Lecture 5 and 6

Chemical Kinetics and Equilibria

By
Dr Geoffrey Bosire
Dr Bosire Geoffrey, University of Nairobi
 Chemical Kinetics

Chemical reactions can be slow, fast, or explosive.

But explosions are in a class by themselves. They are
characterized by instantaneous release of large
quantities of hot gases such as O2, NH3, CO2 and
H2O. The gases expand rapidly and set up a shock
wave of enormous pressure (up to 700,000 atm) that
propagates through the surroundings at speeds of
up to 9000 m/s, causing physical destruction:-
witnessed in movies and television newscasts.
Because the gaseous explosion products are extremely stable, a great deal of
energy is released within a few microseconds during an explosion, e.g. one mole
(227 g) of nitroglycerin, releases 1427 kJ when it explodes!!!!

Dr Bosire Geoffrey, University of Nairobi

 The branch of chemistry concerned with reaction rates
and the sequence of steps by which reactions occur is
called chemical kinetics.
The rates of chemical reactions differ greatly. Some reactions, such as the
combination of sodium and bromine, occur instantly. Other reactions, such
as the rusting of iron, are slow.
The rate of a reaction specifies how fast the concentration of a reactant or a
product changes per unit time.

The thermal decomposition of gaseous dinitrogen pentoxide, to give the brown gas
nitrogen dioxide and molecular oxygen:

Alternatively, concentration changes can be monitored by measuring the intensity of

the brown colour NO2. Note that the concentrations of NO2 and O2 increase as the
concentration of N2O5 decreases. Dr Bosire Geoffrey, University of Nairobi
The reaction rate can be defined either as the increase in the concentration of a
product per unit time or as the decrease in the concentration of a reactant per unit
time.

Change in the molar concentration of oxygen

Change in time

where the square brackets surrounding O2 denote its molar concentration;

Consider the general reaction;

where A and B are the reactants, and a and b are stoichiometric coefficients in
the balanced chemical equation.
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 The dependence of the reaction rate on the concentration
of each reactant is given by an equation called the rate law.

The rate law is usually written in the form;

where k is a proportionality constant called the rate constant. We have arbitrarily

expressed the rate as the rate of disappearance of A
The values of the exponents m and n determine the reaction order with respect
to A and B, respectively. The sum of the exponents m + n defines the overall
reaction order. Thus, if the rate law is

we say that the reaction is second order in A, first order in B, and third order
overall.
The values of the exponents in a rate law must be determined by experiment; they cannot
be deduced from the stoichiometry of the reaction.
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 Example

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Dr Bosire Geoffrey, University of Nairobi
 Integrated Rate Law for a First-Order Reaction

A simple, general first-order reaction is given as:

An example is the decomposition of hydrogen peroxide in basic solution:

Using calculus, it’s possible to convert the rate law to another form, called the
integrated rate law:

ln denotes the natural logarithm, [A]o designates the concentration of A at some

initial time, arbitrarily considered to be t=0 and [A]t is the concentration of A at
any time t thereafter.
Dr Bosire Geoffrey, University of Nairobi
Dr Bosire Geoffrey,
University of Nairobi
 Half-Life of a First-Order Reaction
The half-life of a reaction, symbolized by t1/2 is the time
required for the reactant concentration to drop to one-half of
its initial value.

Dr Bosire Geoffrey, University of Nairobi

 Example

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 SOLUTION

(a) Figure shows that the conc. of N2O5 falls from 0.020 M to 0.010 M during a time
period of approximately 400 s. At 800 s, has decreased by another factor of 2, to
0.0050 M. Therefore, t1/2 = 400 s

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 Second-Order Reactions

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 Half-life of a second-order reaction

Comparative analysis

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 Example

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Dr Bosire Geoffrey, University of Nairobi
 Reaction Rates and Temperature:
The Arrhenius Equation

According to the collision theory model, a bimolecular reaction occurs when two
properly oriented reactant molecules come together in a sufficiently energetic
collision. To be specific, let’s consider one of the simplest possible reactions, the
reaction of an atom A with a diatomic molecule BC to give a diatomic molecule AB
and an atom C:

Between the reactant and product stages, the nuclei pass through a configuration
in which all three atoms are weakly linked together. We can picture the progress
of the reaction as;

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 A---B---C has more potential energy than either the reactants
or the products. Thus, there is a potential energy barrier that
must be surmounted before reactants can be converted to
products, as depicted graphically

The height of the barrier is called the

activation energy, Ea and the
configuration of atoms at the
maximum in the potential energy
profile is called the transition state, or
the activated complex. Since energy is
conserved in the collision, all the
energy needed to climb the potential
energy hill must come from the kinetic
energy of the colliding molecules. If the
collision energy is less than Ea the
reactant molecules can’t surmount the
barrier and they simply bounce apart.
If the collision energy is at least as
great as Ea, however, the reactants can
climb over the barrier and be converted
to products.
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The reaction rate is lower than the collision rate by
a factor p x f because only a fraction of the colliding
molecules have the correct orientation and the
minimum energy needed for reaction:

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This expression is usually written in a form called the Arrhenius equation;

The parameter A ( = pZ) is called the frequency factor (or pre-exponential factor).
The minus sign in the exponent, indicates that, the rate constant decreases as
increases and increases as T increases.

