Study unit 8: Chemical equilibrium / Fundamental

Equilibrium Concepts

• By equilibrium we mean a “state of balance”.

• How would this apply to a chemical reaction?

• Remember, reactions could go from reactants to products, as well as
from products to reactants (at least in theory).
• In other words, a reaction consists of both a forward reaction and a
reverse reaction.
• For example, hydrogen cyanide (HCN) reacts with potassium
hydroxide (KOH) to give potassium cyanide (KCN) and water. This is
the forward reaction.

Forward: HCN + KOH → KCN + H2O

At the same time, KCN and H20 that have formed during the
forward reaction can react backwards to form HCN and KOH. This is
the reverse reaction.
• Reverse: KCN + H2O → HCN + KOH

• To indicate that a reaction consists of both a forward and a reverse

reaction, it is often written with a double arrow:

At equilibrium, the forward rate is equal to the reverse rate

 THE EQUILIBRIUM CONSTANT
• Consider the reaction:

where a, b, c and d are the stoichiometric coefficients of A, B, C and D respectively.

At equilibrium, the forward rate is equal to the reverse rate

The equilibrium constant expression is given by:

Note that the value of Kc does not depend on initial concentrations of reactants or
products. Kc is a function of temperature, so its value changes only if the temperature
changes.
• By definition, Kc is always written as the product of the
concentrations of the substances on the Right-Hand side (RHS) of
the balanced chemical equation divided by the product of the
concentrations of the substances on the LHS.

• In addition, each concentration raised to the power of its

respective stoichiometric coefficients in the balanced chemical
equation.
Homogeneous Equilibria
• A homogeneous equilibrium is one in which all reactants and
products (and any catalysts, if applicable) are present in the same
phase.

• By this definition, homogeneous equilibria take place in solutions.

• These solutions are most commonly either liquid (aq) or gaseous

phases (g)
 Consider the following homogeneous reaction:
• N2 (g) + O2 (g) ↔ 2NO (g),
• Equilibrium constant (Kc) in terms of concentration will be:

The partial pressure of a gas in a gas mixture is proportional to that component’s concentration (C).

or

This proves that partial pressure is proportional to concentration. Similarly, as in Kc the Equilibrium
constant (Kp) in terms of partial pressure will be:
Other examples are shown below
INTERPRETING EQUILIBRIUM CONSTANTS
• The equilibrium constant, Kc, is the ratio of products to reactants. Recall that:

kf and kr are the rate constants of the forward and reverse reactions respectively.

• If kf is larger than kr, then Kc is larger than 1 and there will be more products
than reactants at equilibrium.

• Thus, if KC > 1, then products dominate at equilibrium and the equilibrium lies
to the right of the reaction equation.

• Conversely, if KC < 1, then reactants dominate at equilibrium and the

equilibrium lies to the left of the reaction equation, and there will be more
reactants than products.
 Equilibrium in Heterogeneous reactions

• A Heterogeneous reaction is the reaction in which all the products and reacts are
not in the same phase. A heterogeneous equilibrium involves reactants and
products in two or more different phases, as illustrated by the following
examples:

• Consider the following Gas-Solid equilibrium reaction:

• BaCO3 (s) ↔ BaO (s) + CO2 (g)

• The concentration of any pure solid or liquid is always constant,

because the density of a pure solid or pure liquid is always the same.

• As a result, the pure solids (s) and liquids (l) taking part in
heterogeneous equilibrium are not included in the equilibrium
constant expression.
It follows that the equilibrium constant Kc from the above reaction is:

• Kc = [CO2] ,,., in terms of concentration

• And, Kp = PCO2 ,,,,,in terms of partial pressure

• Similarly, for the following Gas-Liquid equilibrium reaction:

• 2A (ℓ) + 2BC (g) ↔ C2 (g) + A2B2 (ℓ)
Other examples:

Note that concentration terms, [ ] are only included for gaseous and solute species (dissolved species in
aqueous solutions), when we write equilibrium constant in terms of KC, but we include p in terms of KP.
The direction of the reaction
• Consider the reaction: 2A + B ↔ A2B,
• The mass action expression (Q) for the reaction is:

• In this case we do not know if the reaction is in equilibrium. To test

the status for this reaction (reverse, forward, or equilibrium), we must
find a value for Q by substituting the given concentrations in it.
 Example:
• The equilibrium constant for the reaction: 2SO2 (g) + O2 (g) ↔ 2SO3 (g)

• is Kp = 0.14 atm-1 at 900 K.

