REACTION KINETICS AND CHEMICAL EQUILIBRIA

Topic Page
RATES OF REACTION 2

CHEMICAL EQUILIBRIUM 14
Le Chatelier’s Principle 19

ACID/BASE EQUILIBRIA 24
pH Calculations 27
Neutralisation (pH) Indicators 32

BUFFERS AND PH 34

SOLUBILITY PRODUCT 38

REDOX EQUILIBRIA 42
The Standard Hydrogen Electrode 44
Types of Half Cells 45
Cell Statement or Cell Diagram 47
Standard Electrode and Redox Potentials 49
Uses of S.E.P. Values 50
Useful Electrochemical Cells 52

Summary of CAPE Unit 1 Module 2 57

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 REACTION KINETICS AND CHEMICAL EQUILIBRIA

RATES OF REACTION

Chemical reactions occur within a wide range of speeds. Reactions can occur within:

 An instant e.g. explosions

 A few minutes e.g. an acid-base reaction, dissolving salts in water
 A few hours e.g. baking bread or cakes etc.
 A few days e.g. healing of a cut/bruise
 A few weeks e.g. fermentation of sugars to produce alcohol
 A few months e.g. rusting, decomposition of organic material
 A few years e.g. weathering of mountain rocks, growth of human beings
 Even longer periods of time e.g. formation of crude oil from organic debris

Rate of a reaction is defined as change in concentration of a reactant or product per unit time
at a specific temperature.

𝑑𝑒𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛

𝑅𝑎𝑡𝑒 =
𝑡𝑖𝑚𝑒
𝑖𝑛𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛
𝑅𝑎𝑡𝑒 =
𝑡𝑖𝑚𝑒
[𝑅𝑎𝑡𝑒] = 𝑚𝑜𝑙𝑑𝑚−3 𝑠 −1

Experimental Methods to Determine Rates of Reaction

Chemical Analysis – A reaction is carried out under controlled conditions, with known
amounts of reactants. Samples of the reaction are taken via pipette at fixed intervals and the
reaction is stopped either by sudden cooling or dilution of the sample, followed by titration to
find the concentration of a reactant or product.

Physical Methods – a change in volume (or pressure) of gases, in mass of product or reactant,
in the absorption spectrum when the reaction is followed by a spectrophotometer, in pH, in
colour, in electrical properties (e.g. conductance or potential), in thermal conductivity or any
other appropriate physical properties of the reacting system.

Order of Reaction

Rate = k [X]0 → zero order

Rate = k [Y]1 → first order

Rate = k [Z]2 → second order

Rates of reactions can be represented graphically. The gradient or slope of the graph gives the
rate at any point during the reaction. Graphs can be of concentration vs. time, concentration
vs. 1/time or rate vs. time.

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Zero Order

If the experiment shows that the power for the concentration of a reactant in the rate equation
is zero then the reaction is said to be zero order with respect to that reactant. A zero order
reaction is one in the concentration of a reactant has no effect on the rate of reaction. A graph
of rate of reaction against concentration of this reactant is a straight horizontal line.

First Order

If the power is found to be one then the reaction is first order with respect to that reaction. For
a first order reaction a two fold increase on the concentration of a reactant results in the
double of reaction rate, i.e. is rate is directly proportional to concentration. When rate is
plotted against concentration a straight line through the origin is obtained.

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Second Order

The reaction is second order with respect to the second reactant if a two fold increase in the
concentration of the reactant results in a fourfold increase in rate of reaction. When rate is
plotted against concentration a curve is obtained.

Graphical Comparison of Reaction Orders

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Half Life of a Reaction (First Order Reactions Only)

The half-life (t ½) of a chemical reaction is the time taken for the concentration of a reactant
to decrease to half of its initial value. For a first order reaction, the half-life is constant and
hence can be used to identify a first order reaction. If a half-life is known the rate constant (k)
of the first order reaction can be calculated from the reaction.

Rate = k [x]
0.693 ln 2
t1/2 = =
𝑘 𝑘

Experimental Determination of Order of a Reaction

The Method of Initial Rates is used. A series of experiments is set up in which the
concentration of each reactant is different from one experiment to the next. The initial rate of
reaction for each experiment is determined. This allows a relationship between concentration
of that reactant and the rate of reaction is established.

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Worked Example 1:

A+B products

[A] [B] Initial Rate/moldm-3 s-1 Experiment

0.50 1.0 2.0 1
0.50 2.0 3.0 2
0.50 3.0 18 3
1.0 3.0 36 4
2.0 3.0 72 5

a) Determine the rate law or rate equation.

b) Find the value of k.
c) Find the overall order.

General expression for rate: Rate = k [A]X [B]Y

Using the data in the table: Rate = k [A][B]2

Using experiment 1: Rate = k [A][B]2

2 = k × 0.5 × 1.02
k = 4 mol-2 dm6 s-1

Overall order = 2+1 = 3

Worked Example 2:
X+Y Z
[X] [Y] Initial Rate / moldm-3s-1
0.1 0.1 0.030
0.2 0.2 0.240
0.2 0.1 0.120

1. Write rate law.

2. Find the rate constant, k.

General expression for rate: Rate = k [X]a [Y]b

Using the data in the table: Rate = k [X]2 [Y]
Using experiment 1: Rate = k [X]2 [Y]
0.030 = k × 0.12 × 0.1
k = 30 mol-2dm6 s-1

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Why Study Rates of Reaction?

The rate of a process can tell how long/how much time it takes for the process to be
completed. We time many activities unconsciously and consciously. We know how long it
takes for a cake or bread to bake and we know how long it takes to get from place A to B at a
certain velocity.

Scientists often have different chemical routes to synthesise a specific product and they will
have to investigate how various factors such as temperature, pressure, catalysts etc. can
influence the reaction rate, while making a compromise to find the best balance among profit,
yield, cost of reactants, danger to the environment etc. It is important to know how fast a
certain reaction will take place under certain conditions in order to determine whether
industrial or manufacture processes can be feasible. Reactions on a commercial scale will
also need to be economical and have a high yield, while also being as environmentally
friendly as possible. To understand the rate of a reaction, we must understand what is
happening in the reaction at the molecular level. Investigations into the rate of a reaction
under a certain set of conditions are called reaction kinetics studies.

Rate of Reaction & Reaction Mechanisms

Most reactions occur in a series of steps called the reaction mechanism. Some reactions take
place in one step but most organic reactions proceed in a series of steps. Rate equations give
evidence of what the reaction mechanism might be. Only the concentrations of those
reactants which take part in the slowest step appear in the rate equation. It is the rate of
this slowest step which is measured during a kinetic study. This rate is the limiting factor of
the reaction as a whole and is known as the determining step.

NB – The rate law of a particular reaction cannot be determined from the balanced chemical
equation. It must be determined experimentally as previously outlined.

Reactants Products

A B

species Propose a
Orders wrt rate
Experiment involved in reaction
reactants equation
slowest step mechanism

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Kinetics Studies & Reaction Mechanisms in the Hydrolysis of Alkyl Halides

a) Overall reaction:

Experimentally determined rate equation: Rate = k [(CH3)3CCl]

Proposed mechanism: Since the rate equation only has one reactant, this implies that the
organic molecule has to form ions in the slowest step, i.e. bond cleavage involves one
species.

b) Overall reaction:

Experimentally determined rate equation: Rate = k [C3H7Cl][OH-]

Proposed mechanism: Since the rate equation has both reactants, this implies that the organic
molecule has to form a bond with the hydroxide ion in the slowest step, i.e. bond formation
involves two species.

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Molecularity

The molecularity is a reaction is defined as the number of species involved in the rate
determining step. A reaction step in a mechanism with only a single species is called a
unimolecular reaction step; with two species, it is called a bimolecular reaction step; with
three species, trimolecular.

Possible steps in reaction mechanisms:

R.D.S. Molecularity Possible Mechanism

A  products unimolecular Rate = k [A]
A+A  products bimolecular Rate = k [A]2
A+B  products bimolecular Rate = k [A][B]

Factors Affecting Rates of Reactions

a) Concentration of reactions
b) State of subdivision of reactants
c) Pressure
d) Temperature
e) Catalysts
f) Light

Collision Theory

Used to explain the effects of above factors on rates of reactions

In order for a reaction to occur, three requirements are:
1) Particles must collide
2) Upon collision, particles must have the minimum energy required for reactions to
occur called the activity energy, EA
3) Some reactions require that particles must collide with the correct orientation i.e.
correct collision geometry. This is important for enzyme reactions or reactions with
large complex ions.

Collisions in which particles which have all three requirements and are converted into
products are said to be effective or successful collisions.

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Concentration

State of Subdivision

Pressure

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Temperature

This factor has the greatest effect on rate. For every 10 °C rise in temperature, rate
approximately doubles. The rate constant, k, is dependent on temperature (Arrhenius
Equation).

Molecules have energy due to their motion called kinetic energy. At any instant some
molecules have high energies while others have very low energies. Most molecules will have
a range of energies between these extremes. The distribution of energy among molecules at a
particular temperature was calculated by James Maxwell in 1859 and applied by Ludwig
Boltzmann in 1871. The result is the Maxwell – Boltzmann distribution curve of energy.

A comparison of the Maxwell – Boltzmann curves at different temperatures illustrates the

effect on the shape of the curve. The distribution explains why at a particular temperature
only a certain number of collisions are effective. At a higher temperature, a greater proportion
would have energies equal to or above the activation energy, giving more effective collisions.
Hence, increasing the temperature increases the number of particles with the activation
energy and consequently increases the rate of reaction.

