What is chemical kinetics?

The branch of chemistry which deals with the study of the reaction rates is known
as Chemical Kinetics.

Meaning:
The word is derived from the Greek word ‘Kinesis‘ meaning movement.

 In fact, in all chemical reactions, the reacting species move and collide to form
the products.

 Chemical kinetics also involves the investigation of reaction mechanisms, the

conditions of concentration, temperature, pressure, and catalyst which control
the rates of different reactions.
Rate of Formations and Disappearances:
In any chemical reaction, as the reaction proceeds, the amount of reactants
decreases, whereas the amount of products increases. One has to understand that
the rate of the overall reaction depends on the rate at which reactants are
consumed or the rate at which the products are formed.

Graph:
If a graph is plotted between the concentration of reactants and products and
time, the rate of formation of products and the rate of disappearance of reactants
can be easily calculated from the slope of curves for products and reactants. The
overall rate of the reaction may or may not be equal to the rate of formations and
disappearances.
(a) Product concentration is zero at time t = 0
(b) at time t = 0, both reactants and products are present.
Continue...
From the graph, it is understood that the slope of the reactants curve
is negative and that for product curve is positive, indicating the
concentration of reactants and products decreases and increases,
respectively.
Rate of Reaction:
The rate of reaction or reaction rate is the speed at which reactants are converted
into products.

When we talk about chemical reactions, it is a given fact that rate at which they
occur varies by a great deal. Some chemical reactions are nearly instantaneous,
while others usually take some time to reach the final equilibrium.

As per the general definition, the speed with which a reaction takes place is
referred to as the rate of a reaction.
Average Rate of Reaction:
1. The rate of change of concentration of substances for a definite interval of time.
2. It occurs during a large span of time.
3. Average Rate of Change :

4. Average rate = −ΔA/Δt=A2−A1/ T2−T1

Instantaneous Rate of Reaction:
The instantaneous rate of reaction:
1. The rate of a reaction at a specified or particular point of time.
2. It occurs within a short span of time.
3. Instantaneous Rate of change:

4. Instantaneous Rate = dx/dt=dP/dT

Classification of reactions on the basis
of reaction rate:
Different chemical reactions occur at different rates on the basis of
rates, the chemical reactions are broadly divided into three categories.

• Very fast or instantaneous reactions

• Very slow reactions
• Moderate reactions
(a) Very fast or instantaneous reactions:
•These reactions are so fast that they occur as soon as the reactants are
brought together.
•These reactions involve ionic species.
•These reactions take about 10-14 to 10-16 seconds to complete.

Examples:
(i) Precipitation of AgCl when solutions of silver nitrate and sodium chloride are
mixed.
AgNO3+ NaCl → AgCl + NaNO3

Note:
• These reactions are extremely fast, it is therefore not possible to study their rates.
• The spontaneous reactions may not be fast reactions.
(b) Very slow reactions:
• These reactions are extremely slow.
• They may take months together to show any measurable change at room
temperature.

Examples:
• Fermentation of sugar in the presence of yeast takes more than a month.
• Formation of coal and petroleum under earth’s crust.
• The roasting of iron once started, may not be completed even after a year.

Note:
• These reactions are not feasible to study the rates of reaction.
(c) Moderate reactions:
• These reactions proceed at a limited rate and their rates can be measured.

Examples:
(i) Decomposition of hydrogen peroxide:
2H O → 2H₂O + O
2 2 2

(ii) Decomposition of nitrogen pentoxide:

2N₂O → 2N₂O4 + O₂
5

(iii) Hydrolysis of an ester :

CH COOC H + NaOH → CH COONa + C H OH
3 2 5 3 2 5
Factors affecting the reaction rate:
The rates of chemical reactions are influenced by a number of factors. These are:
(i) Concentration of reactants:
The rate of a chemical reaction is proportional to the concentration of the reacting
species taking part in the reaction. It is maximum to start with and slowly
decreases since the concentration of the reacting species decreases accordingly. In
case of reversible reactions, the rate of chemical reaction can be studied separately
for both the forward and backward reactions. In case of gaseous reactions, rate of
reaction increases with increase in pressure.
(ii) Temperature:
Rate of reaction increases with increase in temperature. The energy of the reactant
species increases with the increase in temperature and so will the number of
collisions. It has been observed that in most of the cases, about 10 degree increase
in temperature makes the reaction rate double.
(iii) Presence of catalyst:
In many chemical reactions, the reaction rate is enhanced by certain foreign
substances called catalysts. They don’t consume in the reaction and also do not
undergo any change in chemical characteristics.
The catalyst increases the rate of the reaction by providing a new reaction
mechanism to occur within a lower activation energy.

