CHEMICAL

EQUILIBRIUM

Learning Outcomes
explain, in terms of rates of the forward and reverse reactions,

what is meant by a reversible reaction and dynamic equilibrium state Le Chateliers Principle and apply it to deduce qualitatively (from appropriate information) the effects of changes in temperature, concentration or pressure, on a system at equilibrium deduce whether changes in concentration, pressure or temperature or the presence of a catalyst affect the value of the equilibrium constant for a reaction deduce expressions for equilibrium constants in terms of concentrations, Kc, and partial pressures, Kp calculate the values of equilibrium constants in terms of concentrations or partial pressures from appropriate data

Learning Outcomes
calculate the quantities present at equilibrium, given appropriate

data
describe and explain the conditions used in the Haber process

and the Contact process, as examples of the importance of an understanding of chemical equilibrium in the chemical industry
show understanding of, and use the Brnsted-Lowry theory of

acids and bases

explain qualitatively the differences in behaviour between strong

and weak acids and bases and the pH values of their aqueous solutions in terms of the extent of dissociation

Reversible Reactions
Some changes go in only one direction.

Many other chemical reactions are reversible Reversible reaction can proceed in both directions

Reversible Reactions

Reversible reactions are never complete. Mixture of reactants and products are obtained.

Dynamic Equilibrium
In dynamic equilibrium, the forward and

backward reactions continue, but at equal rates. The concentrations of reactants and products remain constant.

Dynamic Equilibrium

The rate of production of NH3 equals the rate of decomposition

Factors affecting Equilibrium

Changing the conditions can disturb a system at equilibrium. Anything which changes the rate of the forward and backward reactions can shift the balance.

Le Chateliers Principle
When the conditions of a system at equilibrium change, the system responds by trying to counteract the change

Changes in Concentration
When add some amount of reactant or product to a

system

at

equilibrium,

the

system

shift

the

equilibrium in the direction that consumes some of the added reactant or product N2(g) + 3H2(g) 2NH3(g)

[NH3], reactionn will shift toward reactants

Changes in Pressure
Pressure changes can only affect reactions between gases. A decrease in pressure will favor the reaction that

produces the most molecules So we have a shift to the left

P, this equilibrium shifts right

A + 2B

H= - 250 kJ

If P, this equilibrium shifts left

Changes in Pressure

Le Chateliers Principle
For each reaction below, determine whether an increase in pressure would shift the equilibrium position towards the reactants or towards the products.

a) C(s) + H2O(g) + heat CO(g) + H2(g)

b) PCl5(g) + 19 kcal PCl3(g) + Cl2(g) c) N2(g) + 3H2(g) 2NH3(g)

Changes in Temperature
For exothermic reaction heat is produced when the reaction proceeds to the right H2(g) + F2(g)
If T

2HF(g) + heat

, this equilibrium shifts left

When add heat to system at equilibrium, the system

will shift to the left until equilibrium is reestablished.

Le Chateliers Principle
If the temperature for the reaction below is increased, which of the following will also occur ? 3Fe(s) + 4H2O(g) Fe3O4(s) + 4H2(g) + 13.1 kJ a) The concentration of H2 will increase b) The mass of Fe3O4 will increase c) The concentration of H2O will increase d) The mass of iron (Fe) will decrease

Le Chateliers Principle
C(s) + H2O(g) + heat CO(g) + H2(g) In which direction is the equilibrium position shifted as a result of the following changes? a) Lowering the temperature b) Removing hydrogen gas c) Adding water vapor

Equilibrium Constant
Equilibrium constant

Used to describe the extent to which the reactants are

converted into products before equilibrium is reached.

When the [reactants] and [products] are constant

The value is obtained numerically based on the equilibrium constant expression

wA + xB

yC + zD

[C] y [D] z Kc [A]w [B] x

Write an expression for Kc for the following reactions:

N2O4(g)

2NO2(g) 2SO3(g) 2HI(g)

2SO2(g) + O2(g) H2(g)

+

I2(g)

Equilibrium Constant
Kp
applies to reactions involving gases. equilibrium constant can be represented in terms of the

partial pressure of the gases.

H2(g)

I2(g)

2HI(g)

Kp = (pHI) (pH2) (pI2)

Equilibrium Constant Values

Magnitude of an equilibrium constant value:

Conveys information about how far a reaction has proceeded

toward completion (extent of reaction).

Value of Kc Very large (1030) Large (1010) Near unity (103-10-3)

Relative amounts essentially all products more products than reactants comparable amounts

Equilibrium position far to the right to the right neither to right nor left

Small (10-10) Very small (10-30)

more reactants than products essentially all reactants

to the left far to the left

Temperature Dependence of Kc and Kp

Kc and Kp are only affected by changes in temperatures.

