Introduction

The stream of chemistry that governs the rate of reactions along with their mechanisms is termed
as Chemical kinetics derived from a Greek word meaning chemical movement.

Combination of two or more reactants to produce a new product is called reaction.

Elementary Reaction: The reaction that occurs in a single step to give the product is called an
elementary reactions.

Complex reaction: The reactions that occur as a result of sequence of elementary reactions to give
the product is called complex reactions.
Rate of reaction

The rate at which the concentration of reactant or product participating in a chemical reaction alters
is called rate of reaction.

Rate of reaction = change in concentration/ time = (mol/litre)/time

Reactant (R) --> Product.

Rate [R]

Rate = k[R]

k = rate constant or velocity constant.

Let one mole of the reactant A produce one mole of the product B.

Let at time t1

[A]1 and [B]1 = Concentrations of A and B

Let at time t2

[R]2 and [P]2 = Concentrations of A and B

Rate of disappearance of A = Decrease in concentration of R / Time taken = -∆[A]/∆t

Rate of appearance of B = Increase in concentration of P / Time taken = +∆[B]/∆t

When two or more reactants combine with each other the molecules of the respective reactants
collide with each other to form the product. The collision between the molecules increases with the
increase in concentration of the reactants and thereby increases the rate of reaction.

A + B --> C + D

Here molecules of reactant A and B collide to produce molecules of product C and D.

Therefore we can conclude that rate of reaction is directly proportional to the concentration of the
participating reactants.

Rate ∝ [A]x [B]y

Or Rate = k[A]x [B]y

Hg(l) + Cl2 (g) --> HgCl2(s)

Rate of reaction= -∆[Hg]/∆t = ∆[Cl2]/∆t = ∆[Hg Cl2]/∆t

Factors affecting rate of reaction

Nature of reactant

Nature of bonding in the reactants determines the rate of a reaction. The ionic compounds react
faster compared to covalent compounds due to requirement of energy in covalent compounds to
cleave the existing binds.

The reaction between ionic compounds:

Precipitation of AgCl

AgNO3 + NaCl --> AgCl + NaNO3

The reactions between covalent compounds:

Temperature

Rate of reaction increases with the rise in temperature due to increase in average kinetic energy
which in turn increases the number of molecules having greater energy than threshold energy and
consequently increasing the number of effective collisions. The rate of a reaction is doubled (i.e.,
increased by 100%) with 10 oC rise in temperature.

Pressure

Increase in partial pressure increases the number of collisions. Therefore, the rate of reactions
involving gaseous reactants increases with the increase in partial pressures.

Catalyst

A catalyst increases the rate of reaction by giving an alternative path with lower activation energy
(Ea’) for the reaction to proceed.

Concentration of reactants

Increase in concentration increases the number of collisions and the activated collisions between the
reactant molecules. According to the collision theory, rate is directly proportional to the collision
frequency. Consequently, the rate of a reaction increases with the rise in the concentration of
reactant.
Surface area

The rate of a reaction increases with increase in the surface area of solid reactant.

PROBLEM. For the reaction: 2A + B → A2B , The rate = k[A][B]2with k= 2.0 x 10-6mol-2L2s-1. Calculate
the initial rate of the reaction when [A] = 0.1 mol L-1, [B] = 0.2 mol L-1. Calculate the rate of reaction
after [A] is reduced to 0.06 mol L-1.

SOLUTION. Rate = k [A][B]2

= (2.0 × 10 - 6mol - 2L2s - 1) (0.1 mol L - 1) (0.2 mol L - 1)2

= 8.0 × 10 - 9mol - 2L2s - 1

Reduction of [A] from 0.1 mol L - 1to 0.06 mol – 1

The concentration of A reacted = (0.1 - 0.06) mol L - 1 = 0.04 mol L - 1

The concentration of B reacted= 1/2 x 0.04 mol L-1 = 0.02 mol L - 1

The concentration of B available, [B] = (0.2 - 0.02) mol L - 1

= 0.18 mol L - 1

After reduction of [A] to 0.06 mol L - 1

The rate of the reaction

Rate = k [A][B]2

= (2.0 × 10 - 6mol - 2L2s - 1) (0.06 mol L - 1) (0.18 mol L - 1)2

= 3.89 mol L - 1s - 1
Average rate of reaction

The average rate of the reaction is the ratio of change in concentration of reactants to the change in
time. It is determined by the change in concentration of reactants or products and the time taken for
the change as well. As the reaction precedes forward the collisions between the molecules of the
participating reactants reduces thereby decreasing the average rate of the reaction.