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Catalysts

By having its EA lowered with the use of a catalyst does, a reaction occurs at a faster rate. A
catalyst provides an alternative pathway for the reaction to occur with a lower E A. If the
activation energy required for the reaction to occur is lowered, a greater proportion of
molecules will have sufficient energy to now make effective collisions.

Enzymes

An enzyme is a biological catalyst. Almost all enzymes are proteins and are found inside
cells. Enzymes alter the activation energy of a reaction by providing an alternate route for the
reactants to interact without becoming permanently involved in the reaction. They differ from
other catalysts in their very high activity being between 1 million to 20 million times more
efficient than inorganic catalysts. Each enzyme molecule can catalyse the conversion of
thousands of molecules per second. Enzymes are very specific in the reactions they catalyse,
that is, they catalyse just a particular reaction of one chemical. Enzymes have an optimum
temperature between 25 – 40 °C and an optimum pH at which they work best.

In living organisms, enzymes are essential in cellular signalling and regulation, generating
movement, digestion, respiration and metabolism etc. Several chemical industries use
enzymes when highly specialised catalysts are required. Some of these fields include: biofuel
industry, bio-detergents, brewing industry, culinary uses, dairy industry, food processing,
molecular biology and the paper industry.

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CHEMICAL EQUILIBRIUM

A system can be in either of two types of equilibrium:

 Phase equilibrium – this is equilibrium between the physically distinct phases of a

system (e.g. solid, liquid, gas or aqueous)
 Chemical equilibrium – this is equilibrium between species in a reversible reaction

Chemical Equilibrium

Most reactions: Reactants Products

Reversible reactions: Reactants Products

Chemical equilibria are dynamic processes in which the forward and reverse reactions occur
at the same rate. Many reactions do not go to completion and then stop, since the products of
the reactions themselves react to form the original reactants. The reaction mixture then has
both reactants and products and a dynamic equilibrium will be established when the reactants
and products are both reacting at the same rates. When the reactants and products are both
present in the equilibrium mixture, then the reaction is said to be reversible.

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Characteristics of Dynamic Equilibrium

1. Macroscopic properties are constant, that is, at equilibrium, concentrations or partial

pressures of reactants and products are constant.
2. Microscopic properties are continuously changing, that is, molecules of reactants and
products are continuously reacting.
3. Equilibrium can be achieved from any direction.
4. Equilibrium can only be achieved if the system is closed, that is, there is no external
interference or no substance is added or lost.
5. If the system is subjected to a disturbance, it reacts to oppose the disturbance and
return to an equilibrium state.

Types of Chemical Equilibrium

1. Homogeneous equilibrium
Reactants and products are in the same phase
CH3COOH (l) + C2H5OH (l) CH3COOC2H5 (l) + H2O (l)
H2 (g) + I2 (g) 2HI (g)
N2O4 (g) 2NO2 (g)
2. Heterogeneous Equilibrium
Reactants and products are not in the same phase
CO2 (g) + C (s) 2CO (g)
PCl3 (l) + Cl2 (g) PCl5 (s)
Fe3O4 (s) + 4H2 (g) Fe (s) + 4H2O (g)

The Equilibrium Law and KC

For a homogeneous equilibrium represented as

xA + yB wC + zD

The equilibrium expression is given by:

[𝐶]𝑤 [𝐷] 𝑧
𝐾𝑐 =
[𝐴] 𝑥 [𝐵] 𝑦

where Kc is a constant at a particular temperature called the equilibrium constant in terms of

concentration. All concentrations in the expression are equilibrium concentrations.

Kc is the product of the molar concentrations of the products each raised to the power of their
coefficient in the balanced equation divided by the product of the molar concentrations of the
reactants each raised to the power of their coefficients in the balanced equation.

For homogeneous equilibria:

[𝐶𝐻3 𝐶𝑂𝑂𝐶2 𝐻5 ]1 [𝐻2 𝑂]1
𝐾𝑐 = [𝐶𝐻3 𝐶𝑂𝑂𝐻]1 [𝐶2 𝐻5 𝑂𝐻]1
(no units)

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[𝐻𝐼]2
𝐾𝑐 = (no units)
[𝐻2 ]1 [𝐼2]1

[𝑁𝑂2 ]2
𝐾𝑐 = units: moldm-3
[𝑁2 𝑂4 ]1

For heterogeneous equilibria:

[𝐶𝑂]2
𝐾𝑐 = [𝐶𝑂2 ]1 [𝐶]1

Since carbon is a solid, [C] is taken to be constant

[𝐶𝑂]2
Therefore 𝐾𝑐 = units: moldm-3
[𝐶𝑂2 ]1

The Equilibrium Law and K P

For gaseous equilibria, concentration is measured in terms of partial pressure.

Dalton’s Law of Partial Pressures states that the total pressure exerted by a mixture of gases
is the sum of the partial pressures which each gas would exert if it alone were present in the
mixture. The pressure exerted by each gas is called the partial pressure.

𝑃𝑎𝑟𝑡𝑖𝑎𝑙 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑜𝑓 𝑎 𝑔𝑎𝑠 𝑖𝑛 𝑎 𝑚𝑖𝑥𝑡𝑢𝑟𝑒 = 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 × 𝑡𝑜𝑡𝑎𝑙 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒

𝑝𝐴 = 𝑥𝐴 × 𝑝𝑇

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴
𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝐴 =
𝑡𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑎𝑙𝑙 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖𝑛 𝑚𝑖𝑥𝑡𝑢𝑟𝑒
𝑛𝐴 𝑛𝐴
𝑥𝐴 = =
𝑛𝐴 + 𝑛𝐵 + 𝑛𝐶 + ⋯ 𝑛𝑇

Total Pressure = Sum of the Partial Pressures for each gas:

PT = PA + PB + PC etc

For a gaseous homogeneous equilibrium represented as

xA(g) + yB (g) wC(g) + zD(g)

The equilibrium expression is given by:

(𝑝𝐶 )𝑤 (𝑝𝐷 )𝑧
𝐾𝑝 =
(𝑝𝐴 )𝑥 (𝑝𝐵 )𝑦

where Kp is a constant at a particular temperature called the equilibrium constant in terms of

pressure. All partial pressures in the expression are equilibrium partial pressures.

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Kp is the product of the partial pressures of the products each raised to the power of their
coefficient in the balanced equation divided by the product of the partial pressures of the
reactants each raised to the power of their coefficients in the balanced equation.

H2 (g) + I2 (g) 2HI (g)

Kp = (PHI)2
(PH2)(PI2) no units

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

units: Pa-2 or atm-2

What Do Equilibrium Constants Tell Us?

Value of
Equilibrium Extent of Reaction Example
Constant
≈ 10 mol-1dm3
59
Reaction virtually goes to 2NO (g) + 2 CO (g) N2 (g) + CO2 (g)
completion Equilibrium lies to the right
≈1 Concentration of reactants PCl3 (g) + Cl2 (g) PCl5 (g)
and products at equilibrium
are nearly the same
≈ 10-17 mol-1dm3 Reaction virtually does not 2HCl (g) H2 (g) + Cl2 (g)
go forward Equilibrium lies to the left

Position of Equilibrium

y Reactants x Products

[𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠] 𝑥
𝐾𝑐 =
[𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠] 𝑦

The term position of equilibrium is used to describe the extent of reversible reaction. When
the reaction has a large equilibrium constant, the position of the equilibrium is said to lie to
the right hand side of the equation. A reaction with a small equilibrium constant lies to the
left.

NB – Kc gives no information about the rate of reaction.

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Measuring Kc

Three basic stages

1. Combine known amounts of reactants or products under carefully measured and

controlled conditions and allow the reaction to come to equilibrium at a fixed
temperature.
2. Measure accurately the equilibrium concentration of one or more of the substances in
the equilibrium mixture and from this calculate the equilibrium concentrations of all
substances in the mixture.
3. Substitute these equilibrium concentrations into the equilibrium expression.

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Worked Example

If 1 mole of ethanoic acid and 0.5 mole of ethanol react to equilibrium at a certain
temperature, 0.422 moles of ethyl ethanoate form at equilibrium. Calculate Kc.

CH3COOH (l) + C2H5OH (l) CH3COOC2H5 (l) + H2O (l)

Reactant/Products CH3COOH C2H5OH CH3COOC2H5 H2O

Initial moles 1 0.5 - -
Change -0.422 -0.422 + 0.422 +0.422
Equilibrium 1 – 0.422 0.5 – 0.422 0.422 0.422
moles = 0.578 = 0.078

[𝐶𝐻3 𝐶𝑂𝑂𝐶2 𝐻5 ][𝐻2 𝑂]

𝐾𝑐 =
[𝐶𝐻3 𝐶𝑂𝑂𝐻][𝐶2 𝐻5 𝑂𝐻]

Assume volume is Vdm-3

Concentration at equilibrium will be
0.422
[CH3COOC2H5 = H2O] = 𝑉
0.578
[CH3COOH] = 𝑉
0.078
[C2H5OH] = 𝑉
0.422 0.422
( )( )
𝑉 𝑉
Kc = 0.578 0.078
( )( )
𝑉 𝑉
= 3.95

Questions:

1. If one mole of CH3COOH and one mole of C2H5OH react to equilibrium at a certain
temperature, 0.67 moles of ethyl ethanoate form at equilibrium. Calculate K c.
2. 0.6 moles of ethanoic acid, 0.5 moles of ethanol, 0.6 moles of ethyl ethanoate and 0.4
moles of water containing HCl were mixed. At equilibrium, only 0.4 moles of
ethanoic acid remained. Calculate Kc.
3. In an experiment of Bodenstein, 20.57 moles of H 2 and 5.22 moles of I2 were allowed
to react to equilibrium at 450 °C. At equilibrium, the mixture contained 10.22 moles
of HI. Show that Kc is approximately 61.