Example:

A+B

C+D

H =

enthalpy change of forward reaction

For forward reaction is exothermic:

Kc and Kp decreases with increasing T

Kc and Kp increases with increasing T

For forward reaction is endothermic:

Calculations involving Kc and Kp

Ans:

Calculations involving Kc and Kp

H2(g)
+

I2(g)

2HI(g)

When 0.5 mole of H2 and 0.5 mole of I2 were mixed in a closed vessel at 723 K and 2 atm, 0.11 mole of I were found to be present when equilibrium was established. Calculate the value of Kp at 723 K.

Calculations involving Kc and Kp

Solution:

Initial/mol Equilibrium/mol

H2 (g) 0.5 0.11

I2 (g) 0.5 0.11

2HI (g) 0 2(0.5-0.11) = 0.78

Total amount of gas = 0.11 + 0.11 + 0.78 = 1.00 mol pH2 = pI2 = 0.22 atm pHI = 1.56 atm Kp
=

(pHI) (pH2) (pI2)

= 50.3

Haber Process
The Haber Process combines nitrogen from the air with hydrogen derived mainly from natural gas (methane) into ammonia. The reaction is reversible and the production of ammonia is exothermic.

3H2(g) + N2(g) 2NH3 (g)

(H = 92 kJ/mol)

Haber Process
Typical conditions used in the Haber process are:
a pressure of 200 atm moderate temperature of about 500C

iron catalyst
N2 and H2 used in the volume proportion of 1:3.

Contact Process
The Contact Process is the current method of

producing sulfuric acid in the high concentrations needed for industrial processes. Vanadium (V) oxide is the catalyst used.
Reactions in Contact Process: makes sulphur dioxide; convers the sulphur dioxide into sulphur trioxide (the reversible reaction at the heart of the process); converts the sulphur trioxide into concentrated sulphuric acid.

Contact Process

Stage 1 - Preparation and purification of sulphur dioxide (Furnace) Molten sulphur is burnt in dry air (oxygen) to produce sulphur dioxide.The gas produced is purified and cooled. S(l) + O2(g) SO2 (g)

Contact Process
Stage 2 - Catalytic oxidation of sulphur dioxide to sulphur trioxide (Converter)
Sulphur dioxide and excess oxygen gas are passed over a few plates of

vanadium(V) oxide,V2O5 catalyst at 450C to produce sulphur trioxide. 2SO2(g) + O2(g) 2SO3 (g) Stage 3 - Conversion of sulphur trioxide to sulphuric acid (Absorber)
The sulphur trioxide is first reacted with concentrated sulphuric acid to

form a product called oleum,H2S2O7. SO3(g) + H2SO4(l) H2S2O7 (l)

The oleum,H2S2O7 is then diluted with water to produce concentrated

sulphuric acid in large quantities. H2S2O7(l) + H2O(g) 2H2SO4(l)

Bronsted-Lowry Acids and Bases

According to the Bronsted-Lowry theory, Acids donate a proton (H+). Bases accept a proton (H+).

Conjugate Acid-Base Pairs

For a Bronsted-Lowry acid:

An equilibrium is reached in which forward reaction and reverse

reaction occur at the same rate. Example:

HF(aq) + H2O(l)
acid base

H3O+(aq) + F-(aq)
conjugate acid conjugate base

Conjugate acid-base pair (e.g. HF/F-, H3O+/H2O)

two species, one an acid and one a base, that differ from each other through the loss or gain of a proton (H+)

Strengths of Acids
Strong acids completely ionizes (100%) in aqueous

solutions. HCl(g) + H2O(l)

H3O+ (aq) + Cl (aq)

Weak acids dissociate only slightly in water to form a

solution of mostly molecules and a few ions. H2CO3(aq) + H2O(l) H3O+(aq) + HCO3 (aq)

Strong Acids
A strong acid, HA dissolved in water Dissociates into ions. Gives H3O+ and the anion (A-).

Weak Acids
Weak acids dissolved in water, Dissociate only a few molecules. Remain mostly as the undissociated HA(aq) +H2O(l) (molecular) form. Have low concentrations of H3O+ and anion (A-).

H3O+(aq) + A(aq)

Strong Bases
Strong bases Include LiOH, NaOH, KOH, and Ca(OH)2. Dissociate completely in water. KOH(s) K+(aq) + OH(aq)

Weak Bases
Weak bases
Are most other bases.
Dissociate only slightly in

water.
Form only a few ions in water.

NH3(g) + H2O(l) NH4+(aq) + OH(aq)