Topic 7: Equilibrium

7.1 Equilibrium
7.1.1 A state of equilibrium is reached in a close system when the rates of forward and reverse reactions are equal

7.1.2 The equilibrium law describes how the equilibrium constant (Kc) can be determined for a particular chemical reaction

7.1.3 The magnitude of the equilibrium constant indicates the extent of a reaction at equilibrium and is temperature dependent

7.1.4 The reaction quotient (Q) measures the relative amount of products and reactants present during a reaction at a particular
point in time. Q is the equilibrium expression with non-equilibrium concentrations. The position of the equilibrium
changes with changes in concentration, pressure, and the temperature
7.1.5 A catalyst has no effect on the position of equilibrium or the equilibrium constant

7.1.6 The characteristics of chemical and physical systems in a state of equilibrium

7.1.7 Deduction of the equilibrium constant expression (Kc) from an equation for a homogeneous reaction

7.1.8 Determination of the relationship between different equilibrium constants (K c) from an equation for a homogeneous
reaction
7.1.9 Determination of the relationship between different equilibrium constants (K c) for the same reaction at the same
temperature
7.1.10 Application of Le Chatelier’s principle to predict the qualitative effects of changes of temperature, pressure and
concentration on the position of equilibrium and one the value of the equilibrium constant

Dynamic equilibrium
 Chemical equilibrium is a state in which the rate of the forward reaction equals the rate of the backward reaction
 In other words the forward and reverse reactions will continue to occur, but the concentration will stay the same
 Such a system is said to be in a state of dynamic equilibrium. Characteristics of equilibrium include:

Feature of equilibrium state Explanation

The reaction has stopped but both forward and backward reactions are
1 Equilibrium is dynamic
still occurring at the same rate

A closed system prevents exchange of matter with the surroundings, so

2 Equilibrium is achieved in a closed system equilibrium is achieved where both reactants and products can react and
recombine.

The concentrations of reactants and

3 They are being produced and destroyed at an equal rate.
products remain constant

There is no change in macroscopic

4 Color and density do not change as these depend on the concentrations.
properties

Equilibrium can be reached from either

5 The reaction can be started with all reactants, all products or a mixture.
direction (products or reactants)

 Example: In a closed container, liquid bromine is in a dynamic equilibrium with its vapor. There will always be both liquid and
gas bromine in the flask. This state is described as a dynamic equilibrium. Vaporization and condensation are both happening
simultaneously in the flask. Liquid bromine is in dynamic equilibrium with bromine vapour. This can be presented as:
𝐵𝑟2 (𝑙) ⇄ 𝐵𝑟2 (𝑔)
 Dynamic equilibrium can only be established in a closed system where reactants and products cannot escape
Equilibrium Constant: Kc
 An equilibrium reaction can be represented as 𝑎𝐴 + 𝑏𝐵 ⇄ 𝑐𝐶 + 𝑑𝐷
 Lower case letters represent the number of moles (coefficient), the uppercase letters represent the molecule itself
 The equilibrium constant of concentration gives the ratio of concentrations of products over reactants for a reaction that is
at equilibrium. The equilibrium constant expression is written as 𝐾𝑐 and is represented as:

𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠 [𝐶]𝑐 [𝐷]𝑑

𝐾𝑐 = =
𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 [𝐴]𝑎 [𝐵]𝑏
 The value of 𝐾𝑐 represents the position of the equilibrium as equilibrium can either be near the products or reactants
o If 𝐾𝑐 > 1 then equilibrium favors the products
o If 𝐾𝑐 < 1 then equilibrium favors the reactants
 The value of 𝐾𝑐 will remain constant as the system will adjust to keep the concentrations at equilibrium despite its
environment

Le Châtelier’s principle
 Le Châtelier’s principle states that if a dynamic equilibrium is disturbed by changing the conditions the position of
equilibrium shifts to counteract the change to re-establish an equilibrium:

Condition Effect

Increasing concentration shifts the equilibrium to the side with fewer moles of solute
Concentration
Decreasing concentration shifts the equilibrium to the side with more moles of solute

Increasing pressure shifts the equilibrium to the side with fewer moles of gas
Pressure
Decreasing pressure shifts the equilibrium to the side with more moles of gas

