Reaction kinetics

Chemical kinetics is the study of reaction rates, how reaction

Scope of Reaction Kinetics rates change under varying conditions, and what molecular
events occur during the overall reaction.

What variables affect reaction rates?

• Concentrations of reactants. Often the rate of reaction

Factors that affect the increases when the concentration of a reactant is increased.
reaction rate • Catalyst. A catalyst is a substance that increases the rate of
reaction without being consumed in the overall reaction.
• Temperature at which the reaction occurs. Usually, reactions
speed up when the temperature increases.
• Surface area of a solid reactant or catalyst. If a reaction
involves a solid with a gas or liquid, the surface area of the
solid affects the reaction rate.
• Pressure can affect the rate of the reaction if all the reactant
and products are gas
Rate of reaction

The reaction rate is the increase in molar concentration of product of a reaction per
unit time or the decrease in molar concentration of reactant per unit time.
The usual unit of reaction rate is moles per liter per second, mol/(Ls).

2N2O5(g) ➔ 4NO2(g) + O2(g)

Rate of formation of oxygen =

The rate for this reaction could be found by observing the

increase in molar concentration of O2 produced.
Rate of reaction

Reaction rate is the change in the concentration of a reactant or a product with time
(M/s).
A B
Δ[A] Δ[A] = change in concentration of A over
rate = -
Δt time period Δt

Δ[B] Δ[B] = change in concentration of B over

rate =
Δt time period Δt

Because [A] decreases with time, Δ[A] is negative.

Unit: mole L-1 s-1, mole L-1 min-1, mole L-1 h-1 etc.
Average Rate
Instantaneous Rate
Instantaneous rate—that is, the rate at a particular instant
of time. The instantaneous rate is also the value of [O2]/
t for the tangent at a given instant (the straight line that
just touches the curve of concentration
versus time at a given point)
Reaction Rates and Stoichiometry

2A B

Two moles of A disappear for each mole of B that is formed.

1 Δ[A] Δ[B]
rate = - rate =
2 Δt Δt

aA + bB cC + dD

1 Δ[A] 1 Δ[B] 1 Δ[C] 1 Δ[D]

rate = - =- = =
a Δt b Δt c Δt d Δt
Reaction Rates and Stoichiometry

The amounts of products and reactants are related by stoichiometry, so any substance in
the reaction can be used to express the rate of reaction. In the case of the decomposition of
N2O5 to NO2 and O2, the rate is expressed in terms of the rate of formation of oxygen,
Δ[O2]/Δt. However, it can also be expressed in terms of the rate of decomposition of N 2O5.
Reaction Rates and Stoichiometry

▪ Write the rate expression for the following reaction:

CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (g)

Δ[CH4] 1 Δ[O2] Δ[CO2] 1 Δ[H2O]

rate = - =- = =
Δt 2 Δt Δt 2 Δt
Solved Problem: Chemistry (Raymond Chang-10th ) 13.1, 13.2
Dependence of Rate on Concentration: Rate law

A rate law is an equation that relates the rate of a reaction to the concentrations of reactants (and
catalyst) raised to various powers. The following equation is the rate law for the foregoing reaction:

Here k, called the rate constant, is a proportionality constant in the relationship between rate and
concentrations.
aA + bB cC + dD

Rate = k [A]m [B]n

▪ The term k is the rate constant, which is specific for a given reaction at a given temperature.

▪ The exponents m and n are reaction orders and are determined by experiment.
- The values of m and n are not necessarily related in any way to the coefficients a and b.
Rate Constant

The rate constant, k, is a proportionality constant in the relationship between rate and
concentrations.
It has a fixed value at any given temperature, but it varies with temperature. Whereas the
units of rate are usually given as mol/(Ls), the units of k depend on the form of the rate law.

from which you get the following unit for k:

 Order of reaction
aA + bB cC + dD
Rate = k [A]m [B]n

The order of such a reaction is (m + n). The order of a reaction is defined as the sum of the powers of
concentrations in the rate law. The order of reaction can be defined as the power dependence of rate
on the concentration of all reactants.