Mathematically, Average rate of reaction = Change in concentration / Time = (mol/litre)/time

PROBLEM. For the reaction R → P, the concentration of a reactant changes from 0.03 M to 0.02 M
in 25 minutes. Calculate the average rate of reaction using units of time both in minutes and
seconds.

SOLUTION. R2= 0.02 M

R1= 0.03M

t2 - t1= 25 minutes

∆[R]/∆t =∆[R2-R1]/ t2- t1=- (0.02-0.03)/25 = 6.67 X 10-6 Ms-1

=0.005ML-1 min-1

PROBLEM. In a reaction, 2A → Products, the concentration of A decreases from 0.5 mol L-1 to 0.4
mol L-1 in 10 minutes. Calculate the rate during this interval?

SOLUTION. -1/2 (∆[A]/∆t) =-1/2(∆[A2-A1]/∆t) =-1/2 (0.4-0.5/10)

=0.005ML-1 min-1

= 5 X 10-3M min-1

Instantaneous rate of reaction

The ratio of change in concentration in chemical reaction to the time period is termed as
instantaneous rate of the reaction.

-d[R]/dt = change in chemical concentration over short period of time/ the short time elapsed =
(mol/litre) / time

It can be calculated from the slope of the tangent on a concentration- time graph.

For example, consider the following graph.

The rate of reaction at t = 40s in the above graph can be calculated by following method:

Rate of reaction = gradient of the tangent at 40s = (120-70)/(65-5) = 50/60= 0.83 cm3s-1

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Rate expression

The representation of rate of reaction in terms of concentration of the reactants is called rate
equation or rate expression.

For example, in the reaction

2NO(g) + O2(g) --> 2NO2

The rate expression is given as

Rate =k[NO]2[O2]

Let us consider another reaction

BrO3- + 5Br- + 6H+ --> 3Br + 3 H2O

Rate expression for this reaction is given as

k[BrO3-][Br-][H+]2

Order of a reaction

The addition of power of the concentration of reactant in a rate law expression gives the order of
reaction.

Let A + 2B --> C + D be a chemical reaction.

From rate law R = k [A]x [B]y

Now Order of reaction is defined as addition of the order of all the reactants participating in a
chemical reaction.

order w.r.t. A = x

Order w.r.t. B = y

Overall order of the given reaction = (x + y).

Units of order of reaction:

k = rate / [A]n = (mol.L-1s-1/molL-1) n

For 1st order reaction , n=1

k = rate / [A]1 = (mol.L-1s-1/molL-1) 1= s-1

For 2nd order reaction, n=2

k = rate / [A]2 = (mol.L-1s-1/molL-1) 2= L.mol-1s-1

PROBLEM. From the rate expression for the following reactions, determine their order of reaction
and the dimensions of the rate constants.

(i) 3 NO(g) → N2O(g) Rate = k[NO]2

(ii) H2O2 (aq) + 3 I - (aq) + 2 H+→ 2 H2O (l) + I3- Rate = k[H2O2][I - ]

(iii) CH3CHO(g) → CH4(g) + CO(g) Rate = k [CH3CHO]3/2

(iv) C2H5Cl(g) → C2H4(g) + HCl(g) Rate = k [C2H5Cl]

SOLUTION. (i) Rate = k[NO]2

Order of the reaction = 2

Dimension of k = Rate / [NO]2

= mol L-1 s-1 / (mol L-1)2

= mol L-1 s-1 / mol2 L-2

= L mol-1 s-1

(ii) Rate = k[H2O2][I - ]

Order of the reaction = 2

Dimension of k = Rate / [H2O2][I - ]

= mol L-1 s-1 / (mol L-1) (mol L-1)

= L mol-1 s-1

(iii) Rate =k [CH3CHO]3/2

Order of reaction = 3/2

Dimension of k = Rate / [CH3CHO]3/2

= mol L-1 s-1 / (mol L-1)3/2

= mol L-1 s-1 / mol3/2 L-3/2

= L½ mol-½ s-1

(iv) Rate = k [C2H5Cl]

Order of the reaction = 1

Dimension of k = Rate / [C2H5Cl]

= mol L-1 s-1 / mol L-1

= s-1

PROBLEM. For a reaction, A + B → Product; the rate law is given by, r = k [A]½ [B]2. What is the
order of the reaction?