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Factors Affecting Chemical Equilibrium

Le Chatelier’s Principle:

If a system in equilibrium is subjected to any change, the equilibrium will shift if possible in
the direction which causes an opposite change.

Effect of Concentration

xA + yB wC + zD

[𝐶]𝑤 [𝐷] 𝑧
𝐾𝑐 =
[𝐴] 𝑥 [𝐵] 𝑦

If either A or B are added to the equilibrium mixture, more C and D are formed so that the
new concentration terms in the equilibrium expression will still equal to Kc. The equilibrium
is said to shift from left to right. Addition of more C and D, causes a shift from right to left
with no effect on the value of Kc.

Functioning of Indicators

Acid Base indicators are weak organic acids represented as HIn

Indicator in Water:

HIn + H2O H3O+ + In-

One colour another colour

In solution, an equilibrium mixture would contain both HIn and In-. Addition of acid would
increase the concentration of H3O+ ions. By Le Chatelier’s Principle, the equilibrium reacts to
decrease the H3O+ concentration by forming more reactants. The equilibrium shifts to the left
to give the colour of HIn. If base is added, OH- reacts with H3O+ to give water. The
concentration of H3O+ decreases and the equilibrium reacts by shifting to the right. In so
doing, In_ is formed and its colour is observed.

Acidification of Potassium Dichromate

2CrO42- (aq) + 2H+ Cr2O72- (aq) + H2O (l)

Yellow Orange

Add H+  shifts the equilibrium to the right  orange colour observed

Add OH-  shifts the equilibrium to the left yellow colour observed

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Effect of Pressure

For example, in the Haber process the following equilibrium exists in the process of
manufacturing ammonia.

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

At equilibrium,

Increase pressure  equilibrium reacts to decrease pressure  equilibrium shifts to the side
with less molecules  shifts to the right with no change to Kc or Kp

Decrease pressure  equilibrium reacts to increase pressure  equilibrium shifts to the side
with more molecules  shifts to the left with no change to Kc or Kp

H2 (g) + I2 (g) 2HI (g)

Since both sides have equal number of molecules, pressure has no effect on the equilibrium
of this reaction.

Effect of Catalyst

A catalyst affects the rate of a reaction. It has the same effect on both the forward and reverse
reactions in an equilibrium mixture. Hence, there is no overall effect on the composition of
the mixture. The equilibrium mixture is just obtained more rapidly with a catalyst present.
There is no effect on the value of Kc or Kp.

Effect of Temperature

In a reversible reaction, change in temperature will affect the rates of both forward and
reverse reactions but not to the same extent. Change of temperature causes a shift of
equilibrium and a change in the value of Kc or Kp depending on whether the reaction is
exothermic or endothermic.

Exothermic Reaction

N2 (g) + 3H2 (g) 2NH3 (g) ΔHө = - 92 kJmol-1

(𝑝𝑎𝑚𝑚𝑜𝑛𝑖𝑎 )2
𝐾𝑝 =
(𝑝𝑛𝑖𝑡𝑟𝑜𝑔𝑒𝑛 )(𝑝ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛 )3

At equilibrium,

Increase temperature  equilibrium reacts to decrease temperature  equilibrium shifts to

endothermic side  shifts to the left  Kp decreases

Decrease temperature  equilibrium reacts to increase temperature  equilibrium shifts to

exothermic side  shifts to the right  Kp increases
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Endothermic Reaction

N2O4 (g) 2NO2 (g) ΔHө = + 58 kJmol-1

(𝑝𝑛𝑖𝑡𝑟𝑜𝑔𝑒𝑛 𝑑𝑖𝑜𝑥𝑖𝑑𝑒 )2
𝐾𝑝 =
(𝑝𝑑𝑖𝑛𝑖𝑡𝑟𝑜𝑔𝑒𝑛 𝑡𝑒𝑡𝑟𝑜𝑥𝑖𝑑𝑒 )

At equilibrium,

Increase temperature  equilibrium reacts to decrease temperature  equilibrium shifts to

endothermic side  shifts to the right  Kp increases

Decrease temperature  equilibrium reacts to increase temperature  equilibrium shifts to

exothermic side  shifts to the left  Kp decreases

Worked Example 1

Under standard conditions (298 K, 1 atmosphere), 1 mole of ethene and 1 mole of steam give
0.74 moles of ethanol at equilibrium. Calculate Kp.

Reaction C2H4 (g) + H2O (g) C2H5OH (g)

Initial moles 1 1 0

Change – 0.74 – 0.74 +0.74

Equilibrium 0.26 0.26 0.74

0.26 0.26 0.74
Mole fractions
0.74+0.26+0.26 0.74+0.26+0.26 0.74+0.26+0.26

0.26 0.26 0.74

Partial pressures × 1 × 105 × 1 × 105 × 1 × 105
1.26 1.26 1.26

(𝑝𝑒𝑡ℎ𝑎𝑛𝑜𝑙 )
𝐾𝑝 =
(𝑝𝑒𝑡ℎ𝑒𝑛𝑒 )(𝑝𝑠𝑡𝑒𝑎𝑚 )

5.87 × 104
𝐾𝑝 =
(2.06 × 104 )2

𝐾𝑝 = 1.38 × 104 Pa-1

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Worked Example 2

When a 2 : 1 ratio of sulphur dioxide and oxygen at a total initial pressure of 3 atmosphere is
passed over a catalyst at 430 °C, the partial pressures of sulphur trioxide at equilibrium is 1.9
atmospheres. Calculate:

1. The initial partial pressures of sulphur dioxide and oxygen

2. The equilibrium partial pressures of sulphur dioxide and oxygen
3. Kp

Reaction 2SO2 (g) + O2 (g) 2SO3 (g)

Initial moles 2 1 0

Initial partial press. 2 atmos. 1 atmos.

Change −1.9 −0.95 +1.9

Equilibrium press. 2 – 1.9 1 – 0.95 1.9

(𝑝𝑡𝑟𝑖𝑜𝑥𝑖𝑑𝑒 )2
𝐾𝑝 =
(𝑝𝑜𝑥𝑦𝑔𝑒𝑛 )(𝑝𝑑𝑖𝑜𝑥𝑖𝑑𝑒 )2

1.92
𝐾𝑝 =
(0.05)(0.1)2

𝐾𝑝 = 7220 atm-1

Question

1 mol of H2(g) and 1 mol of I2(g) were mixed and allowed to reach equilibrium at 300K and 1
[Link] amount of HI (g) present at equilibrium was 1.5 moles. Calculate Kp at 300K.

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 REACTION KINETICS AND CHEMICAL EQUILIBRIA

ACID – BASE EQUILIBRIA

The definitions of acids and bases depend on which theory is used.

Theory Acid Base

Ostwald−Arrhenius A substance which produces A substance which produces
H+ ions in aqueous solution OH- ions in aqueous solution
Brønsted−Lowry A proton donor A proton acceptor
Lewis An electron pair acceptor An electron pair donor

With the Brønsted−Lowry model, acid/base strength can be treated quantitatively, unlike with
the Lewis model.

H+ (aq) + OH- (aq) H2O (l)

Conjugate Pairs

A H+ (aq) + B- (aq)
acid base

A and B are said to be a conjugate pair.

A is the conjugate acid of base B
B is the conjugate base of acid A
Acid Conjugate Base
HCl Cl-
H2SO4 HSO4-
H2O OH-
H3PO4 H2PO4-
H3O+ H2O
NH4+ NH3
C6H5NH3+ C6H5NH2
HSO4- SO42-
H2PO4- HPO42-
OH- O2-

Some substances like H2O, OH-, H2PO4- can act as both acids and bases. Hence they are
amphoteric or amphiprotic.

The Strength of Conjugate Pairs

A H+ (aq) + B- (aq)

A is a strong acid if the above equilibrium is well to the right. B - is a strong base if the
equilibrium is well to the left. The conjugate base of a strong acid is a weak base. The
conjugate acid of a strong base is a weak acid.

When an acid reacts with a base by donating a proton, a second acid and base are formed.
This can be shown as follows:

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Acid (I) + Base (II) Base (I) + Acid (II)

Acid (I) is the conjugate acid of base (I)
Base (II) is the conjugate base of acid (II)

HCl (g) + H2O (l) Cl- (aq) + H3O+ (aq)

Acid (I) + Base (II) Base (I) + Acid (II)

The equilibrium position in such reaction will depend on the relative strengths of the acids
and bases. If acid (I) is stronger than acid (II), then base (II) will be stronger than base (I) and
hence the equilibrium will lie to the right. When acid (I) is weaker than acid (II) the
equilibrium will lie to the left.
H2O (l) + H2O (l) OH- (aq) + H3O+ (aq)
Acid (I) + Base (II) Base (I) + Acid (II)

An acid-base titration in water: H3O+ vs. OH-

HCl (aq) H+ (aq) + Cl- (aq)
NaOH (aq) Na+ (aq) + OH- (aq)

NH3 (l) + NH3 (l) NH2- (aq) + NH4+ (aq)

Acid (I) + Base (II) Base (I) + Acid (II)
An acid-base titration in liquid ammonia: NH4+ vs. NH2-
NH4Cl NH4+ + Cl-
NaNH2 Na+ + NH2-

Measuring Acidity & Basicity

A strong acid is fully dissociated in aqueous solution.