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 Using the Arrhenius Equation

Taking the natural logarithm of both sides of the Arrhenius

equation, we obtain the logarithmic form;

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 Another form of the Arrhenius equation can be derived that
allows us to estimate the activation energy from rate constants
at just two temperatures. At temperatures T1 and T2;

Example

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 Solution

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Dr Bosire Geoffrey, University of Nairobi
Dr Bosire Geoffrey, University of Nairobi
 Lecture 6
Chemical Equilibrium

Outline
✓ The Equilibrium State
✓ The Equilibrium Constant
✓ The Equilibrium Constant
✓ Heterogeneous Equilibria
✓ Using the Equilibrium Constant
✓ Factors That Alter the Composition of an Equilibrium Mixture

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 Chemical Equilibrium

Two important questions about chemical reactions:

How fast does a reaction happen? The kinetics of the reaction

To what extent does it happen? This lecture

CHEMICAL EQUILIBRIUM
The state reached when the For example
concentrations of reactants and
products remain constant over time
 The Equilibrium Constants

For the equilibrium reaction;

Equilibrium Constant, Kp
Equilibrium equations for gas-phase reactions are often written using
partial pressures rather than molar concentrations. For example, the
equilibrium equation for the decomposition of N2O4 can be written as for
the reaction;

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 The constants Kc and Kp for the general gas-phase
reaction are related because the
pressure of each component in a mixture of ideal gases is
directly proportional to its molar concentration. For
component A, for example,

is the number of moles of gaseous products

minus the number of moles of gaseous reactants.
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 Examples

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Dr Bosire Geoffrey, University of Nairobi
Heterogeneous Equilibria
Reactants and products are present
in more than one phase.
For example, the thermal decomposition of solid calcium carbonate, a reaction used in
manufacturing cement;

As a general rule, the concentrations of pure solids and pure liquids are not included when
writing an equilibrium equation because their concentrations are constants that are
incorporated into the value of the equilibrium constant.

Dr Bosire Geoffrey, University of Nairobi

 Predicting the Direction of Reaction

Consider

The subscript t on the concentration symbols means that the concentrations were
measured at some arbitrary time t, not necessarily at equilibrium.) If we substitute
these concentrations into the equilibrium constant expression, we obtain a value called
the reaction quotient

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 More examples
Take a scenario where we know the initial concentrations
but do not know any of the equilibrium concentrations.

Solution

Solving x = 0. 0791 or 0.136 M. Because the initial concentrations of and are 0.100 M, x
can’t exceed 0.100 M. Therefore, discard 0.136 as chemically unreasonable Calculate
the equilibrium concentrations from the calculated value of x: Check the results by
substituting them into the equilibrium equation: Dr Bosire Geoffrey, University of Nairobi
Dr Bosire Geoffrey, University of Nairobi
 Factors That Alter the Composition of an Equilibrium Mixture

Questions
1. Discuss the Factors That Alter the Composition of an Equilibrium Mixture
2. A platinum catalyst is used in automobile catalytic converters to hasten the
oxidation of carbon monoxide:

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 Solubility Equilibria
Many biological and environmental processes involve the
dissolution or precipitation of a sparingly soluble ionic compound.

Tooth decay, for example, begins when tooth enamel, composed of the
mineral hydroxyapatite, Ca5(PO4)3OH.

Consider the solubility equilibrium in a saturated solution of calcium

fluoride in contact with an excess of solid calcium fluoride.

Solubility
product
constant, or Generally;
simply the
solubility
product

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 Example

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 Factors Affecting Solubility
a) Common ion effect,
b) Formation of complex ions,
c) pH

1. The Common-Ion Effect (consider the MF2 example)

Example

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The common-ion effect. The
solubility of MgF2 at 25°C decreases
markedly on addition of F- ions.

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 2. Formation of complex ions
The solubility of an ionic compound increases dramatically if
the solution contains a Lewis base that can form a coordinate
covalent bond to the metal cation.
• Silver chloride, for example, is insoluble in water and in acid, but it dissolves in an
excess of aqueous ammonia, forming the complex ion [Ag (NH3)2]+
• A complex ion contains a metal cation bonded to one or more small molecules
or ions, such as NH3, CN-, or OH-
• According to Le Châtelier’s principle, ammonia shifts the solubility equilibrium to
the right by tying up the Ag+ ion in the form of the complex ion:

Formation constant (or stability constant)

 3. The pH of the Solution

An ionic compound that contains a basic anion

becomes more soluble as the acidity of the
solution increases.
The solubility of CaCO3 for example, increases with decreasing pH
As carbonate ions are removed
from the solution, the solubility
equilibrium shifts to the right.

The solubility of CaCO3 at 25°C increases as the

solution becomes more acidic because the
carbonate ions combine with protons.

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 Quantitative Measurement of pH

✓ In case of acids, relative strength can be compared by measuring the

concentration of hydrogen ions or by measuring their pH.
✓ The “p” in pH comes from German word “potenz” meaning power and
“H” from [H+] concentration of hydrogen
✓ The pH of a solution is the negative logarithm to base 10 of the molar
hydrogen ion concentration i.e. pH = − lg[ H + (aq) ]

Notice that the accepted abbreviation for logarithm to base 10 is lg not

log.

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 Examples

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 Buffer Solutions

Are solutions that resist change in pH on addition of

acid or alkali.
A buffer solution requires two components, one which is able to neutralize
acids, and the other able to neutralize bases.

But of course the two components must not neutralize each other.
Common buffer solutions are described either as a mixture of:
▪ a weak acid and its conjugate base or
▪ a weak base and its conjugate acid.

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 The Henderson–Hasselbalch Equation

The H3O+ concentration in a buffer solution depends on the dissociation

constant of the weak acid and on the concentration ratio [weak
acid]/[conjugate base]:
Dr Bosire Geoffrey, University of Nairobi
What is the pH a buffer solution made from 0.1 M
acetic acid and 0.1 M sodium acetate solution, given
Ka (acetic acid=1.8x10-5 M)?

Solution

[conjugatebase]
pH = pK a + lg
[acid ]
0.10
pH = − lg(1.8 x10 ) K a + lg
5

0.10

4.74

END OF LECTURE 5 and 6