Characteristics of the reaction order for a chemical reaction

•Reaction order represents the number of species whose concentration directly affects the rate of
reaction.
•It can be obtained by adding all the exponents of the concentration terms in the rate expression.
•The order of reaction does not depend on the stoichiometric coefficients corresponding to each species
in the balanced reaction.
•The reaction order of a chemical reaction is always defined with the help of reactant concentrations
and not with product concentrations.
•The value of the order of reaction can be in the form of an integer or a fraction. It can even have a
value of zero.
 Order of reaction
For the reaction between nitrogen monoxide and
ozone,
nA → products
NO(g) + O3(g) → NO2(g) + O2(g)
rate= -d[A]/dt =k[A]n
the rate law is, Rate = k[NO][O3]
Consider first the simplest case, a reaction This reaction is first order with respect to NO and first
with only one reactant, A: A → products order with respect to O3, so it is second order overall.
• First order: Rate =k[A]1 = k[A]
• Second order: Rate =k[A]2
• Zero order: Rate =k[A]0 = k Fractional Order
CHCl3(g) + Cl2(g) = CCl4(g) +HCl(g)
Rate = k[CHCl3][Cl2]1/2

Negative reaction order means the rate decreases when the concentration of that component
increases. Negative orders are often seen when the rate law includes products. For example,
2O3(g) = 3O2(g) The rate law is Rate =k[O3]2[O2]-1
If [O2] doubles, the reaction precedes half as fast. This reaction is second order in O 3 and negative first
order in O2, so it is first order overall [-2+1=1]
Order of reaction
Order of reaction

2N2O5(g) ➔ 4NO2(g) + O2(g)

In Experiment 2, the initial concentration of N2O5 is twice that in

Experiment 1.
In Experiment 2, initial rate of disappearance of N2O5 is twice
that in Experiment 1.
Order of reaction
The Order of a Reaction - Problems
Molecularity of a Reaction

▪ Chemical reactions are classified into two types-

✓ Elementary reactions - occurs in a single step
✓ Complex reactions - occurs in two or more steps

▪ For elementary reactions, molecularity is defined as the number of molecules involved

in the reaction.
▪ Examples:
Br2 2Br Unimolecular
H2 + I2 2HI Bimolecular
2NO + O2 2NO2 Termolecular
Molecularity of a Complex Reaction

▪ Most chemical reactions are complex reactions. These occur in a series of steps.
▪ Each step is an elementary reaction.
▪ Some of the steps will be fast, and others will be slow. A reaction can proceed no faster than
its slowest step.
▪ Thus, the slowest step is the rate determining step of the reaction.
▪ Molecularity of a complex reaction is defined as the number of molecules or atoms taking
part in the rate-determining step.
2N2O5 ⎯⎯→ 4NO2 + O2
Step 1: 2N2O5 ⎯⎯→ 2NO2 + 2NO3 ; Fast
Step 2: NO2 + NO3 ⎯⎯→ NO2 + NO + O2 ; Slow
Step 3: NO + NO3 ⎯⎯→ 2NO2 ; Fast

Thus step 2 in the above mechanism is rate-determining and has molecularity ‘2’ which could be
considered as the molecularity of the decomposition reaction of N 2O5.
 Order Molecularity
Sum of powers of the concentration terms in Number of reactant molecular involved in a
the rate law expression. reaction
It is experimentally determined value. It is a theoretical concept.

It can have a fractional value. It is always a whole number.

Order of reaction can be zero. Molecularity can never be zero.

Order of reaction can change with conditions For a chemical reaction, molecularity is always
like temperature, pressure, concentration etc. same.
Half life of a Zero order reaction, t ½ = a/2k0
Solved problem: Ebbing (9th)-13.6
Chang (10th)-13.4, 13.6
Collision theory

The collision theory of reaction rate attempts to account for the observed kinetics of reactions in
terms of molecular behavior of reacting system. In collision theory, in order to a reaction to happen,
the reactant molecules must
a. Collide
b. Possess or collide with sufficient energy for them to be activated
c. Collide with proper orientation
Thus, according to the theory, the rate constant for a reaction is given by the product of three factors
(i) The collision frequency (z): It can be defined by the number of molecules colliding per area per
time in a reacting system containing 1 mole of reactant in 1 liter.
(ii)The fraction of collision having energy equal to or greater than the energy of activation. It can be
expressed by f
(iii)The fraction of collision that occurs with reactant molecules properly oriented, sometimes called
steric factor and can be expressed as p
𝐸𝑎
−𝑅𝑇
𝑘= 𝑝𝑧𝑒
Transition State Theory

▪ An effective collision between particles leads to the formation of a transition state or activated
complex.
▪ During the collision, the reactant molecules form a transition state or activated complex which
decomposes to give the products.

▪ The transition state is an unstable species that contains

partial bonds.
▪ It’s a transitional pathway between reactants and
products.
▪ Transition states cannot be isolated.