H2SO4 (aq) 2H+ (aq) + SO42- (aq)

A strong base is fully dissociated in aqueous solution.

NaOH (aq) Na+ (aq) + OH- (aq)

A weak acid is partially dissociated in aqueous solution.

CH3COOH (aq) CH3COO- (aq) + H+ (aq)

A weak base is partially dissociated in aqueous solution.

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

Common strong acids Common strong bases

HNO3 LiOH
HCl NaOH
HBr KOH
HI RbOH
H2SO4 CsOH

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HClO4 Mg(OH)2
Ca(OH)2
Sr(OH)2
Ba(OH)2

Weak Acids
Consider a weak acid, HA:
HA (aq) H+ (aq) + A- (aq)
The relevant equilibrium expression is given by:

[𝐻 + (𝑎𝑞) ][𝐴− (𝑎𝑞) ]

𝐾𝑎 =
[𝐻𝐴(𝑎𝑞) ]
Ka is the equilibrium constant for a weak acid and is called the acid dissociation constant.
Ka is constant for a given acid at a particular temperature.
The larger the Ka value is, the stronger is the weak acid, since this indicates that the [H +] is
greater. Since the Ka values can be small in magnitude, a more convenient measure is used.

𝑝𝐾𝑎 = − log 𝐾𝑎
The strongest acids will have a high Ka value and a low pKa value.

Acid Formula Ka/moldm-3 pKa

Chloroethanoic CH2ClCOOH 1.4 × 10-3 2.9 (strongest)
Methanoic HCOOH 1.8 × 10-4 3.8
Ethanoic CH3COOH 1.8 × 10-5 4.8

Weak Bases
Consider a weak base, B:
B (aq) + H2O (l) BH+ (aq) + OH- (aq)
The relevant equilibrium expression is given by:

[𝐵𝐻 + (𝑎𝑞) ][𝑂𝐻− (𝑎𝑞) ]

𝐾𝑏 =
[𝐵(𝑎𝑞) ]

NB – Since the concentration of water is so large, it is not included in the K b expression as it

is taken to be constant compared to the concentrations of the base and its ions.
Kb is the equilibrium constant for a weak base and is called the base dissociation constant.
Kb is constant for a given base at a particular temperature.
The larger the Kb value is, the stronger is the weak base, since this indicates that the [OH-] is
greater. Since the Kb values can be small in magnitude, a more convenient measure is used.

𝑝𝐾𝑏 = − log 𝐾𝑏
The strongest bases will have a high Kb value and a low pKb value.

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Base Formula Kb/moldm-3 pKb

Ammonia NH3 1.8 × 10-5 4.8
Methylamine CH3NH2 4.0 × 10-4 3.4
Ethylamine C2H5NH2 6.5 × 10-4 3.2 (strongest)

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The pH Scale

A substance can be classified as acidic, basic/alkaline, neutral or amphoteric. The pH scale is

used to measure acidity or alkalinity of a substance by measuring the concentration of
aqueous H+ ions.

𝑝𝐻 = − log10 [𝐻+ ]

Self Ionisation of Water and K w

The pH of water at 25 °C is 7.
Thus 7 = − log10 [𝐻+ ]
Therefore, [H+] = 10-7 moldm-3
Water is a weak electrolyte: H2O (l) H+ (aq) + OH- (aq)
So if, [H+] = 10-7 moldm-3, then [OH-] = 10-7 moldm-3.
[𝐻 + ][𝑂𝐻 − ]
The equilibrium expression is given by 𝐾𝐶 = [𝐻2 𝑂]
Since [H2O] is so large it is taken as a constant
Thus the expression becomes 𝐾𝑤 = [𝐻+ ][𝑂𝐻− ] where Kw is the ionic product of water.
The value of Kw at 25 °C is 𝐾𝑤 = [𝐻+ ][𝑂𝐻− ] = 10−7 × 10−7 = 10−14 𝑚𝑜𝑙 2 𝑑𝑚−6
Kw is an equilibrium constant and is affected by temperature.

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Kw increases with temperature because

H2O (l) H+ (aq) + OH- (aq) ΔHө = +58 kJmol-1

ΔH is positive in the forward direction. If temperature increases, the equilibrium reacts to

decrease the temperature by Le Chatelier’s Principle by going to the right. Hence more water
molecules will ionise into H+ and OH- ions, thereby increasing the Kw.

At 25 °C,

pKw = – log10 (1 × 10-14) = 14

pH Calculations

1. Strong Acids – fully dissociated

Calculate the pH of 0.001 M HCl
HCl H+ + Cl-
0.001 0.001 0.001
+
[H ] = 0.001 M
pH = – log10 (1 × 10-3) = 3

2. Strong Bases – fully dissociated

Calculate the pH of 0.02 M NaOH
NaOH Na+ + OH-
0.02 0.02 0.02
-
[OH ] = 0.02 M
Use Kw to find [H+]
Kw = [H+][OH-]
𝐾𝑤 1 ×10−14
[H+]= = = 5 × 10-14 moldm-3
[𝑂𝐻 − ] 0.02
pH = – log10 (5 × 10-14) = 13.3

3. Weak Acids – partially dissociated

The Ka of methanoic acid is 1.6 × 10-4 moldm-3. Calculate the pH of 0.5 M HCOOH.
HCOOH H+ + HCOO-

Initial moles 0.5 0 0

At equil. 0.5 – [H+] [H+] [H+]

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[𝐻+ ][𝐻𝐶𝑂𝑂− ] [𝐻+ ]2

𝐾𝑎 = =
[𝐻𝐶𝑂𝑂𝐻] 0.5 − [𝐻+ ]

Since the acid is weak, the concentration of the acid would be much greater than the
[H+] ion concentration so, it is reasonably safe to assume that 0.5 – [H+] ≈ 0.5. Thus,

[𝐻+ ]2
𝐾𝑎 =
0.5

[𝐻 + ] = √0.5 𝐾𝑎 = √0.5 × 1.6 × 10−4

[H+]=8.9 × 10-3 moldm-3

pH = – log10 (8.9 × 10-3) = 2.1

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4. Weak Bases – partially dissociated

The Kb of ammonia is 1.8 × 10-5 moldm-3. Calculate the pH of 0.1 M NH3.
NH3 + H2O NH4+ + OH-
Initial moles 0.1 0 0
At equil. 0.1 – [OH ]
- -
[OH ] -
[OH ]
+ −
[𝑁𝐻4 ][𝑂𝐻 ] [𝑂𝐻 ]2
−
𝐾𝑏 = =
[𝑁𝐻3 ] 0.1 − [𝑂𝐻− ]
Since the base is weak, the concentration of the base would be much greater than the
[OH-] ion concentration so, it is reasonably safe to assume that 0.1 – [OH−] ≈ 0.1.
Thus,
[𝑂𝐻− ]2
𝐾𝑏 =
0.1
−
[𝑂𝐻 ] = √0.1 𝐾𝑏 = √0.1 × 1.8 × 10−5
[𝑂𝐻 − ] = 1.34 × 10−3 𝑚𝑜𝑙𝑑𝑚−3
Use Kw to find [H+]
Kw = [H+][OH-]
𝐾𝑤 1 ×10−14
[H+]= = 1.34 × 10−3 = 7.46 × 10-12 moldm-3
[𝑂𝐻 − ]
pH = – log10 (7.46 × 10-12) = 11.1

Questions

Calculate the pH of:

1. 0.001 M of HNO3
2. 0.001 M of H2SO4
3. 0.001 M of NaOH
4. 0.001 M of Ba(OH)2

5. For a weak base BOH with Kb = 5.4 × 10-4 M in 0.1 M solution, calculate [OH-] and
pH.
6. The pH of a 0.1 M solution of a weak base RNH 2 is 10.5. Calculate [H+], [OH-] and
Kb and pKb.

7. A mixture of 0.50 mol ethanoic acid and 1 mole of ethanol was shaken for a long time
to reach equilibrium. The whole mixture was then quickly titrated with 1 moldm-3
sodium hydroxide and 80 cm3 of NaOH were required.
a) i) Write an equation for the reaction between ethanoic acid and ethanol
ii) Why was the mixture titrated quickly?
b) Using the titration results,
i) How many moles of ethanoic acid remained at equilibrium?
ii) How many moles of ethanoic acid had reacted?
iii) How many moles of ethanol were left in the equilibrium mixture
c) Write the expression for Kc for the equation in a) i) and find its value.

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pH Changes During Acid Base Titrations

As an alkaline solution is run into an acidic solution (or vice versa) during a titration, there is
a change in the pH value at the end point. The change may be a sharp one which can be
detected by an indicator. The way in which the pH changes during the course of a reaction
depends on the nature of the acid or alkali used as follows:

Titration of a Strong Acid Against a Strong Alkali

e.g. 25 cm3 of 0.1 M HCl and 0.1 M NaOH

The graph shows that there is a sudden change in pH from 4 to 10 near the end point. When
equivalent amounts of acid and alkali are present the solution is exactly neutral, with a pH of
7.