• If a reaction vessel is filled with SO3 at a partial pressure of 0.10 atm and with
O2 and SO2 each at a partial pressure of 0.20 atm, is the reaction at
equilibrium? If not, in what direction will it proceed?

• Now, Q > K, and the reaction is not at equilibrium. The reaction will proceed
to decrease the value of Q – thus, more S02 and O2 will be formed, and SO3
will decrease, i,e, the reaction will proceed to the LHS to eventually reach the
equilibrium.
The principle of Le Chatelier’s Principle.

• Le Chatelier ‘s principle states that:

• When a chemical system is in equilibrium and one of the factors

affecting the reaction is changed so that the system is no longer in
equilibrium, the system itself will change so as to counteract the
external change and that a new equilibrium is re-established.
Summary of Factors that affect the position of equilibrium reaction
mixture at equilibrium.

• For a Temperature increase in a chemical reaction:

A decrease in reaction temperature will cause the opposite of above to occur.

Increase of pressure of the reaction system:
• Le Chatelier’s states that the reaction will react by changing in such a way that
the pressure change will decrease. This can be achieved by having a smaller
number of gas molecules in a balanced chemical reaction. The equilibrium will
shift to the side having least / smaller number of gas molecules in a balanced
chemical reaction.

• Consider the reaction: 4A3 (g) + 3BC (g) ↔ 3ABC (g) + 9A (s)

• Note that there are 7 moles on the LHS and only 3 on the RHS

• An increase of pressure of the above reaction system, will cause the equilibrium
to shift to the RHS (the side will smaller number of gas molecules, 3 in this case)

• A decrease of pressure will cause the opposite (i,e, the equilibrium to shift to the
LHS (the side will higher number of gas molecules, 7 in this case)

In a reaction with the same number of moles of gas in the products and reactants, changing the pressure has
no effect on the equilibrium.
Addition of a catalyst

• Catalysts or inert substances (such as Helium, Argon) does not affect

the position of equilibrium at all.

• No change will occur if we increase the total gas pressure by the

addition of a gas that is not involved in the reaction, for example an
inert gas such as helium, neon or argon.

• In other words, helium, neon or argon are considered catalysts in this

case.
 Effect of Concentration

In the above table, RHS = products,

and LHS = reactants
Examples
• We are reacting nitrogen with hydrogen according to the reaction:
• N2 (g) + 3 H2 (g) ↔ 2 NH3 (g)

• The reaction is initially at equilibrium. How will the system react if by

accident, the nitrogen valve is opened, and more N2 is pumped into
the system? i,e. more of N2 in increased .

• Answer:

• Note that p is proportional to C, so an increase of N2 (LHS) will cause

the equilibrium to shift to the RHS (i,e, more NH3 will form).
Example:
• For the equilibrium:

• 2 SO2 (g) + O2 (g) ↔ 2 SO3 (g) ΔHo = -198 kJ

• What will be the effect on the equilibrium concentration of SO3 of

each of the following changes?
(i) Doubling the volume of the reaction vessel
(ii) Increasing the temperature at constant volume
(iii) Adding more O2 to the reaction vessel
(iv) Adding helium to the reaction vessel at constant volume
Answers
(i) According to Boyle’s law: an increase in volume is equivalent to a
decrease in pressure, so a decrease in pressure of the reaction system
will cause the reaction system to shift to the higher number of gas
molecules (in this case to the LHS, so [SO3] will decrease).
(notice that there are 3 moles on LHS and 2 on RHS)

(i) The reaction is Exothermic (a negative value of ΔHo ), equilibrium shift

to LHS, so the [SO3] will decrease
(iii) Increase of LHS (O2), will cause the Equilibrium to shift to the
RHS, so [SO3] will increase

(iv) Helium is an inert substance, there will be no effect.