 In order to find how temperature change affects equilibrium conditions the sign of the reaction enthalpy must be known to
determine whether the reaction is exothermic or endothermic
 Temperature is the only condition that can change the value of 𝑲𝒄 and the position of the equilibrium

In an exothermic reaction heat can be considered a product, so increasing the temperature will shift the
equilibrium towards the reactants,
Temperature
In an endothermic heat can be considered as a reactant, so decreasing the temperature will shift the
equilibrium towards the products

 A catalyst will lower the activation energy an equal amount for both the forward and reverse reaction
 Therefore catalysts have no effect on the equilibrium constant

Manipulation of Kc
Condition Effect on 𝑲𝑪

Inverse Reaction 1 [𝐴]𝑎 [𝐵]𝑏

𝐾𝑐′ = =
𝐾𝐶 [𝐶]𝑐 [𝐷]𝑑

Multiple of a reaction [𝐶]2𝑐 [𝐷]2𝑑

𝐾𝑐𝑥 =
[𝐴]2𝑎 [𝐵]2𝑏

Adding two reactions 𝐾𝑐1 × 𝐾𝑐2

 Reaction Quotient
 The reaction quotient (𝑄) measures the relative amounts of products and reactants present during a reaction at a particular
point in time. The 𝑄 value can be compared to the Equilibrium Constant, 𝐾𝑐 , to determine the direction of a reaction
o If 𝐾𝐶 = 𝑄 the reaction is at equilibrium
o If 𝐾𝐶 > 𝑄 then Q will increase and produce more products
o If 𝐾𝐶 < 𝑄 then Q will decrease and therefore create more reactants
 The main difference between 𝐾𝑐 and 𝑄 is that 𝐾𝑐 describes a reaction that is at equilibrium, whereas 𝑄 describes a reaction
that is not at equilibrium. To determine 𝑄, the concentrations of the reactants and products must be known:
 A system not at equilibrium can be described as “lying to the left”, indicating that there is a greater amount of reactants or
“lying to the right”, indicating that there is a greater amount of products
 As time passes and the reaction continues, the concentrations of all reaction components change and eventually reach the
equilibrium concentrations. In other words, the value of Q will eventual become 𝐾𝑐

17.1 The equilibrium law

17.1.1 Le Chatelier’s principle for changes in concentration can be explained by the equilibrium law

17.1.2 The position of equilibrium corresponds to a maximum value of entropy and a minimum of the Gibbs free energy

17.1.3 The Gibbs free energy changes of a reaction and the equilibrium constant can both be used to measure the position of an
equilibrium reaction and are related by the equation, ∆𝐺 = −𝑅𝑇𝑙𝑛𝐾
17.1.4 Solution of homogeneous equilibrium problems using the expression for K c

17.1.5 Relationship between ∆𝐺 and the equilibrium constant

17.1.6 Calculations using the equation ∆𝐺 = −𝑅𝑇𝑙𝑛𝐾

Equilibrium calculations
 The equilibrium law can be used either to find the value of the equilibrium constant or to find the value of an unknown
equilibrium constant. The easiest approach for calculating equilibrium concentrations is to use an ICE table, which is an
organized method to track which quantities are known and which need to be calculated. ICE stands for:
o I: The initial concentration or amount
o C: The change in concentration from the initial state to equilibrium
o E: The equilibrium concentration

Calculating the equilibrium concentrations given KC and initial conditions

The equilibrium constant KC for the reaction

SO3 (g) + NO(g) ⇌ NO2 (g) + SO2(g)
was found to be 6.78 at a specified temperature. If the initial concentrations of NO and SO3 were both 0.03 mol
dm-3, what would be the equilibrium concentration of each component?

SO3(g) + NO(g) ⇌ NO2(g) + SO2(g)

Initial 0.03 0.03 0.00 0.00

Change -x -x x x

Equilibrium 0.03 - x 0.03 - x x x

[NO2 ][SO2] 𝑥2
𝐾𝐶 = = = 6.78
[SO3][NO] (0.03 − 𝑥)2

Solving a quadratic gives the value of 𝑥.

 Make sure the volume of the vessel is 1. Otherwise divide the equilibrium
Gibbs free energy and Equilibrium
 Equilibrium occurs when the reaction is at a minimum value of Gibbs free energy and a maximum value of entropy
 The formula for Gibbs free energy is:

∆𝐺 𝜃 = 𝑅𝑇 ln 𝐾