Titration of a Weak Acid Against a Strong Alkali

e.g. 25 cm3 of 0.1 M CH3COOH and 0.1 M NaOH

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CH3COOH (aq) + NaOH (aq) CH3COONa (aq) + H2O (l)

Hydrolysis of salt: CH3COONa (aq) + H2O (l) CH3COOH (aq) + NaOH (aq)
The pH at the end point when equivalent amounts of weak acid and alkali are present is
greater than 7. This is because a mixture of equal amounts of a strong alkali and a weak acid
forms an alkaline solution. The salt formed is hydrolysed, that is, interacts with water.
CH3COONa is fully ionised and the Na+ and CH3COO- ions interact with OH- and H+ ions
respectively from water. The interaction is not equal. Formation of molecules of weakly
ionised CH3COOH removes some H+ ions from solution but there is no compensating
removal of OH- ions because NaOH is fully ionised. The solution therefore contains an
excess of OH- ions and is alkaline. Marked change in pH at end-point between 7.5-10.5.

Titration of a Strong Acid Against a Weak Alkali

e.g. 25 cm3 of 0.1 M HCl and 0.1 M NH3

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HCl (aq) + NH4OH (aq) NH4Cl (aq) + H2O (l)

Hydrolysis of salt: NH4Cl (aq) + H2O (l) HCl (aq) + NH4OH (aq)
The pH at the end point when equivalent amounts of acid and weak alkali are present is less
than 7. This is because a mixture of equal amounts of a strong alkali and a weak acid forms
an acidic solution. The salt formed is fully ionised and is hydrolysed again with unequal
interactions. Formation of molecules of weakly ionised NH4OH removes some OH- ions from
solution but there is no compensating removal of H+ ions because HCl is fully ionised. The
solution therefore contains an excess of H+ ions and is acidic. Marked change in pH at end-
point between 3.5-6.5 approx.

Titration of a Weak Acid Against a Weak Base

e.g. 25 cm3 of 0.1 M CH3COOH and 0.1 M NH3

The pH changes in the reaction between a weak acid and a weak alkali are gradual. Since
there is no significant change in pH at the end point, the end point of these reactions cannot
be accurately detected by any indicator. No marked change can be detected.

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Neutralisation (pH) Indicators

HIn (aq) + H2O (l) H3O+ (aq) + In-

One colour different colour

Indicators are substances which vary in colour according to the [H +] of the solution to which
they are added. They are themselves weak acids or weak bases. They can be used to measure
[H+] or to detect the changes in [H+]. Different indicators change colour over different ranges
of pH. In an acid-base titration it is important to choose an indicator which changes colour
over the range in which there is a marked or significant pH change at the end point.

Indicator ‘Acidic’ colour ‘Alkaline’ colour pH Range

Thymol blue (first transition) Red Yellow 1.2 – 2.8
Bromophenol blue Yellow Blue 3.0 – 4.6
Methyl orange Red Yellow 3.1 – 4.4
Screened methyl orange Red Green 3.2 – 4.2
Methyl red Red Yellow 4.4 – 6.2
Litmus Red Blue 4.5 – 8.3
Bromothymol blue Yellow Blue 6.0 – 7.6
Thymol blue (second transition) Yellow Blue 8.0 – 9.6
Phenolphthalein Colourless Pink 8.3 – 10.0

Choosing Appropriate Indicators for Titrations

Titration Marked pH Change Appropriate Indicator
Strong acid vs. Strong alkali 4 – 10 Almost any indicator
Weak acid vs. Strong alkali 7.5 – 10.5 Phenolphthalein
Strong acid vs. Weak alkali 3.5 – 6.5 Methyl red or screened methyl orange
Weak acid vs. Weak alkali No marked change No indicator is accurate for end point
detection

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BUFFERS

A buffer solution is one which maintains a fairly constant pH even when small amounts of
acid or alkali are added to it.

Types of Buffer Solution

Acidic Buffer Solution

These are made by mixing a weak acid and a salt of the same weak acid.

e.g. CH3COOH and CH3COONa

CH3COONa is fully ionised as shown and the CH3COO- ions it produces suppress the
ionisation of the CH3COOH (aq) so that the mixture contains more acid molecules and more
ethanoate ions than a simple solution of CH3COOH (aq).

CH3COOH (aq) CH3COO- (aq) + H+ (aq)

CH3COONa (aq) CH3COO- (aq) + Na+ (aq)

High concentration of CH3COO- and CH3COOH

The excess CH3COO- ions react with any added H+ ions while the excess CH3COOH
molecules react with any added OH - ions.

Add H+: CH3COO- (aq) + H+ (aq) CH3COOH (aq)

Add OH-: CH3COOH (aq) + OH- (aq) CH3COO- (aq) + H2O (l)

Calculating the pH of Acidic Buffers

[𝐶𝐻3 𝐶𝑂𝑂 − ][𝐻 + ]
Ka = [𝐶𝐻3 𝐶𝑂𝑂𝐻]
[𝐶𝐻 𝐶𝑂𝑂𝐻]
+
[H ] = 𝐾𝑎 × [𝐶𝐻3 𝐶𝑂𝑂 −]
3
Since the [CH3COOH] and [CH3COO-] are high, assume:
 [CH3COOH] = [acid]
 [CH3COO-] = [salt]
[𝑎𝑐𝑖𝑑]
[H+] = 𝐾𝑎 × [𝑠𝑎𝑙𝑡]
pH = – log[H+]
[𝑎𝑐𝑖𝑑]
– log[H+] = – log Ka – log [𝑠𝑎𝑙𝑡]
[𝑠𝑎𝑙𝑡]
pH = pKa + log[𝑎𝑐𝑖𝑑] Henderson−Hasselbalch equation

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Alkaline Buffer Solution

These are made by mixing a weak base with a salt of the same weak base.
e.g. NH3 (aq) and NH4Cl (aq)

NH4Cl is fully ionised as shown and the NH4+ ions it produces suppress the ionisation of the
NH3 (aq) so that the mixture contains more ammonia molecules and more ammonium ions than
a simple solution of NH3 (aq).

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

NH4Cl (aq) NH4+ (aq) + Cl- (aq)

High concentration of NH3 and NH4+

The excess NH3 molecules react with any added H+ ions while the excess NH4+ molecules
react with any added OH- ions.

Add H+: NH3 (aq) + H+ (aq) NH4+ (aq)

Add OH-: NH4+ (aq) + OH- (aq) NH3 (aq) + H2O (l)

Calculating the pH of Alkaline Buffers

[𝑁𝐻4 + ][𝑂𝐻 − ]
Kb = [𝑁𝐻3 ][𝐻2 𝑂]
Since [H2O] is so large, it is considered to be a constant and is excluded from the equilibrium
expression.
[𝑁𝐻 ]
[OH-] = 𝐾𝑏 × [𝑁𝐻 3+]
4

Use Kw to find the [H+]

Kw= [H+][OH-]
[𝐾 ]
[H+] = [𝑂𝐻𝑤−]
Since the [NH3] and [NH4+] are high, assume:
 [NH3] = [base]
 [NH4+] = [salt]

[𝑏𝑎𝑠𝑒]
[OH-] = 𝐾𝑏 × [𝑠𝑎𝑙𝑡]

𝐾𝑤 𝐾𝑤 [𝑁𝐻4 + ]
[𝐻+ ] = =
[𝑂𝐻− ] 𝐾𝑏 [𝑁𝐻3 ]

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 REACTION KINETICS AND CHEMICAL EQUILIBRIA

𝐾 [𝑠𝑎𝑙𝑡]
[H+] = 𝐾𝑤 × [𝑏𝑎𝑠𝑒]
𝑏
pH = – log[H+]
[𝑠𝑎𝑙𝑡]
– log[H+] = – log Kw – – log Kb + – log[𝑏𝑎𝑠𝑒]
[𝑏𝑎𝑠𝑒]
pH = pKw – pKb + log [𝑠𝑎𝑙𝑡]

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 REACTION KINETICS AND CHEMICAL EQUILIBRIA

Alternatively,
[𝑁𝐻 ]
[OH-] = 𝐾𝑏 × [𝑁𝐻 3+]
4
[𝑏𝑎𝑠𝑒]
pOH = pKb + – log [𝑠𝑎𝑙𝑡]
[𝑠𝑎𝑙𝑡]
pOH = pKb + log[𝑏𝑎𝑠𝑒]
Since Kw = [H+][OH-]
pKw = pH + pOH

Since Kw = 1 × 10-14 mol2dm-6, pKw = 14

14 = pH + pOH

pH = 14 – pOH

Questions

1. If an aqueous solution of 0.1 M in a weak acid HA and 0.5 M in its salt, NaA and the
acid has a Ka of 1.65 × 10-6 M. Calculate pH.
2. An aqueous solution is 0.2 M in a weak acid HB and 0.6 M in its salt NaB and the
acid has a pH of 5.43. Calculate:
a. [H+]
b. Kb
3. The pKb value of a base is 3.27. Calculate
a. Its Kb value
b. The pH of a 0.1 M solution of the base
c. The pH of a solution that is 0.1 M in the base and 0.4 M in its chloride salt.

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Biological Importance of Buffers

 Buffer solutions are necessary to keep the correct pH for enzymes in many organisms
to work.

 Many enzymes work only under very precise conditions; if the pH moves outside of a
narrow range, the enzymes slow or stop working and can denature. In many cases
denaturation can permanently disable their catalytic activity.

 A buffer of carbonic acid (H2CO3) and bicarbonate (HCO3−) is present in blood

plasma, maintaining a pH between 7.35 and 7.45.

 Other buffers perform a more minor role than the carbonic acid-bicarbonate buffer in
regulating the pH of the blood. The phosphate buffer consists of phosphoric acid
(H3PO4) in equilibrium with dihydrogen phosphate ion (H2PO4-) and H+. The pKa for
the phosphate buffer is 6.8, which allows this buffer to function within its optimal
buffering range at physiological pH. The phosphate buffer only plays a minor role in
the blood, however, because H3PO4 and H2PO4- are found in very low concentration in
the blood.