(iv) Nature of reactants:

The nature of reacting species may also influence the reaction rate. For example,
combustion of nitric oxide (NO) is faster as compared to carbon monoxide(CO).

2NO (g) + O (g) → 2NO (Fast)

2 2

2CO (g) + O (g) → 2CO (Slow)

2 2
(v) Surface area:
An increase in surface area provided more opportunities for the reactants to come in
contact or collide with each other resulting an increased reaction rate.
Example: we use granulated zinc metal in laboratory while preparing hydrogen gas
on reacting with dilute hydrochloric acid or dilute sulphuric acid. Actually,
granulated zinc has a greater surface area available for the attack by the acid than a
lump of zinc. Therefore, it reacts at a faster rate.
(vi) Exposure to radiation:
The photochemical reactions are carried out in the presence of sunlight.
𝐻2+𝐶𝑙2 →𝑆𝑢𝑛𝑙𝑖𝑔ℎ𝑡 2𝐻𝐶𝑙
𝐶𝐻4+𝐶𝑙2 → 𝑆𝑢𝑛𝑙𝑖𝑔ℎ𝑡 𝐶𝐻3𝐶𝑙+𝐻𝐶𝑙
In these reactions, the photons of light are the source of energy which helps in
breaking the bonds in the reacting molecules so that they can react and form
product,
 Rate Law:
The rate law (also known as the rate equation) for a chemical reaction is an
expression that provides a relationship between the rate of the reaction and the
concentrations of the reactants participating in it .​

Expression​:
For a reaction given by:​
aA + bB → cC + dD​
where a, b, c, and d are the stoichiometric coefficients of the reactants or products,
the rate equation for the reaction is given by:​

Rate ∝ [A]x[B]y ⇒ Rate = k[A]x[B]y​

 where,
• [A] & [B] denote the concentrations of the reactants A and B.

• x & y denote the partial reaction orders for reactants A & B (which may or
may not be equal to their stoichiometric coefficients a & b).

• The proportionality constant ‘k’ is the rate constant of the reaction.

It is important to note that the expression of the rate law for a specific reaction
can only be determined experimentally. The rate law expression cannot be
obtained from the balanced chemical equation (since the partial orders of the
reactants are not necessarily equal to the stoichiometric coefficients).
 Reaction Orders​:
The sum of the partial orders of the reactants in the rate law expression gives the
overall order of the reaction.​
If Rate = k[A]x[B]y; overall order of the reaction (n) = x+y​

The order of a reaction provides insight into the change in the rate of the reaction
that can be expected by increasing the concentration of the reactants. For example:​
• If the reaction is a zero-order reaction, doubling the reactant concentration will
have no effect on the reaction rate.​
• If the reaction is of the first order, doubling the reactant concentration will double
the reaction rate.​
• In second-order reactions, doubling the concentration of the reactants will
quadruple the overall reaction rate.​
• For third-order reactions, the overall rate increases by eight times when the
reactant concentration is doubled.​
 Rate Constants​:

Rearranging the rate equation, the value of the rate constant ‘k’ is
given by:​
k = Rate/[A]x[B]y​
Therefore, the units of k (assuming that concentration is represented
in mol L-1 or M and time is represented in seconds) can be calculated
via the following equation.​
k = (M s-1)*(M-n) = M(1-n) s-1​
 The units of the rate constants for zero, first, second, and n -order
th

reactions are tabulated below.

 Differential Rate Equations​
Differential rate laws are used to express the rate of a reaction in terms of
change in the concentration of reactants (d[R]) over a small interval of time
(dt).
Therefore, the differential form of the rate expression provided in the previous
subsection is given by:
​
-d[R]/dt = k[A]x[B]y​
Differential rate equations can be used to calculate the instantaneous rate of a
reaction, which is the reaction rate under a very small-time interval.