SOLUTION. The order of the reaction = 1/2 + 2

= 2 1/2

= 2.5

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Zeroth order reaction

If the rate of reaction is independent of concentration of the reactant participating in the reaction
then the reaction is called Zeroth order reaction.

A --> B

At time t = 0 concentration of A (reactant) is a and B (product) is 0. At time t = t the concentration of

A (reactant) is (a-x) and that of B (product) is x.

-d[A]/dt = k0[A]0 => dx/dt = k0(a-x)0

dx/dt = k0

∫ 0x dx =k0 ∫0 x dt

X = k0t

Second order reaction

A reaction with order equal to two is called a second order reaction.

r = k[A]2

or r = k [A][B]

PROBLEM. The decomposition of NH3on platinum surface is zero order reaction. What are the rates
of production of N2and H2if k = 2.5 x 10-4mol-1L s-1?

SOLUTION. 2NH3 --> N2 + 3H2

Rate of zero order reaction

-1/2 (d[NH3]/dt) = d[N2]/dt = 1/3 (d[H2]/dt)

-1/2 (d[NH3]/dt) = d[N2]/dt = 1/3 (d[H2]/dt)= k = 2.5 x 10-4 mol L-1 s-1

Rate of production of N2

d[N2]/dt = 2.5 x 10-4 mol L-1 s-1

Rate of production of H2

d[H2]/dt = 3 x 2.5 x 10-4 mol L-1 s-1

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First order reaction

If the rate of reaction depends on the concentration of single reactant participating in chemical
reaction raised to the first power then it is called a first order reaction.
A --> B

At time t = 0 concentration of A (reactant) is a and B (product) is 0. At time t = t the concentration of

A (reactant) is (a-x) and that of B (product) is x.

-dx/dt ∝ (a-x) = dx/dt = k1(a-x)

∫ 0x dx/(a-x) = k1∫ 0t dt

dx/dt = k0(a-x)0

dx/dt = k0

∫0 x dx = k0∫ 0t dt

ln (a/a-x) = k1t => t = 1/ k1 ln (a/a-x) = 2.303/ k1 log (a/a-x)

k1 = 2.303 log (a/a-x)

PROBLEM. A first order reaction has a rate constant 1.15 10-3s-1. How long will 5 g of this reactant
take to reduce to 3 g?

SOLUTION. From the question, we can write down the following information:

Initial amount = 5 g

Final concentration = 3 g

Rate constant = 1.15 10 - 3s - 1

We know that for a 1st order reaction,

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

(2.303/1.15X10-3)log[5]/[3]

(2.303/1.15X10-3) X 0.2219 = 444.38 s = 444 s

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Second order reaction

A reaction with order equal to two is called a second order reaction.

r = k[A]2

or r = k [A][B]

Pseudo order reaction

The reaction that appears to be an nth order reaction but belongs to some different order is called
Pseudo order reaction.

For example, a pseudo first order reaction is a chemical reaction between two reactants participating
in a chemical reaction and therefore should be a second order reaction. But it resembles to be a first
order reaction due to the presence of reactants in negligible quantity.

Let R` + R`` --> P

Rate = k[A]1[B]1

Order of reaction = 2.

Let us consider another reaction,

CH3Br + OH−→ CH3OH+Br−

Rate law for this reaction is

Rate = k [OH−][CH3Br]

Rate = k [OH−][CH3Br] = k(constant)[CH3Br]=k′[CH3Br]

As only the concentration of CH3Br would change during the reaction, the rate would solely depend
upon the changes in the CH3Br reaction.

Molecularity

 As we know that molecules need to collide to bring about a chemical reaction, so the
number of molecules participating in an elementary chemical reaction that collides to bring
about the chemical reaction is called molecularity of a reaction.