 Amino acids and proteins in the blood also act as a buffering system since they
contain acid and base functional groups within the same molecule and can respond to
small changes in pH, thereby minimising the effect of a pH change. Large changes in
pH can cause coagulation of blood proteins.

 In the pharmaceutical industry, most of the medicines are prepared in aqueous

solution of different chemicals so these aqueous solutions require a constant pH in
order to assure the stability and clinical effectiveness of a medicines and this is done
through buffers. Buffers are also added in pharmaceuticals to improve patient comfort
and to make longer transportation of medicines possible.

Industrial Importance of Buffers

 Buffers are also used in foods to maintain the acidity of the food in order to preserve
the flavour and appearance of food. Buffers maintain the physical, chemical and
microbiological stability of foods. Actually, food additives act as buffers usually
consist of metal salts and weak acids found naturally within the food to be preserved.
For example, the addition of sodium citrate to a food containing citric acid will create
a buffer solution.

 Buffer solutions are used in fermentation processes and in setting the correct
conditions for dyes used in colouring fabrics. They are also used in chemical analysis
and calibration of pH meters.

 The majority of biological samples that are used in research are made in buffers,
especially phosphate buffered saline (PBS) at pH 7.4.

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SOLUBILITY PRODUCT

The term insoluble is not totally accurate. No ionic substance is completely insoluble in
water. The dissociation process takes place even with substances which are called insoluble
such as barium sulphate, calcium carbonate and silver chloride.

The term insoluble should be taken to mean that the solubility of a substance is extremely
low. In a saturated solution of a sparingly soluble electrolyte, the product of the
concentrations of the ions raised to the power as indicated by the formula is a constant
at a particular temperature. This constant is called the solubility product constant (K s
or Ksp).

Derivation of the Solubility Product

BaSO4 (s) + H2O (l) Ba2+ (aq) + SO42- (aq)

[𝐵𝑎 2+ ][𝑆𝑂4 2− ]
The equilibrium expression is: 𝐾𝑐 = [𝐵𝑎𝑆𝑂4 ]

Water is excluded from the equilibrium expression as it is in such a large quantity that its
concentration is assumed to be constant. Furthermore, since the barium sulphate is a solid,
then its concentration is constant, that is, [BaSO4] = constant. The solubility product constant
is thus defined by the equation:

Ksp = [Ba2+][SO42-]

Main Uses of Solubility Product

The main use of solubility product is concerned with the conditions under which an
electrolyte will dissolve or will come out of solution as a solid, that is, form a precipitate. The
solubility product only applies to saturated solutions.

For a sparingly soluble electrolyte, AB, the ionic product is defined as the product of the
concentrations of ions A+ and B-

𝐼𝑜𝑛𝑖𝑐 𝑝𝑟𝑜𝑑𝑢𝑐𝑡, 𝑄𝑆𝑃 = [𝐴+ ][𝐵− ]

 If a solution has an ionic product that is less than its Ksp value at that temperature, the
solution is unsaturated and more AB can dissolve.
 If a solution has an ionic product that is equal to its Ksp value at that temperature, the
solution is saturated and no more AB can dissolve.
 It is impossible to obtain ionic products greater than the K sp value at a particular
temperature, as excess ions immediately will precipitate out to reach the K sp value.
Hence, if a solution has an ionic product that is ‘more’ than its Ksp value at that
temperature, the solution is supersaturated and solid AB will precipitate out of
solution until the ionic product attains the Ksp value.

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Selective Precipitation

If an aqueous solution of an anion, X- (aq) is added drop-wise to a mixture of cations which

form sparingly soluble compounds with the X - ion, the compound with the lowest Ksp value
will be precipitated first.

Given,

Ksp (PbS) = 4.0 × 10-28 mol2dm-6

Ksp (FeS) = 6.3 × 10-18 mol2dm-6

If H2S is bubbled through an equimolar mixture of Pb2+ (aq) and Fe2+ (aq) then the Pb2+ (aq) is
more completely precipitated than the Fe2+ (aq) due to its lower Ksp value.

If the [S2-] added can be controlled, this can be used to separate the cations by selective
precipitation.

The Common Ion Effect

The Common Ion Effect is defined as the effect which causes the repression of the
dissociation of a compound by the addition of a common cation or anion and results in
decreased solubility of the compound. This effect affects the equilibrium composition but
not the ionisation constant.

If sodium chloride is added to a saturated solution of silver chloride, the increase in

concentration of the chloride ion will force the dissociation equilibrium to the left by Le
Chatelier’s Principle.

AgCl (s) Ag+ (aq) + Cl- (aq)

NaCl (aq) Na+ (aq) + Cl- (aq)

As the equilibrium shifts to the left, this leads to a decrease in the solubility of the silver
chloride. The condition for equilibrium is that the ionic product [Ag+][Cl-] is equal to the Ksp
(AgCl). The increased [Cl-] results in decreased [Ag+] in order to keep the ionic product equal
to the Ksp value. Thus, the equilibrium shifts to the left resulting in precipitation of more
silver chloride.

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Calculating Solubility Product

Worked Example

[Link] calculate the Ks given Solubility:

Example:

Calculate the Ks of silver chloride given its solubility is 10 -5 moldm-3 at 18 °C.

AgCl (s) Ag+ (aq) + Cl- (aq)

1 1 1

Thus if [AgCl] = 10-5 moldm-3, then [Ag+] = [Cl-] = 10-5 moldm-3

Ksp = [Ag+][Cl-]

= 10-5 × 10-5

=1 x 10-10 mol2dm-6

2. To calculate Solubility given Ks:

Example: Silver Chromate (VI) has a Ks of 2.5 x 10-12 mol3 dm-9 . Calculate it’s solubility.

Ag2CrO4 (s) 2Ag2+(aq) + CrO42- (aq)

Let the solubility of Ag2CrO4 be x mol dm-3.

Therefore, [Ag+] = 2x mol dm-3

[CrO42-] = x mol dm-3

Ks = , [Ag+]2 [CrO42-]

2.5 x 10-12 = (2x)2(x)

2.5 x 10-12 = 4x3

X = 8.55 x 10-5 mol dm-3

3. To Calculate Solubility in a solvent with a Common Ion.

Example: Calculate the solubility of AgCl to which 0.1M HCl was added. Given Ks of AgCl
= 1 x 10-10 mol2dm-6.

AgCl (s) Ag+ (aq) + Cl- (aq)

HCl(aq) H+ (aq) + Cl- (aq)

0.1M 0.1M

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Since the AgCl is only slightly dissociated and the HCl is fully dissociated, The [Cl-] is taken
as that from the HCl i.e. 0.1M

Take the [Ag+] as the new Solubility.

[Ag+][Cl-] = 1 x 10-10

[Ag+] x 0.1 = 1 x 10-10

[Ag+] = 1 x 10-9 mol dm-3 From Example 1 , the solubility of AgCl has
decreased from 1 x 10-5 mol dm-3 to 1 x 10-9 mol dm-3 in the presence of the Cl- common ion.

Practical Applications of Solubility Product

Selective Precipitation

Selective precipitation can be used in qualitative analysis to design methods for separating
ions in solution. Selective precipitation is used to form a solid with one of the ions in solution
without disturbing the other ions.

Worked Example

A litre of 0.2 M SrCl2 solution is contaminated with 0.01 moles of BaCl2. Given the Ksp of
BaSO4 = 1.5 × 10-9 mol2dm-6 and Ksp of SrSO4 = 7.6 × 10-7 mol2dm-6, 0.001 M Na2SO4
solution is added to the mixture to separate the Ba2+ and Sr2+. If selective precipitation be
used to separate the metals, which ion will precipitate first?

Using the Ksp values of each precipitate, the sulphate concentration at which each of the ions
will be converted to precipitate is calculated.

𝐾𝑠𝑝 = [𝐵𝑎2+ ][𝑆𝑂4 2− ] = 1.5 × 10−9

𝐾𝑠𝑝 = [𝑆𝑟 2+ ][𝑆𝑂4 2− ] = 7.6 × 10−7

𝐾 1.5 × 10−9
BaSO4 will precipitate when [SO42-] reaches [𝐵𝑎𝑠𝑝2+ ] = = 1.5 × 10−7 𝑀
0.01

𝐾 7.6 × 10−7
SrSO4 will precipitate when [SO42-] reaches [𝑆𝑟𝑠𝑝
2+ ] = = 3.8 × 10−6 𝑀
0.2

The 0.001 Na2SO4 solution is carefully added in µL until volume added is 0.15 mL. A fine
white precipitate of BaSO4 may begin to be observed. Addition of Na2SO4 may continue to a
volume of 3.75 mL. If the volume added exceeds 3.8 mL, SrSO 4 will also begin to
precipitate. In this way nearly all of the Ba2+ contaminant can be removed as precipitate,
which may then be filtered off.

Formation of Kidney Stones

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Kidney stones are solid pieces of mass, which are made up of tiny crystals and are found in
the kidney and/or the ureter. Kidney stones occur when there is a constant build up of certain
substances in the kidney, such as calcium ions. Calcium oxalate is a very common kidney
stone.