It can be noted that the ordinary rate law is a differential rate equation since it
offers insight into the instantaneous rate of the reaction.​
 Integrated Rate Equations​:
Integrated rate equations express the concentration of the reactants in a chemical
reaction as a function of time.
Therefore, such rate equations can be employed to check how long it would take for
a given percentage of the reactants to be consumed in a chemical reaction.
It is important to note that reactions of different orders have different integrated
rate equations
 Integrated Rate Equation for Zero-Order Reactions​:
The integrated rate equation for a zero-order reaction is given by:​
kt = [R0] – [R] (or) k = ([R0] – [R])/t​
Where,​
• [R0] is the initial concentration of the reactant (when t = 0)​
• [R] is the concentration of the reactant at time ‘t’​
• k is the rate constant
 Integrated Rate Equation for First-Order Reactions​

The integrated rate law for first-order reactions is:​

kt = 2.303 log([R0]/[R]) (or) k = (2.303/t) log([R0]/[R])​

 Integrated Rate Equation for Second-Order Reactions​:

For second-order reactions, the integrated rate equation is:​

kt = (1/[R]) – (1/[R0])
 Solved Examples on the Rate Law​:
Example 1​
For the reaction given by 2NO + O2 → 2NO2, The rate equation is:​
Rate = k[NO]2[O2]​
Find the overall order of the reaction and the units of the rate constant.​

The overall order of the reaction = sum of exponents of reactants in the

rate equation = 2+1 = 3​
The reaction is a third-order reaction. Units of rate constant for ‘n th’
order reaction = M(1-n) s-1​
Therefore, units of rate constant for the third-order reaction = M (1-3) s-1
= M-2 s-1 = L2 mol-2 s-1​
The Collision Theory Of Chemical Reactions
 History:
The study of Collision theory of chemical reactions and their kinetics has made
great developments that play a pivotal role in today’s fast-paced world. Be it the
packaged drinking water, the water bottles or the steel manufacturing plant or the
fastest motor vehicles or the synthetically designed biological implants, some way
or the other there is a chemical reaction associated with them.

In order to get a better insight into these chemical reactions, Max Trautz and
William Lewis in 1916-1918 developed Collision Theory of Chemical Reactions
based on the kinetic theory of gases. All of us have heard about the kinetic theory
of gases. It explains the behaviour of gases by considering them many particles,
molecules or atoms that are constantly moving in random directions.
Statement:
According to the collision theory, “the molecules of reactants are assumed to be
hard spheres and the reactions are assumed to occur only when these spheres
(molecules) collide with each other”.
So it was important to quantify the number of collisions occurring in order to
form products so that we can have a clear picture of the reaction, and hence came
the term collision frequency.

Collision Frequency can be understood as the number of collisions per second

per unit volume of the reacting mixture.
• It is generally denoted by Z.
Let’s consider the following bimolecular elementary reaction:

P + Q → Product
Now as per the collision theory, the rate of the above reaction can be given by:

Rate=ZPQ ρ e−Ea/RT
Where:
• ZPQ = collision frequency of reactants P and Q

• Ea = Activation Energy

• R = Universal Gas Constant

• T = Temperature in absolute scale

• ρ = is the steric factor

Continue...
• One more parameter that affected the rates of chemical reactions significantly
is activation energy (Ea). The term activation energy was given
by Arrhenius, it is the minimum amount of energy that the reactants must
possess in order to form a product during a chemical reaction.
• As per the Arrhenius Equation, all the molecules that have energy greater
than or equal to activation energy will collide to form products. But this
postulate was not true for all the reactions. A significant amount of deviation
was observed in reactions involving complex molecules.
• Some molecules having sufficient energy (activation energy) did not collide to
form the product. Only a few of them made effective collisions, collisions that
led to the formation of products. The scientists found that the kinetic energy
of the molecules is not the only parameter that governs the reaction.
Continue...
They concluded that only those molecules that have the threshold energy
(activation energy) and proper orientation during the collision will form
products. They introduced a probability factor P to account for the effective
collisions.

So now the rate of a reaction is given by:

Continue...
In conclusion, we can say that the activation energy and proper orientation of
the reacting molecules together determine the condition for a collision that will
result in the formation of products that is an effective collision. So in collision
theory, both activation energy and effective collision govern the rate of a
reaction.
Activation Energy:
The activation energy is the minimum amount of energy needed by the
reacting particles in any particular reaction for that reaction to take place.

To start a chemical reaction chemical

bonds need to be broken in the
reactants, which requires energy. The
energy needed to start the reaction is
known as activation energy.
Sometimes the activation energy is
low so that the reaction can start at
room temperature without heating.
 Order and Molecularity of reaction
What is the order of reaction?
The order of reaction is defined as

“ the sum of the coefficients (or power ) of the reacting species that are
involved in the rate equation for the reaction.”

The definition of order of reaction is valid both for elementary as well as complex
reactions. The order of the reaction is always determined experimentally.
Determination of order of reactions:
Let us consider a general reaction:
aA + bB + cC → Product
Let active moles of A, B and C be α, β and γ respectively. Then the rate of
reaction may be given as:
Rate = k [A]α [B]β [C]γ
The order of the reaction is equal to the sum of power of concentration terms
involved in rate law expression.
Order = α + β + γ
When α + β + γ = a + b +c, then order of reaction = molecularity of reaction
Note:
(i) Order is an experimentally determined quantity.
(ii) It may be equal to zero, positive, negative, whole number or fractional
number.
Examples:

(i) Reaction between H2 and Br2 to form HBr.

