than reactants and
therefore lies toward the reactant side. The equilibrium-constant expression and the equilibrium constant of the
reverse of a reaction are the reciprocals of those of the forward reaction. If a reaction is the sum of two or more
reactions, its equilibrium constant will be the product of the equilibrium constants for the individual reactions.

Equilibria for which all substances are in the same phase are called homogeneous equilibria; in heterogeneous
equilibria, two or more phases are present. Because their activities are exactly 1 the concentrations of pure solids
and liquids are left out of the equilibrium-constant expression for a heterogeneous equilibrium.

If the concentrations of all species in an equilibrium are known, the equilibrium-constant expression can be used to
calculate the equilibrium constant. The changes in the concentrations of reactants and products on the way to
achieving equilibrium are governed by the stoichiometry of the reaction.

The reaction quotient, Q, is found by substituting reactant and product concentrations or partial pressures at any
point during a reaction into the equilibrium-constant expression.
• If the system is at equilibrium, Q = K.
• If Q ≠ K, however, the system is not at equilibrium.
• When Q < K, the reaction will move toward equilibrium by forming more products (the reaction proceeds from
left to right).
• When Q > K, the reaction will move toward equilibrium by forming more reactants (the reaction proceeds from
right to left).
Knowing the value of K makes it possible to calculate the equilibrium amounts of reactants and products, often by
the solution of an equation in which the unknown is the change in a partial pressure or concentration.

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Le Châtelier’s principle states that if a system at equilibrium is disturbed, the equilibrium will shift to minimize the
disturbing influence. Factors that may affect include:
1. Concentration: adding or
removing a reactant or
product. If a substance is
added to a system at
equilibrium, the system reacts to consume some of the substance. If a substance is removed from a system,
the system reacts to produce more of substance.
2. Pressure: changing the pressure by changing the volume. At constant
temperature, reducing the volume of a gaseous equilibrium mixture
causes the system to shift in the direction that reduces the number of
moles of gas.
3. Temperature: If the temperature
of a system at equilibrium is
increased, the system reacts as if
we added a reactant to an
endothermic reaction or a product to an exothermic reaction. The equilibrium shifts in the direction that
consumes the “excess reactant,” namely heat.

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