BABCOCK UNIVERSITY, ILISHAN-REMO, OGUN STATE, NIGERIA

COURSE TITLE: GENERAL CHEMISTRY

COURSE CODE: CHEM 101
Lecturer: Feyisara Banji Adaramola

TOPIC: CHEMICAL KINETICS

Definition
Chemical kinetics deals with the rate at which a chemical reaction takes place and these rates vary from
one reaction to another. One of the main goals of chemical kinetics is to understand the steps by which a
reaction takes place. This series of steps is called the reaction mechanism. At very advanced level, it
describes in details the order in which bonds are broken or formed and the changes in relative positions of
the atom in the course of the reaction. Also, the number of molecules participating as reactants in a reaction
is called Molecularity of a reaction. When a single molecule is involved in a reaction, the reaction is said
to be Unimolecular, when two reactant molecules are involved, it is bimolecular while trimolecular
when three are involved.

Reaction Rates
The rate of a chemical reaction is determined by how rapidly the reaction occurs. The rates of a reaction
can be as fast as taking place within fractions of seconds (e.g explosions) and can be as slow as taking
millions of years (e.g the formation of diamonds or other minerals in the Earth’s Crust). Other examples
involves rusting of iron nail which takes some days. Formation of silver chloride by the addition of AgNO 3
solution to HCl solution is an example of a laboratory reaction that occurs almost immediately.
AgNO3(aq) + HCl(aq) → AgCl(s) + HNO3(aq)
Reaction rate can be defined as the change in the concentration of reactants or products per unit time. The
unit for reaction rate is usually molarity per second (i.e. M/s) which implies the change in concentration
(measured in molarity) divided by the time interval (measured in second).
Reaction rates can be expressed either as the rate of disappearance of reactant or as the rate of appearance
or formation of product.
Change∈concentration of reactant∨product
Generally, the rate of a given reaction =
Time taken for the change of occur
∆ [R]
In terms of reactant disappearance, rate of a reaction = - while
∆t
∆ [P]
In terms of appearance of product, rate of a reaction =
∆t
In other cases, rate of a reaction can also be given as; = mass of reactant consumed or product formed (g)
Time taken for the reaction to occur (sec)

By convention, rates are always expressed as positive quantities. Because [R] is decreasing with time, ∆ [R]
is a negative number; so we use the negative sign to convert it to a positive value. Note: The symbol [ ] is
used to indicate the concentration of a substance in molarity while symbol ∆ indicate change in a given
quantity.
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Consider the decomposition of Nitrogen dioxide to nitric oxide and oxygen as follows:
2NO2 (g) 2NO (g) + O2(g)

Assume in a particular experiment we start with a flask of nitrogen dioxide at 300 oC and measure the
concentrations (mol/dm3) of nitrogen dioxide, nitric oxide and oxygen as nitrogen dioxide decomposes.
The results of this experiment are summarized in table below.

2NO2 (g) 2NO (g) + O2(g) (at 300 oC)

Concentrations of Reactant and Products as a Function of Time for the Reaction

Time (± 1 s) NO2 NO O2
0 0.0100 0 0

50 0.0079 0.0021 0.0011

100 0.0065 0.0035 0.0018

150 0.0055 0.0045 0.0023

200 0.0048 0.0052 0.0026

250 0.0043 0.0057 0.0029

300 0.0038 0.0062 0.0031

350 0.0034 0.0066 0.0033

400 0.0031 0.0069 0.0035

Note from the results that the concentration of the reactant (NO 2) decreases with time and the
concentrations of the products (NO and O2) increase with time.