½
H2 + Br2 → 2HBr ; rate = k [H2] [HBr]
order of reaction = 1 + ½ = 3/2.

(ii) Reaction between CO and Cl2 to form COCl2.

CO + Cl2 → COCl2
rate = k [CO]2 [Cl2]½
order of reaction = 2 + ½ = 5/2.
What is the molecularity of reaction?
The number of reacting particles (molecules, atoms, or ions) that collide
simultaneously in a rate determining step to form a product is called
molecularity of a reaction.
In general, the molecularity of simple reactions is equal to the sum
of the number of molecules of reactants involved in the balanced
stoichiometric equation.

Examples:
• PCl5 → PCl3 + Cl2 (Unimolecular reaction)
• 2SO2 + O2 → 2SO3 (Trimolecular reaction)
• NO + O3 → NO2 + O2 (Bimolecular reaction)
 Note:​

(i) Molecularity of a reaction is always in the whole number.​

(ii) It is never fractional.​

(iii) Molecularity is a theoretical concept.​

(iv) Molecularity cannot be greater than three because more than

three molecules may not mutually collide with each other.
Difference between order and molecularity of reactions
 Types of Order of reaction:
• Pseudo-first-order reaction
• First- order reaction
• Second- order reaction
• Third- order reaction

Pseudo-first-order reaction:
 Pseudo-first-order reactions are reactions that are not first-order but appear to
be first-order due to larger concentrations of one or more reactants than the
other reactants.
Here pseudo means “fake”.
The reaction is bimolecular but whose order is one.
Example:
• One example is acid-catalyzed hydrolysis of ethyl acetate.
• Consider a reaction in which one reactant is in excess, say hydrolysis of ethyl
acetate. During the hydrolysis of 0.01 mol of ethyl acetate with 10 mol of water,
the reaction goes like this,
CH3COOC2H5(l)+H2O(l)→CH3COOH(l)+C2H5OH(l)
As the concentration of water does not get altered much during the process
( because it is in excess), take it as constant.
• So in the rate equation,
Rate = k'[CH3COOC2H5][H2O] and the term [H2O] can be taken constant. Thus,
the equation becomes
Rate = k[CH3COOC2H5]where k=k'[H2O]
Therefore, the order of reaction now becomes one, that is the reaction is now a
first-order reaction. Such reactions are called pseudo-first-order reactions.
First-Order Reaction:
A first-order reaction can be defined as a chemical reaction in which the
reaction rate is linearly dependent on the concentration of only one reactant. In
other words, a first-order reaction is a chemical reaction in which the rate
varies based on the changes in the concentration of only one of the reactants.
Thus, the order of these reactions is equal to 1.

Examples of First-Order Reactions:

• SO2Cl2 → Cl2 + SO2
• 2N2O5 → O2 + 4NO2
• 2H2O2 → 2H2O + O2
Differential Rate Law for a First-Order Reaction:
A differential rate law can be employed to describe a chemical reaction at a
molecular level. The differential rate expression for a first-order reaction can be
written as:
Rate = -d[A]/dt
= k[A]1
= k[A]
Where,
• ‘k’ is the rate constant of the first-order reaction, whose units are s -1.
• ‘[A]’ denotes the concentration of the first-order reactant ‘A’.
• d[A]/dt denotes the change in the concentration of the first-order reactant ‘A’
in the time interval ‘dt’.
Graphical Representation of a First-Order Reaction
The concentration v/s time graph for a first-order reaction is provided below.
For first-order reactions, the equation ln[A] = -kt + ln[A]0 is similar to that of a
straight line (y = mx + c) with slope -k. This line can be graphically plotted as
follows.
 Second Order Reaction:
From the rate law equations given above, it can be understood that second order
reactions are chemical reactions which depend on either the concentrations of
two first-order reactants or the concentration of one-second order reactants.

