Chemical Equilibria

1. General Equilibria

1.1 Reversible and irreversible reactions

1.2 Chemical Equilibrium Condition

1.3 Homogeneous and Heterogeneous Equilibria

1.4 Equilibrium constants

1.5 Writing Equilibrium Constants

1.6 Le Chartelier’s Principle

1.7 Factors Affecting Equilibrium

1.8 Predicting Shifts in Equilibrium

2. Ionic Equilibria

2.1 Acid Base Theories

2.2 Strength of Acids and Bases

2.3 PH, pOH, Ka, Kb, Kw

2.4 Buffer Solutions

3. Solubility Equilibria

3.1 Partially Soluble Solids

3.2 Solubility and solubility Product

3.3 Common ion Effect

1.1 Reversible and Irreversible Reactions

Often reactions are assumed to proceed to completion, which means that reactants or one
of them (limiting reagent) run out. This is true for a number of reactions. The amount of
products formed are dependent on the quantity of the limiting reactant if the reactants
were not mixed in stoichiometric ratio. Such reactions that proceed to completion are called
irreversible reactions.

On the other hand, there are reactions that do not go to completion. Eventually it is noted
that there is no change in the quantities of substances present in the reaction mixture with
time. Both reactants and products will be present. However if certain conditions such as
temperature or pressure, are altered, the quantities in the mixture do change. Reactions
that do not go to completion are referred to as reversible reactions.

Reversible reactions consist of two reactions that occur at the same time. A forward and a
backward reaction.

Reactants react to form products and as soon as products are formed they in turn react or
decompose to reform the reactants. (Double arrow ndiyo inoreva kuti reaction iri reversible/
idouble arrow itsho ukuba ireaction irreversible)

The two reactions proceed at different rates initially, and a net increase /decrease in
products/reactants is observed. With time, a state in which there is no change in the
quantities of reactants and products is reached. Analysis of the reaction mixture would
reveal that both reactants and products are present. At this point the reaction is perceived
to have stopped, however, in reality the reaction does not stop but it reaches a point where
the rate of the forward reaction equals the rate of the backward reaction. This is called the
position of equilibrium. It is a position where the rates of the opposing reactions balance up.
The reactions do not stop (they are not static) hence the state is referred to as dynamic
equilibrium.

Consider, the decomposition of N2O4 to form NO2. The two graphs below illustrate what
happens to two parameters i.e concentration of reactants and productions with time and,
Rate (speed) of forward and backward reactions with time.
The dotted lines denote the instances when equilibrium is attained. The graphs flatten
thereafter showing no further change with time.

Consider the Haber process, i.e the formation of NH3 from H2 and N2. The forward reaction
would be the formation of ammonia and the backward reaction is the decomposition of
NH3. Equilibrium can be illustrated either starting with reactants ( H2 and N2) or with NH3.
Remember what is started with exists and has a concentration greater than 0 (zero) and the
substance that is being formed does not exist initially and therefore in a graph its initial
concentration is zero.
 Note that the concentrations of the components of the reaction at equilibrium are the same
in each graph illustrating that, the same equilibrium is achieved from either direction.

1.2 Chemical Equilibrium Condition

The State of equilibrium is achieved if reaction takes place in a closed system. None of the
reactants and products should escape.
Equilibrium lies to the right if at equilibrium, there are more products than reactants and
equilibrium lies to the left if at equilibrium there are more reactants than products.
The thermodynamic nature of reversible reactions is always such that if the frward reaction
is endothermic, then the backward reaction is exothermic and vice versa.

1.3 Homogeneous and Heterogeneous Equilibria

This classification is based on the physical state of reactants and products. The states
referred to are (s) for solid, (g) for gas, (l) for pure liquid and (aq) for aqueous solutions.

Two ways of classification of equilibria based on the above description are: Homogeneous
equilibria and Heterogeneous equilibria.

Homogeneous equilibria

Reactants and products are in the same phase

N2(g) + 3H2(g) ↔ 2NH3(g) All Gaseous

2SO2(g) + O2(g) ↔ 2SO3(g) all gaseous

CH3CO2H (aq) ↔ CH3CO2-(aq) + H+(aq) all aqueous

Heterogeneous equilibria

At least one reactant or product is in a different state to others

CaCO3 (s) ↔ CaO(s) + CO2(g) solid and gas

present

Zn (s) + Cu2+(aq) ↔ Zn2+(aq) + Cu(s) solid and aqueous

1.4 Equilibrium constants

 To what extent does a reaction go?
What is the amount of product at equilibrium?

