Chemical Kinetics

Rate of a Chemical Reaction

• Expressed in terms of −

• Rate of decrease in concentration of any one of the reactants

• Rate of increase in concentration of any one of the products

• For a reaction R → P

One mole of R → One mole of P

• [R]1 and [P]1 are the concentrations of [R] and [P] respectively at time t1

[R]2 and [P]2 are the concentrations of [R] and [P] respectively at time t2

∴Rate of disappearance of R

(Since Δ[R] is a negative quantity, it is multiplied by −1 to make the rate a positive quantity.)

And, rate of appearance of P

• Equations (1) and (2) represent the average rate of a reaction.

• The dependence of the average rate upon the change in the concentration of the reactants or
products, and the time taken for that change to occur, is shown in the given figures.
• Instantaneous rate − The rate of a particular moment of time

• Obtained when the average rate at the smallest time interval, say dt (i.e., when Δt approaches zero)
is considered

• Mathematically, for an infinitesimaly small (dt), instantaneous rate is given by

 As Δt → 0

• For the reactions −

Rate of reaction

Rate of reaction

When the stoichiometric coefficients of the reactants or products are not equal to one, the rate of
disappearance of any of the reactants or the rate of appearance of any of the products is divided by
their respective coefficients.

• For a gaseous reaction −

• At constant temperature, concentration is directly proportional to the partial pressure of a species

• Rate can be expressed as the rate of change in partial pressure of the reactants or the products

Factors Influencing Rate of a Reaction

• Rate of a reaction depends upon

• Concentration of reactants (pressure in case of gases)

• Temperature
• Catalyst

Dependence of Rate on Concentration

• At a given temperature, the rate may depend on the concentration of one or more reactants and
products.

• Rate law

• Representation of the rate of reaction in terms of the concentration of the reactants

• Also known as rate equation or rate expression

Rate Expression and Rate Constant

• For a general reaction

Where,a, b,c, d= Stoichiometric coefficients of reactants and products

• Rate of reaction generally increases when reactant concentrations increase.

xand y may or may not be equal to aand b.

‘k’ is called rate constant

• Equation (1) is called rate law or rate expression.

• Rate Law − An expression in which the rate of reaction is given in terms of the molar concentration
of the reactants, with each term raised to some power, which may or may not be the stoichiometric
coefficient of the reacting species in a balanced chemical equation.

• Example:

(Experimentally determined)
 Differential form of rate expression is

• For this reaction, the exponents of the concentration terms are the same as their stoichiometric
coefficients in the balanced chemical equation.

• Some other examples −

• CHCl3 + Cl2 → CCl4 + HCl

(Experimentally determined)

• →

(Experimentally determined)

Here, the exponents of the concentration terms are not the same as their stoichiometric
coefficients.

• Rate law cannot be predicted by looking at the balanced chemical equation. It must be determined
experimentally.

Order of Reaction

• For a reaction with rate equation,

Overall order = x + y

• Can be 0, 1, 2, 3, and even a fraction

• Zero order reaction − Rate of reaction is independent of the concentration of the reactants

Unit of Rate Constant

• For a general reaction

aA + bB → cC + dD

• Rate = k [A]x [B]y

• x + y = n = Order of the reaction

• SI units of concentration and time are mol L−1 and s respectively.

• Taking the SI units of concentration and time, the units of rate constant (k) for different reactions
are listed in the given table.

Reaction Order Units of rate constant

Zero order reaction 0

First order reaction 1

Second order reaction 2

Molecularity of Reaction

• Number of reacting species (atoms, ions or molecules) taking part in an elementary reaction, which
must collide simultaneously in order to bring about a chemical reaction

• Example:

Molecularity = 1 (Unimolecular)
•

Molecularity = 2 (Bimolecular)

Molecularity = 3 (Trimolecular)

• Complex reactions involving more than three molecules must take place in more than one step.

• The overall rate of the reaction is controlled by the slowest step in the reaction, called the rate-
determining step.

• For example:

• The given decomposition reaction of H2O2 takes place in two steps:

• The species is the intermediate.

• First step is slow and it is the rate-determining step.

Thus, the rate of formation of the intermediate will determine the rate of this reaction.

Integrated Rate Equations for Zero and First Order Reactions

Integrated rate equations

• Concentration dependence of rate is called differential rate equation.