Since second order reactions can be of the two types described above, the rate of
these reactions can be generalized as follows:
r = k[A]x[B]y
Where the sum of x and y (which corresponds to the
order of the chemical reaction in question) equals two.
Examples of Second Order Reactions​:
A few examples of second order reactions are given below:​
𝐻(+) + 𝑂𝐻(−) →𝐻2𝑂​
𝐶+𝑂2→𝐶𝑂+𝑂​
The two examples given above are the second order reactions
depending on the concentration of two separate first order reactants.​

2𝑁𝑂2→2𝑁𝑂+𝑂2​
2𝐻𝐼→𝐼2+𝐻2​
These reactions involve one second order reactant yielding the product.​
Graph of a Second Order Reaction:
Generalizing [R]t as [R] and rearranging the integrated rate law equation of
reactions of the second order, the following reaction is obtained.
1[𝑅]=𝑘𝑡+1[𝑅]0
Plotting a straight line (y=mx + c) corresponding to this equation (y = 1/[R] , x =
t , m = k , c = 1/[R]0)

It can be observed that the slope of the straight line is equal to the value of the rate
constant, k.
Third Order Reaction:
A third order reaction is a chemical reaction where the rate of reaction is
proportional to the concentration of each reacting molecule. In this reaction, the rate
is usually determined by the variation of three concentration terms.

Examples of Third Order Reactions:

For example, let us consider a chemical reaction, where
A+2B ⇢ C+D
According to the rate formula,
Rate, R= k [A]ˣ [B]ʸ
Here, the order with respect to A is given by x, and the order with respect to B is
given by y. So, the complete order of the reaction is the sum of x and y.

For a third-order reaction, the order of the chemical reaction will be 3.

Continue...
Let,
aA + bB + cC ⇢ Product

By rate formula,
R = k [A]ˣ [B]ʸ [C]z
The third-order reaction for the above chemical reaction is given by,
Order = x+y+z

To summarize, the order of reaction can be defined as the sum of the exponents
of all the reactants present in that chemical reaction. If the order of that reaction is
3, then the reaction is said to be a third-order reaction.
Different Cases in Third Order Reaction​:

When we are dealing with a third order reaction, there can be different cases
involved. It could be,​

(i) All three reactants have the same level of concentration.​

(ii) Two reactants have equal concentrations, but one has a different concentration.​

(iii) All three reactants have different or unequal concentrations.​

Third Order Reaction Examples:
● Let us consider the reaction between nitric oxide and chloride
2 NO +Cl ⇢ 2 NOCl
2

Rate, R= k[NO]2 [Cl2]

Order of above reaction = Sum of exponent of nitric oxide and chloride order
=2+1=3
● Let us consider the reaction between nitric oxide and oxygen
2 NO + O2 ⇢ 2 NO2
R= k[NO]2 [O2]
Order = 2 + 1 = 3
The unit of third-order reaction, when a rate is constant, is given by, rate of
reaction= k[Reactant]³
The unit of rate is given by,
R = mol/ Ls = mol L⁻¹ s⁻¹ mol L⁻¹ s⁻¹ = k ( mol L⁻¹ )³ k =L² mol⁻² s⁻¹
 Rate units:
Activation Energy Definition:

Activation energy is defined as the minimum amount of extra energy required by

a reacting molecule to get converted into a product. It can also be described as
the minimum amount of energy needed to activate or energise molecules or
atoms so that they can undergo a chemical reaction or transformation.

SI Unit of Activation Energy:

Activation energy is denoted by Ea. It is usually measured in joules (J) and or

kilojoules per mole (kJ/mol) or kilocalories per mole (kcal/mol) .
Factors Affecting Activation Energy
Activation energy depends on two factors:
1. Nature of Reactants :
In the case of ionic reactant, the value of (Ea) will be low because there is an
attraction between reacting species. While in the case of covalent reactant the
value of Ea will be high because energy is required to break the older bonds.

2. Effect of Catalyst:
Positive catalyst provides such an alternate path in which the value of E a will be
low, while the negative catalyst provides such an alternate path in which the value
of Ea will be high.
Note: Activation energy does not depend upon the temperature, pressure,
volume, concentration, or coefficients of reactant.
Activated Complex:
When reactant molecules collide with each other at its highest energy point,
an intermediate is formed which remains in equilibrium with the main
reactant. If this intermediate complex has an energy equal to or greater than
the Threshold Energy, it will be converted into a product.
Activation Energy Formula:
The formula used to find the value of Activation Energy, Ea is;
K = Ae-Ea/RT
Where;
K = Rate Constant
A = Arrhenius Constant
E = Activation Energy
a

R = Gas constant
= 8.34JK/mol
=8.314/1000 KJ/K/mol
= 2 cal /K/mol
= 0.0821 lit atm/K/mol
Taking log on both sides​;

ln K = ln A – (Ea/RT)ln e​
2.303 log K = 2.303 log A – Ea/RT​
log K = log A – Ea /2.303RT​
​