Ca(C2O4) (s) Ca2+ (aq) + C2O42- (aq)

𝐾𝑠𝑝 = [𝐶𝑎2+ ][𝐶2 𝑂4 2− ]

• A diet with a high intake of calcium (dairy products) will shift the equilibrium to the
left by the common ion effect and cause calcium oxalate crystals to form in the kidney
due to its reduced solubility.

• A diet with a high intake of oxalate (chocolate, spinach etc.) will also shift the
equilibrium to the left by the common ion effect and cause solid calcium oxalate to
build up.

Other common kidney stones are calcium phosphate, magnesium ammonium phosphate
(struvite) and uric acid.

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REDOX EQUILIBRIA

A piece of metal contains metal cations arranged in a lattice with a cloud of delocalised
electrons moving through the metal crystal. When a strip of metal is placed in a solution of its
ions, two processes may occur:

1. Metal cations from the strip may dissolve into the solution causing the strip to become
negatively charged.
2. Metal cations from the solution can accept electrons from the strip of metal become
discharged and thereby make the strip positively charged.

An equilibrium is set up between these two processes and the charge on the metal strip is
dependent on the metal used and the concentration of ions from the solution at the surface of
the metal strip.

M+ (aq) + e- M (s)

M (s) – e- M+(aq)

Overall equilibrium: M+ (aq) + e M(s)

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Formation of Helmholtz Double Layers

For the Zn metal in the Zn2+ solution the equilibrium lies to the left. The Zn cations on the
metal go into solution leaving electrons on the rod which acquires a negative charge as a
result. The solution around the rod has an increase in positive charge. This gives one type of
double layer.

The Cu metal in the Cu2+ solution, the equilibrium lies to the right. The Cu 2+ ions in solution
attract electrons out of the rod and become discharged. The discharged atoms will deposit on
the surface of a rod and acquires a positive charge. The solution near the rod loses positive
ions and negatively charged giving another type of double layer.

Standard Electrode Potentials

When a metal rod is immersed in a solution of its ion, a charge accumulates on the metal rod
and the metal rod can be measured to find its electrode potential. If the concentration of the
solution is 1 moldm-3 and the temperature is kept at 25 °C, then the potential acquired under
these standard conditions is the standard electrode potential (SEP) of that metal Eө.

Finding/Measuring Electrode Potentials

If a cell is constructed from a standard electrode, that is, one of known potential and an
electrode of unknown potential, the electromotive force (EMF) of cells can be measured
using a voltmeter and be used to find the unknown electrode potential.

Eөcell = Eөelectrode of unknown potential – Eөstandard electrode

There are two standard electrodes used to measure the S.E.P. of other half cells.

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The Standard Hydrogen Electrode

The reaction taking place in S.H.E. is: 2H+ (aq) + 2e- H2 (g)

Under standard conditions, the EMF of the S.H.E. is taken to be 0.00V.

EөSHE = 0.00V or EөH2(g)/ H+(aq) = 0.00V

NOTE: The platinised platinum electrode is used in the standard hydrogen electrode for three
reasons;

1. The platinum metal is inert as it has very little tendency to ionise in the acid solution.
2. Platinum is able to adsorb hydrogen gas and thereby act as a solid source of molecular
hydrogen.
3. The coat of finely divided platinum, also known as platinum black, increases the
surface area of the metal and thus allows the reaction to reach equilibrium quickly.

The Saturated Calomel Electrode

The (S.H.E) is not a convenient standard electrode due to difficulty in maintaining a stream
of hydrogen gas at 1 atmosphere. Therefore, a secondary standard is used as a reference
electrode. The Saturated Calomel Electrode contains mercury liquid and solid mercury (I)
chloride (calomel) in contact with a saturated solution of potassium chloride. An equilibrium
is set up:

Hg+(aq) + e- Hg (l)

The EMF of the saturated calomel electrode compared to the standard hydrogen electrode is
0.244 V under standard conditions.

Eөcell = Eөsaturated calomel electrode – Eөstandard hydrogen electrode = 0.244 V – 0.00 V = 0.244 V

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Types of Half Cells

The constituents of a redox equilibrium make a half cell. Half-cell equilibrium is shown by a
half equation which is expressed as a reduction reaction.

Oxidised species + ne- → Reduced species

Examples: Zn2+ (aq) + 2e- Zn (s)

Cl2 (g) + 2e- 2Cl- (aq)

MnO4-(aq) + 8H+ (aq) + 5e- Mn2+ (aq) + 4H2O (aq)

There are four types of half cells;

1) The metal/metal ion half cell: a metal in contact with one of its cells
e.g. Zn(s)/Zn2+ (aq)
2) The non-metal/non-metal ion half cell: in this half-cell, equilibrium is established
between a non-metallic element and ion derived from that element in solution.
e.g. Cl2 (g)/Cl- (aq)
The non-metal is usually gaseous and bubbled through a solution of its ions. The
redox equilibrium is established at the surface of an inert metal conductor.

3) The ion/ ion half cell

e.g. Fe2+ (aq)/Fe3+ (aq)

Half equation: Fe3+ (aq) + e- Fe2+(aq)

In this half-cell an inert electrode e.g. Pt is in contact with a solution containing 2
types of ions derived from the same element but each is a different oxidation state.
Each ion has a concentration of 1M.

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4) Redox half cell

e.g. MnO4, H+/Mn2+
In this half-cell, an inert electrode e.g. Pt, is in contact with a 1M solution of a redox
reagent e.g. KMnO4, K2Cr2O7, Na2S2O3, H2O2, etc…
Oxidising agents often require H+ ions in solution for the equilibrium to be
established.

Combining Half Cells to Form Electrochemical Cells

The type of cell in which a chemical reaction results in the production of an electric current is
called an electrochemical cell (also known as a galvanic cell or voltaic cell). The
electromotive force of the cell is a measure of the tendency of electrons to flow through the
external circuit.

In the Daniell cell, the zinc/ Zn2+ half-cell is connected to Cu/ Cu2+ half-cell. A salt bridge is
used to complete the circuit and thus allows the conduction of electricity without allowing the
solutions in each of the half-cells to mix. The salt bridge contains an electrolyte such as
potassium chloride (KCl) or sodium chloride (NaCl).

Cells are always shown with the more negative electrode on the left hand side. In this case,
zinc is more negative than copper, hence the zinc half-cell is shown on the left.

Salt Bridge

In the Daniell cell, the zinc atoms go into solution as Zn2+ and the Cu2+ ions come out of
solution. The solution in the Zn half cell becomes richer in positive ions. If this positive
charge builds up, then the electrons on the zinc electrode are attracted by the solution. In the
copper half cell, positive ions are lost from solution, so that the attraction for electrons is
reduced. In this situation, electrons would not travel from zinc to copper and the cell would
not work. The salt bridge provides positive and negative ions (K+ and Cl-) which travel into
the two solutions. This keeps the charge in both cells in balance.

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Cell Statement or Cell Diagram

Cells can be represented by a cell diagram or statement. The half-cell in which

oxidation occurs is on the left hand side. The one where reduction occurs is on the right hand
side. Each half cell is written so that the dominant chemical process taking place in each half
cell may be read left to right. A salt bridge is shown by two vertical broken lines. Phase
boundaries are shown by a single vertical line. The half-cell with the more positive electric
potential is placed on the left is written as an oxidation, the one on the right is written as a
reduction. If an inert electrode is used (Pt) it is placed next to the more reduced species in the
correct half-cell.

If the members of a half cell are both in the same phase, they are separated by a comma. An
inert electrode is shown next to the more reduced species in the half cell which it is used.

Electrodes in an Electrochemical Cell

The electrode at which oxidation takes place is called the anode and the electrode at which
reduction takes place is called the cathode.

In the Daniell cell, the zinc electrode is the anode and the copper electrode is the cathode.

These definitions also apply to electrolysis.

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Questions:

Given:

(i) Cu2+(aq)/Cu(s) +0.34 V

Ag+(aq)/Ag(s) +0.80V

(ii) Al3+(aq)/Al(s) -1.66V

Fe2+(aq)/Fe(s) -0.44V

(iii) Br2(aq)/Br (aq) +1.07V

Pb2+(aq)/Pb(s) -0.13 V

(iv) Sn4+(aq)/Sn2+(aq) +0.15 V

Fe3+(aq)/Fe2+(aq) + 0.77 V

(a) Write the Cell Statement.

(b)Calculate Eөcell.

(c) Write the overall cell reaction.

Points to Note:

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 For half cells, the SEP values given for the reduction reaction, consequently SEP’s are
also called Standard Reduction Potential.
 The half-cell on the left hand side of an electrochemical cell will undergo the
oxidation reaction provided that EөRHS − EөLHS is positive.
 The half-cell on the right hand side of an electrochemical cell will undergo the
reduction reaction provided that EөRHS − EөLHS is positive.

Cases

1. Given Zn2+ (aq) | Zn (s) = − 0.76 V and Cu2+ (aq) | Cu (s) = + 0.34 V
2. Given Ag+ (aq) | Ag (s) = + 0.80 V and Cu2+ (aq) | Cu (s) = + 0.34 V
3. Given Li+ (aq) | Li (s) = − 3.04 V and Zn2+ (aq) | Zn (s) = − 0.76 V

For each of the above cases:

a. Draw the electrochemical cell or cell diagram.

b. Calculate the Eөcell using Eөcell = EөRHS − EөLHS
c. Write overall reaction

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Standard Electrode and Redox Potentials

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Uses of S.E.P Values

1) Predicting Feasibility of Reactions.