• Not convenient to determine the instantaneous rate; difficult to determine the rate law and hence,
the order of reaction

• To avoid the difficulty, the differential rate equation is integrated to give a relation between
concentrations at different times and rate constant, which is called integrated rate equation.

Zero order reactions

• Rate of reaction is proportional to zero order of the concentration of the reactant.

• Derivation of rate equation

For the reaction, R → P

Integrating both sides,

[R] = − kt + I …(i)

I is the constant of integration.

When t = 0, [R] = [R]0

[R]0 = Initial concentration of the reactant

Substituting [R] = [R]0 in equation (i),

[R]0 = −k × 0 + I

Or, [R]0 = I

Substituting value of I in equation (i),

[R] = −kt + [R]0

If [R] is plotted against time (t), a straight line is obtained as shown in the given figure.
 Slope = −k

Intercept = [R]0

Simplified rate equation for zero order reaction is

• Examples:

• Some enzyme-catalysed reactions

• Some reactions which occur on metal surface

For example, decomposition of gaseous ammonia on hot platinum surface at high

pressure:

Rate = k[NH3]0 = k

• Thermal decomposition of HI on gold surface

First Order Reactions

• Rate of reaction is proportional to the first power of the concentration of the reactant R.

• Derivation of rate equation

For the reaction, R → P

Integrating this equation,

ln [R] = − kt + I …(ii)

I = Integration constant

When t = 0, [R] = [R]0

[R]0 = Initial concentration of the reactant

Substituting [R] = [R]0 in equation (ii),

ln [R]0 = − k × 0 + I

Or, ln [R]0 = I

Substituting the value of I in equation (ii),

ln [R] = − kt + ln [R]0 …(iii)

From equation (iii),

At time t1, ln [R]1 = − kt1 + ln [R]0 …(iv)

At time t2, ln [R]2 = − kt2 + ln [R]0 …(v)

[R]1 = Concentration of reactant at time t1

[R]2 = Concentration of reactant at time t2

(iv) − (v) ⇒ ln [R]1 − ln [R]2 = − kt1 − (−kt2)

 Equation (iii) can also be written as

Taking antilog on both sides,

[R] = [R]0 e−kt …(vii)

Plot of ln [R] against t is shown in the figure below.

Slope = −k

Intercept = ln [R]0

• First order rate equation can also be written as

Plot of log [R]o / [R] vs. t is shown in the figure below.

• Examples:

• Hydrogenation of ethene

C2H4(g) + H2(g) → C2H6(g)

Rate = k [C2H4]

• All natural and artificial radioactive decay of unstable nucleus

Rate = k [Ra]

• Decomposition of N2O5 and NO2

First Order Gas Phase Reaction

A(g) → B(g) + C(g)

pi = Initial pressure of A

pt = Total pressure at time ‘t’

Total pressure, pt = pA + pB + pC

pA , pB, and pC are the partial pressures of A, B, and C respectively.

If x atm is decrease in pressure of A at time t and one mole each of B and C is being formed, then the
increase in pressure of B and C will also be x atm each.
 Where, pi is the initial pressure at t = 0

pt = (pi − x) + x + x

⇒ pt = pi + x

⇒ x = pt − pi

Where, pA = pi − x = pi − (pt − pi)

= 2 pi − pt

Half-Life of a Reaction

• The time in which the concentration of a reactant is reduced to one half of its initial concentration

• Denoted by

Half-Life for a Zero Order Reaction

• Rate constant for a zero order reaction is

Rate constant at becomes

• for a zero order reaction is directly proportional to the initial concentration of the reactants,
i.e., .

• for a zero order reaction is inversely proportional to the rate constant.

Half-Life for a First Order Reaction

• Rate constant for the first order reaction is

• For a first order reaction, the half-life period is constant, i.e., is independent of [R]0.

The given table summarises the mathematical features of integrated laws of zero and first order
reactions.

Order Reaction Differential Integrated rate Straight Half- Units of

rate law law line plot life k
type
 0 R→P d[R] /dt = −k kt = [R]0 − [R] [R] vs t [R]0/2k conc
time−1 or
mol
L−1s−1

1 R→P d[R]/dt = −k[R] [R] = [R]0e−kt or kt = ln [R] vs t ln 2/k time−1 or

{[R]0/[R]} s−1

What are Pseudo First Order Reactions?

• The order of the reactions can sometimes be altered. For example, consider a chemical reaction
between two substances when one reactant is present in excess.