The equilibrium constant (Kc) is a tool that enables us to make quantitative measurements
regarding equilibrium. It is based on the law of mass action which for a reaction of this
general nature:

can be expressed as

Large Caps represent reactants and products

Exponents in the Kc expression are derived from small caps which are coefficients used to
balance the reaction

[ ] refer to concentration (i.e square brackets)

At a specific temperature, Kc is constant
Equilibrium lies to the left if Kc has a small value and equilibrium lies to the right when Kc
has a large value.

When conditions are such that, equilibrium is not established, then the ratio of the product
to the reactants gives a reaction quotient instead of the equilibrium constant.
(formula ye Kc yakafanana ne ye reaction Quotient (Q ) kurutive rwe rudyi. zvakafanana asi
zvinopa ma results akasiyana nekuti chimiro /state ye reaction inenge yakasiyana. Q
inoshandiswa kana reaction isiri pa state of equilibrium. I formula ye Kc leye reaction
quotient ziyafana on the right. Umehluko yisikhathi le ndawo lapho okusetshenziswa
lamaformula. I reaction Quotient isetshenziswa ma I reaction ingeko ku state of equilibrium)

1.5 Writing Equilibrium Constants (Kunyora ma Constants/ Ukubhala amaconstants)

These are written basing on the expression for Kc above. It is important to know that state
symbols or phases are critical in coming up with the correct Equilibrium Expression.
The starting point is always the general expression given above.
Pure liquids, hence (l) and solids (s) have a uniform composition and their concentrations are
constant. As such equilibrium expressions are based on aqueous and gas phases. The
symbols change to Kc for aqueous systems and Kp for gaseous systems.

To write the Kc expression we start with the general expression:

(zvisineyi kuti ma reactants nemaproducts ari mu physical form ipi tinonyora zvese zviri mu
reaction equation/ kungenani ukuthi amacomponents enza ireaction akusipi isimo
(physically) , siwabhala onke njengoba eku reaction equation)

Since Partial pressures are proportional to concentration, for gaseous systems the
expression becomes

P stands for partial pressure.

For Homogeneous reactions such as

H2(g) + I2(g) ↔ 2HI(g)

Kc = [HI]2/[H2][I2] Kp = (PHI)2/(PH)(PI2)

PCl5(g) ↔ PCl3(g) + Cl2(g)

Kc = ([PCl3][Cl2])/[PCl5] Kp = ((PPCl3)(PCl2))/(PPCl5)

If reaction is aqueous, leave at Kc

For Heterogeneous reactions;

CaCO3(s) ↔ CaO(s) + CO2(g)

Keq = ([CaO][CO2])/[CaCO3]

CaCO3 and CaO are in solid state , therefore rearrangement gives a new constant

Kc = [CO2] Kp = PCO2

Always, we assign a value of 1 to the components that are in solid or liquid state in the
Constant’s general expression to come up with the final equilibrium constant expression.
(trick)
 Reason: concntrations of solids and pure liquids are deemed constant. The combined
constants result in a new constant.

The equilibrium constant should be expressed according to the nature of reaction i.e
aqueous or gaseous after eliminating liquid and solid components.

1.6 Le Chartelier’s Principle

The principle states that;

If a system at equilibrium is subjected to change in temperature, pressure or concentration ,
it will shift so as minimise or counteract the effect of the change.

1.7 Factors Affecting Equilibrium

The following factors are usually analysed;

Temperature
Pressure
Concentration and
Catalyst
Questions normally enquire the effect of factors on 1. Position of equilibrium and 2. On
equilibrium constant. The first normally refers to the direction of shift of equilibrium in
response to introduced stress. The second is about whether a new value of the constant is
formed.

Temperature affects both

Pressure only affects gaseous reactions provided there is a difference in the numbers of
moles of products and reactants
Concentration affects aqueous reactions
A catalyst has no effect on equilibrium

1.8 Predicting Shifts in Equilibrium

Keq is changed only by change of temperature. All other factors do not change the value of
Kc. Equilibrium for the later shifts so as to restore Kc.

Temperature

Effect depends on the thermodynamic nature of the reaction. The endothermic direction is
favoured by an increase in temperature. A decrease in temperature favours the exothermic
direction.

N2(g) + O2(g) ↔ 2NO2(g) ∆H = + 180 JMol-1

The forward reaction is endothermic and the backward reaction is exothermic. If

temperature is increased, equilibrium shifts to the right. Kc increases.

If temperature is decreased, equilibrium shifts to the left. c decreases

Concentration or Partial Pressure
Value of K is not affected
If conc of reactant increased: equilibrium shifts right. If decreased, equilibrium shifts left.

 is achieved faster.