The reaction below has a positive Eө cell value:
Cu2+(aq) + Zn(s) Cu(s) + Zn2+(aq) Eөcell = +1.10V
The opposite reaction will have a negative Eөcell value.
Cu(s) + Zn2+(aq) Cu2+(aq) + Zn(s) Eөcell= –1.10V
Positive cell EMF’s indicates that a reaction is feasible and energetically favourable
whereas negative EMFs indicate that a reaction is unlikely to occur.

2) The Electrochemical Series

When all the redox systems are arranged in order of standard electrode potentials, the
electrochemical series is obtained. The electrochemical series is arranged in
increasing order of magnitude of the SEP values. Strong reducing agents with
negative SEP values are at the top while strong oxidising agents with positive SEP
values are at the bottom.

3) Calculating Cell Emf’s

When two half cells are combined to form an electrochemical cell, the E өcell value
must be positive in order for the cell reaction to occur spontaneously, that is, without
significant external energy input. A redox reaction will tend to the right for a cell
where Eөcell ≥ 0.3 V unless the reaction occurs too slowly for it to be feasible. Thus,
rate of reaction (kinetic factor) can influence the spontaneity of the reaction even if
the reaction is energetically feasible, i.e. the energy of the products favours the
reaction (thermodynamic factor).
Example:
The copper half cell and the SHE have a E өcell value of 0.34 V
H+(aq), H2 (g) /Pt || Cu2+ (aq)/ Cu (s) Eөcell = 0.34 V
But no reaction occurs when they are copper mixes with dilute acid as the reaction
occurs too slowly.

4) Determining Electron Flow Between Electrodes In A Full Cell

When half cells are connected to form a full cell, the difference in SEP values (the
potential difference) can result in a current flowing through an external circuit. While
conventional current shows the flow of positive charges (holes) in a circuit, electrons
will flow in the opposite direction as they are negatively charged. Electrons flow from
the electrode with the smaller (more negative) SEP value to the electrode with the
larger (more positive) SEP value.

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The Effect of Changing Concentration on Eө Values

Ag+ (aq) + e- Ag (s)

If the concentration of species on either side of an equilibrium is changed, Le Chatelier’s

Principle dictates that the equilibrium will shift in the direction that reduces this change.
Since solid silver metal would not have a concentration, the concentration of Ag+ (aq) will
affect the equilibrium.

 In a more dilute solution than 1 M Ag+ (aq), the solid metal will dissolve into solution
in order to increase the concentration of Ag+ (aq) resulting in an excess of electrons on
the electrode  electrode potential decreases from SEP value.
 In a more concentrated solution than 1 M Ag+ (aq), ions from solution will become
discharged in order to decrease the concentration of Ag+ (aq) resulting in a deficit of
electrons on the electrode  electrode potential increases from SEP value.

The pHmeter

A pHmeter contains a glass electrode containing a sealed platinum wire in a buffer solution
connected to a saturated calomel reference electrode. The potential of the glass electrode
depends on the concentration of ions in solution and the temperature of the solution. Thus the
potential of the glass electrode is proportional to the H + ion concentration and thus also the
pH of the solution; the pH is displayed on the instrument.

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Useful Electrochemical Cells

Primary Cells (non-rechargeable)

The Daniell Cell

Made of zinc and copper half cells. Eөcell = 1.10 V

At Zn cathode: Zn (s) – 2e- Zn2+ (aq)
At Cu anode: Cu2+ (aq) + 2e- Cu (s)

Dry Cells

These were invented to prevent electrolyte leakage of cells with a similar arrangement to the
Daniell cell. The electrolyte is made into a paste instead.

Le Clanché Dry Cell

The dry cell produces a maximum of 1.5 V and is used in radios, flashlights etc. Dry cells are
leak proof because the components are solids or pastes which are sealed from the
environment. They are relatively inexpensive, but their voltage tends to drop quickly and they
cannot be reused. The zinc anode encloses the cell and the cathode is a central graphite rod,
immersed in a paste consisting of a mixture as shown in the diagram. When a high current is
demanded from the battery, the hydrogen gas cannot react quickly enough. The reaction
slows down as there is a build up of gas and the voltage drops.

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At Zn anode: Zn (s) – 2e- Zn2+ (aq)

At cathode: 2NH4+ (aq) + 2e- 2NH3 (aq) + H2 (g)
H2 (g) + 2MnO2 (s) Mn2O3 (s) + H2O (l)

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The Alkaline Battery

The alkaline battery produces a voltage slightly above 1.5 V. The reaction at the anode is
oxidation of zinc but under alkaline conditions. At the cathode, manganese (IV) oxide is
reduced to manganese (III) oxide with OH- ions being generated. The alkaline battery does

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not produce hydrogen or any other gas. Hence it does not suffer a voltage drop of a common
dry cell when worked hard.

At Zn anode: Zn (s) – 2e- Zn2+ (aq)

At cathode: H2O (l) + 2MnO2 (s) 1 + 2e 2Mn2O3 (s) + 2OH- (aq)

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Secondary Cells (rechargeable)

The Lead-Acid Accumulator consists of six 2.0 V cells connected in series. Lead-acid
batteries are found in cars and trucks. They are made from a combination of secondary cells.
A typical battery has two types of metal plates. One has lead as the anode and the other is a
cathode made of lead and coated with lead (IV) oxide. The plates are separated by an inert
material and immersed in a solution of 30% sulphuric acid of density 1.25 gm-3. The lead
(IV) oxide plates are the positive electrode and the lead the negative electrode.

At the negative plates: Pb (s) + SO42- (aq) PbSO4 (s) + 2e-

At the positive plates: PbO2 (s) + SO42- (aq) + 2e- + 4H+ (aq) PbSO4 (s) + H2O (l)

The reactions both go to the right when current is being drawn, that is, lead sulphate is made
at both positive and negative plates, however this happens by two different reactions and for
each mole of lead sulphate formed, 2 moles of electrons travel through the external circuit.
These electrons make the lights, radio etc. work.

When the vehicle moves, an electric current is generated by the alternator. This current is
passed into the battery in the direction that forces the two reactions to go to the left, that is,
lead sulphate is decomposed. This charging and discharging can go on indefinitely. However
the sulphuric acid decomposes and with time the structure of the plates change. If a battery
spends most of its time in a discharged state, then so much lead sulphate builds up that it is
impossible to remove.

Find out about rechargeable batteries!

Fuel Cells

A fuel cell is a primary cell of a special type. The chemicals that produce electricity are
constantly replaced as soon as they are used. The hydrogen- oxygen fuel cell generates
electricity using a porous carbon electrode and a solution of an alkali. The hydrogen gas
diffuses through the porous anode. When it comes into contact with the potassium hydroxide,
it is oxidised to water and electrons are released. The electrons travel to the positive terminal
where oxygen is used up. The oxygen diffuses through the electrode and is reduced to OH-
ions. The cell provides a reliable supply of electricity and it also produces water. This type of
fuel cell is used in space exploration, where the water can be used by the astronauts on board.

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 REACTION KINETICS AND CHEMICAL EQUILIBRIA

Questions

1. Are the following reactions feasible? Give reasons for your answers.
i. Pb2+ (aq) + Sn4+ (aq) Pb4+ (aq) + Sn2+ (aq)
ii. 3Mg (s) + 2MnO4- (aq) + 8H+ (aq) 3Mg2+ (aq) + 2MnO2 (s) + 4H2O (l)
iii. Fe2+ (aq) + VO2+ (aq) + 2H+ (aq) Fe3+ (aq) + VO2+ (aq) + H2O (l)
iv. 2Cr2+ (aq) + Cl2 (g) 2Cr3+ (aq) + 2Cl- (aq)

2. In the following pairs of half cells, state from which half cell electrons will flow.
i. Zn2+ | Zn and H2O2 | H2O
4+ 2+
ii. Pb | Pb and V3+ | V2+
iii. Ni2+ | Ni and SO42- | SO2
iv. Cu2+ | Cu+ and Cu+| Cu

3. Calculate the overall Eө values and write a balanced equation for any reactions
between:
i. Acidified KMnO4 and Br- (aq)
ii. Fe2+ and Cl2
iii. SnCl2 and acidified H2O2
iv. I2 (aq) and Cr3+ (aq)

4. Is the reaction between [Fe(CN)6]4- and 1 moldm-3 H+ (aq) feasible? Show your
calculations that made you come to this conclusion. Suggest one reason why this
reaction may not occur in reality.

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REACTION KINETICS AND CHEMICAL EQUILIBRIA

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 REACTION KINETICS AND CHEMICAL EQUILIBRIA

UNIT 1: CHEMICAL APPLICATIONS AND PRINCIPLES I

SUMMARY OF MODULE 2: KINETICS AND EQUILIBRIA

 Rates of reactions: terms and definitions, Rate equations, Order of a reaction, factors
affecting rates, half-life (1st order), effect of temperature and catalysts on Boltzmann curves
 Chemical equilibrium: Dynamic equilibrium, Kc, Kp, Le Chatelier’s Principle
 Acid/Base equilibria: Strong/weak acids & bases, Brønsted-Lowry theory, Ka, pH, pKa,
Kb, pKb, Kw, pKw, indicators, effectiveness of indicators, choosing indicators for titrations
 Buffers and pH: buffer solutions, calculations of buffer pH, importance of buffers
 Solubility product: Ksp, common ion effect, selective precipitation
 Redox equilibria: Standard electrode potentials, standard cell potentials, standard hydrogen
electrode, measuring SEPs, calculating standard cell potentials from half cells, using SEPs to
determine if a reaction will occur, effect of concentration on electrode potential, redox
processes in energy storage devices

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