Rate = Change in [NO2] = Concentration of NO2 at time t2 – Concentration of NO2 at time t1

Time elapsed t 2 – t1

EXAMPLE 1
Calculate the average rate at which the concentration of NO2 changes over the first 50 seconds of the
reaction using the data given in the table
Rate = - [NO2] t = 50 - [NO2] t = 0
50 s - 0 s

= -(0.0079 mol / L – 0.0100 mol / L)

50 s

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 = -(-4.2 x 10-5 mol / Ls) = 4.2 x 10-5 mol / L .s

EXAMPLE 2
Given a reaction A → B. At the start of the reaction the concentration of A was 1.00moldm -3; after 20s the
concentration of A drops to 0.54Moldm-3 while that of B rises to 0.46M. After 40s, the concentration of A
is 0.30moldm-3 while that of B is 0.70moldm-3. Calculate the rate at which A disappears over the time
interval from 20s – 40s. Also, determine the rate of formation of B.

∆ [ A] 0.3 m−0.54 m
Average rate of disappearance of A = - = = 1.2x10-2 M/s
∆t 40s −20s

EXAMPLE 3
What is the rate of a reaction of 0.37g of K 2CO3 which completely reacts in excess dilute hydrochloric acid
if it took the reaction 30 min to reach completion?

When the stoichiometric relationships among the products and reactants are not one to one; for instance
2HI(g) → H2(g) + I2(g)
Because 2 moles of HI disappear for each mole of H 2 or I2 that forms, the rate of disappearance of HI is
twice the rate of appearance of either H 2 or I2. To equate the rates, the rate of disappearance of HI must be
divided by 2.
∆ [HI ] ∆[ H 2 ] ∆[ I 2 ]
i.e Rate of the reaction = - ½ = =
∆t ∆t ∆t
Generally, for a reaction of the form aA + bB → cC + dD ; the rate is given thus;
1 ∆ [ A ] −1 ∆[B ] 1 ∆[C] 1 [D]
Rate = - = = =
a ∆t b ∆t c ∆t d ∆t

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Factors affecting rates of reaction
1. Physical state or nature of the reactants: The more readily molecules of reactants collide with
each other, the more rapidly they react especially when they are in gaseous or liquid state (i.e same
phase). For reactants in different phases, (e.g gas/solid), the reaction is limited to their area of
contact. Thus reaction that involve solids tend to proceed faster if the surface area of the solid is
increased. For instance, a powdered drug dissolves in the stomach and enters the bloodstream more
rapidly than the same medic in tablet form.
2. Concentration of reactants: Most chemical reactions proceed faster if the concentration of one or
more of the reactants is increased. As concentration increases, the frequency with which reactant
molecules collide increases resulting in increased rates. For example, the reaction between a strong
acid and a strong base proceeds faster than if otherwise. Note: that rates of reactions decreases as
the reaction proceeds because the concentration of reactants decreases.
3. Temperature:- The rates of chemical reactions increase as the temperature of which the reactions
occur increases. This accounts for one reason whey perishable foods spoil faster at room
tempertaute as against at refrigerator’s temperature. The bacterial reactions that lead to the spoiling
of milk proceed much more rapidly at room temperature than they do at the lower temperature of a
refrigerator. Increase in temperature increases the kinetic energies of molecules. As there molecules
move more rapidly, they collide more frequently and also with higher energy, leading to increased
reaction rates.
4. The presence of Catalyst: Catalysts are chemical substances that alter reaction rates without being
used up. Catalysts affect the kind of collisions that lead to the reaction. On a molecular level,
reaction rates depend on the frequency of collisions between molecules. The greater the frequency
of collisions, the greater the rate of reaction. A catalyst exerts its effect on a chemical reaction by
generally lowering the overall activation energy of the reaction.
5. Pressure: pressure can only affect a chemical reaction involving gases. In this case, raising the
pressure also raises the rate of such reaction and vice-versa