Hydrolysis of ethyl acetate −

Rate =

The concentration of water does not change much during the course of the reaction. Thus, the term
[H2O] can be taken to be constant.

• Thus, the given reaction behaves as a first order reaction. Such reactions are called pseudo first
order reactions.

Another example: Inversion of cane sugar

Temperature Dependence of Rate of a Reaction & Effect of Catalyst

Temperature Dependence of Rate of a Reaction

• Increase in temperature accelerates the rate of reaction.

• With the rise in temperature by 10°, the rate constant of a chemical reaction is nearly doubled.

• The temperature dependence of the rate of a chemical reaction can be accurately explained by
Arrhenius equation.

A = Arrhenius factor or frequency factor or pre-exponential factor

R = Gas constant

Ea = Activation energy (in J mol−1)

• Formation of HI through the intermediate in the reaction is shown in the

figure below.

• According to Arrhenius, the reaction can take place only when H2 and I2 molecules collide to form
unstable intermediate.

• Energy required to form this unstable intermediate (called activated complex) is called activation
energy.

• Energy is released when the complex decomposes to form products (that is HI).

• Final heat of the reaction depends upon the nature of reactants and products.

• The distribution curve showing the energies of the molecules is shown in the figure below.
• The peak of the curve corresponds to the most probable kinetic energy.

Most probable kinetic energy − Kinetic energy of maximum fraction of molecules

• When the temperature is raised, the maximum of the curve moves to a higher energy value.

• There is greater proportion of molecules with much higher energies.

• Increase in temperature of the substance increases the fraction of molecules, which collide with
energies greater than Ea.

• In the curve at (t + 10), it is evident that the area showing the fraction of molecules having energy
equal to or greater than activation energy gets doubled, leading to doubling the rate of a reaction.

Arrhenius Equation

Factor represents the fraction of molecules that have kinetic energy greater than Ea.

Taking natural logarithm on both sides of equation (1), we obtain

 Plot of vs gives a straight line (shown in figure).

Slope

Intercept = ln A

• At temperature (T1),

At temperature (T2),

Now we obtain,

• Increase in temperature or decrease in activation energy will result in an increase in the rate of the
reaction and this increase is exponential.

Effect of Catalyst

• Catalyst − Substance that alters the rate of a reaction without itself undergoing any
permanent chemical change
• For the reaction − ,

MnO2 catalyses the reaction by increasing the rate

• Catalyst reduces the activation energy between the reactants and products and hence, lowers the
potential energy barrier (shown in figure).

• Lower the value of activation energy, faster will be the rate of reaction.

• Catalyst does not alter Gibbs energy ( ) of the reaction.

• It catalyses spontaneous reactions, but not non-spontaneous reactions.

• In helps in attaining the equilibrium faster (that is, it catalyses forward as well as backward
reactions to the same extent).

Collision Theory of Chemical Reactions

• Developed by Max Trautz and William Lewis in 1916-18

• Gives energetic and mechanistic aspects of reactions

• Based on kinetic theory of gases

• Assumptions − Reactant molecules are assumed to be hard spheres and reaction is postulated to
occur when molecules collide with each other.

• Factors which affect the rate of reactions:

• Collision frequency (Z) = Number of collisions per second per unit volume of the reaction mixture

• Activation energy

• For a bimolecular reaction,

 Rate of reaction =

ZAB = Collision frequency of reactants (A and B)

= Fraction of molecules with energies equal to or greater than Ea

• As compared with Arrhenius equation, A is related to collision frequency (Z).

• All collisions do not lead to the formation of products.

• Effective collisions:

• Collisions in which molecules collide with sufficient kinetic energy (called threshold energy) and
proper orientation, so as to facilitate breaking of bonds between reacting species and formation of
new bonds to form products

Threshold energy = Activation energy + Energy possessed by reacting species

• Example − Formation of methanol from bromomethane requires proper orientation of reactant

molecules.

• Proper orientation of reactant molecules − Bond formation

• Improper orientation of reactant molecules − No products are formed

• To account for effective collisions, another factor P is introduced.

Now, Rate =
• P is called probability or steric factor.

• It takes into account the fact that in collision, molecules must be properly oriented.

• Thus, in collision theory, the factors that determine the criteria for effective collisions, and hence
the rate of a chemical reaction, are:

• Activation energy

• Proper orientation of molecules

• Drawback − It considers atoms/molecules to be hard spheres and ignores their structural aspect.