Catalysis
A catalyst is a substance that changes or alters the speed or rate of a chemical reaction without
undergoing a permanent chemical change itself in the process. A catalyst can be homogenous or
heterogeneous.
A catalyst that is present in the same phase as the reacting molecules is known as a homogeneous catalyst.
An example is the decomposition of aqueous hydrogen peroxide, H2O2(aq) into water and oxygen.
2H2O2(l) → 2H2O(l) + O2(g) which occurs extremely slowly in the absence of a catalyst. One of the
substances that is used to catalyzed this reaction is Bromide ion, Br- [from NaBr].
By adding a small amount of NaBr (aq) to H2O2(aq), the solution turns brown because Br2 is formed and the
buildup of Br2 leads to rapid evolution of O2. Meanwhile a colorless solution of NaBr(aq) remains after the
complete decomposition of H2O2(aq). NaBr catalysizes the reaction but its not consumed during the process.
A heterogeneous Catalyst is one which exists in a different phase from the reacting molecules; for
example as a solid in contact with either gaseous reactants or with reactants in a liquid solution.
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Heterogeneous catalysts are often times composed of metals or metal oxides. Catalyst (heterogeneous) are
normally prepared in such a way that they have adequately large surface area because catalyzed reactions
occur at the catalyst surface.
The initial step in heterogeneous catalysis is usually adsorption of reactants. Adsorption refers to the
binding of molecules to a surface while absorption refers to the uptake of molecules into the interior of
another substance.
A typical example of heterogeneous catalysis is the hydrogenation of ethylene to form ethane;
C2H4(g) + H2(g) → C2H6(g) ∆ H0 = 137KJ/mol
Even though this reaction is exothermic; it occurs very slowly in the absence of a catalyst but the reaction
occurs easily and more quickly at room temperature in the presence of powdered metallic nickel, palladium
or platinum.

Enzymes
Enzymes are biological catalysts which are essential for controlling the biochemical reactions in biological
system. Most enzymes are large proteins molecules with molecular weights ranging from about 10,000 to
about 1million amu
Although an enzyme is a large molecule, the reaction is catalyzed at a very specific location in the enzyme
called the active site. The substances that undergo reaction at this site are called substrates. The
combination of the enzyme and the substrate is called the enzyme-substrate complex.
The activity or efficiency of an enzyme is destroyed if some molecules in the solution is able to bind
strongly to the active site and hence block the entry of the substrates. Such substances that destroy activity
of an enzyme are called Enzyme inhibitors.

Characteristics of a catalyst
(1) It alters the rate of a chemical reaction (2) A catalyst remains unchanged in chemical nature and mass of
the end of a reaction (3) A catalyst does not start a reaction (4) It is specific in action (5) It does not affect
the type of product formed in a chemical reaction.

The Rate Law

An equation which shows how rate of a reaction depends on the concentration of reactants is called a rate
law.
For a general reaction; aA + bB → cC + dD the rate law generally has the form;
Rate = K[A]a [B]b

For the decomposition of nitrogen dioxide, 2NO2 (g) 2NO (g) + O2 (g)

Rate = k [NO2]n

Such an expression which shows how the rate depends on the concentrations of reactants is called a rate
law. The proportionality constant k, is called rate constant and n is the order of the reactant and both must
be determined by experiment. The order of a reactant can be an integer (including zero) or a fraction.
For example, we might choose to define the reaction rate in terms of the consumption NO2

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 Rate = - ∆ [NO2] = k [NO2]n
∆t
Alternatively, we could define the rate in terms of production of O2:

Rate` = ∆ [O2] = k` [O2]n

∆t
Types of Rate Laws
A rate law that expresses how the rate depends on the concentration is called the differential rate law or
simply called the rate law. A rate law which expresses how the concentration depends on time is the
integrated rate law.

Reaction Order
Order of a reaction can be defined as the power to which each concentration of reactants must be raised to
give the appropriate dependence of rate on concentration. The overall order of a given reaction is the sum
of the exponents of the concentration of reactants as contained in the experimentally determined rate law.
For a reaction of the form;
aA + bB → cC + dD the rate law has the form
Rate = K[A]a [B]b The exponents a and b in the rate law are called reaction orders.

Consider the following reaction

NH+4(aq) + NO-2(aq) → N2(g) + 2H2O(l)
In this reaction, rate is proportional to [NH+4] and [NO-2], the rate expression is thus;
Rate = K[NH+4]1 [NO-2]1
Since the exponent of [NH+4] is 1, the rate is 1st order with respect to NH+4 while the rate is also 1st order
with respect of NO-2 since the exponent of [NO -2] is also 1. The overall order of this reaction is the sum of
the orders with respect to each reactant in the rate law. Thus, the rate law has an overall reaction order of 1
+ 1 = 2 and the reaction is thus 2nd order overall
Other examples are;
2N2O5(g) →4NO2(g) + O2(g) Rate = K[N2O5]
CHCl3(g) + Cl2(g) → CCl4(g) + HCl(g) Rate = K[CHCl3] [Cl2]1/2
H2(g) + I2(g) → 2HI(g) Rate = K[H2] [I2]

Note: Although the exponents in a rate law are sometimes the same as the coefficients in a balanced
equation, this is not necessarily the case. These values of exponents must be determined experimentally.
Note also; that if the rate depends on the square of the concentration of reactant A i.e [A] 2, than the reaction
is 2nd order with respect to A. In a situation where the concentration of the reactant does not affect the rate
of reaction such reaction is Zero order.

First order Reactions

A first-order reaction is one whose rate depends on the concentration of a single reactant raised to the first
power. For a reaction of the type A → P, the rate law may be 1st order as in;
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 ∆ [ A]
Rate = - =¿ K[A]
∆t
This form of a rate law which expresses how rate depends on concentration is called the differential rate
law. Using the integration operation, this relationship can be transformed into an equation that relates the
concentration of A at the start of the reaction; [A]0 to its concentration at any other time t, [A]t
[ A ]t
In[A]t – In[A]0 = -Kt or In =-Kt
[ A ]0
This form of the rate law is called the integrated rate law. The rate of a first order equation can also be
expressed thus; rate = K (a - x).
Note that K = 2.303 log10 [a/ a-x] and from this we have t = 2.303 log10 [a/ a-x]
t K
Where a = amount of reactant, x = amount of product, t = time taken, K is the rate constant

Second-order Reaction
A second-order reaction is one whose rate depends on the reactant concentration raised to the 2 nd power or
on the concentrations of two different reactants each raised to the first power.
Consider the reaction of type A → Products or A + B → Products that are 2nd order in just one reactant A:
∆ [ A]
Rate = - = k[A]2
∆t
1 1
The integrated rate is given as; =kt +
[ A ]t [ A ]0

Half-Life
The half-life of a reaction t ½ is the time required for the concentration of a reactant to reach ½ of its initial
value, i.e [A]t1/2 = ½ [A]0. The half-life as used to describe how fast a reaction occurs especially if it’s a 1 st
order reaction. A fast reaction will have a short half-life.
The half-life of a 1st order reaction is given as
1
[ A ]0
In 2 Kt½
=¿
[ A ]0
In ½ = -Kt½
¿ 1/2 0.693
t½=- =
k k
The half-life (t1/2 ) of a 1 order rate law does not depend on the starting concentration. As a result the half-
st

life remains constant throughout the reaction.

In contrast to 1st order reactions, the half-life of 2nd order and other reactions depends on concentrations of
reactants and hence changes as the reaction progresses.
The half-life for a 2nd order reaction is given as;
1
t½=
K [ A ]0
The lower the initial concentration of reactants for a 2nd order reaction, the greater the half-life.

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Assignment

1. The reaction 2NO (g) + Cl2 (g) 2NOCl (g) was studied at – 10 oC. The following results
were obtained where

Rate = - ∆[Cl2]
∆t

[2NO]0 (mol / L) [Cl2]0 (mol / L) Initial Rate

(mol / L . min)

0.10 0.10 0.18

0.10 0.20 0.36

0.20 0.20 1.45

a) What is the value of the rate constant

b) Calculate its half-life

2. The following data were obtained for the gas-phase decomposition of dinitrogen pentaoxide

2N2O5 (g) 4NO2 (g) + O2 (g)

[N2O5]0 (mol / L ) Initial Rate

(mol / L . s)

0.0750 8.90 x 10-4

0.190 2.26 x 10-3

0.275 3.26 x 10-3

0.410 4.85 x 10-3

Defining the rate as - ∆ [N2O5] / ∆t write the rate law and calculate the value of the rate constant.

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