 The value of molecularity of a reaction is always a positive value.

 Let us consider a following reaction:

A + 2B --> C + D

Here reactants are: 1 molecule of A ,2 molecules of B

Products are: 1 molecule of C , 1 molecule of D.

Therefore we can conclude that reaction is trimolecular.

A reaction with molecularity =1 is called unimolecular.

Example, PCl5 --> PCl3 + Cl2

 A reaction with molecularity =2 is called bimolecular.

Example, Cl + CH4 --> HCl + CH3

 A reaction with molecularity =3 is called trimolecular.

2FeCl3 + SnCl2 --> 2FeCl2 + SnCl4

 It is theoretical value and does not determine the rate of reaction. Nor does it depend upon
external factors like temperature or pressure, etc.

 Integrated rate equation


 Consider the reaction
 aA + bB --> cC + dD
 Rate = k [A]x[B]y
 -dR/dt = k[A]x[B]y
 dR/dt is instantaneous rate.
 Integrated rate equation for zero order reaction
 -dR/dt = k[R]0=k
 dR/dt = -k
 ∫ dR = -k ∫ dt
 [R]=-kt +I
 At t = 0
 R0= -k .0 + I
 I = R0
 So the equation becomes R = -kt + R0
 Graph for this is as follows:


 Integrated rate equation for first order reaction
 Rate = -dR/dt = k[R]2
 ∫ dR/R= - ∫ kt
  ln R = -kt + I
 At t = 0
 R = R0
 ln R0=-k X 0 +I
 I = ln R0
 So equation becomes
 ln R = -kt + ln R0
 ln [R0/ R]=-kt

Rate law

 The representation of rate of reaction in terms of molar concentration of the reactants

participating in a reaction raised to some power is called rate law.

 It is also called rate expression or rate equation.

 Consider a reaction:

2NO (g) + O2 (g) --> 2NO2

Rate ∝ [NO]2

Rate ∝ [O2]

Combining these two rates we derive

Rate ∝ [NO]2 [O2]

Rate =k [NO]2 [O2]

 Where k is the proportionality constant with a definite value at a specific temperature for a
specific reaction and is called Rate Constant.

 Rate law expression = -d[R]/ dt = k [NO]2 [O2]

 Half life reactions : The time elapsed in reduction of the

concentration of a reactant participating in a chemical reaction to
one half of its original concentration is called half-life reaction and is
represented by t1/2.
 Half-life for zero order reactions:
 A --> B
 At time t = 0 concentration of A (reactant) is a and B (product) is 0.
At time t = t the concentration of A (reactant) is (a-x) and that of B
(product) is x.
  x = k0t à a/2 = k0t1/2 = a/2k0
 t1/2 =a/2k0
 a=(2k0)(t1/2)
 y = mx
 t = Independent variable. It is taken at x-axis.
 m = 2k0
 Half-life for first order reactions:
 t = 2.303/k1 log a/(a-x)
 For half-life x = a/2; t = t 1/2
 t ½ = 2.303/k1 log a/(a-a/2) --> t1/2 = 2.303/k1 log2
 t ½ = 2.303/k1 X 3.010
 t ½ = 0.693/ k1

Rate determining step

 The slowest step during a chemical reaction determines the overall speed of a reaction
towards completion is called rate determining step.

 Let us consider the following reaction,

NO2(g)+CO(g)→NO(g)+CO2(g)

 The elementary steps of the reaction are as follows:

Step 1: NO2+NO2→NO+NO3 (Rate constant = k1, slow)

Step 2: NO3+CO→NO2+CO2 (Rate constant = k2, fast)

 As the first step is the slowest step in the reaction it will determine the rate of the overall
reaction. Therefore Step1 is the rate determining step of the given reaction and hence the
rate expression for the given reaction is the product of rate constant and the reactants of this
step.

Rate = k1[NO2][NO2]=k1[NO2]2

Activation energy

 The minimum quantitiy of external energy required for the conversion of reactant into
product or to produce an unstable intermediate is called activation energy. It is E

 Rate of reaction is inversely proportional to the activation energy.

 Therefore, greater value of activation energy leads to lower rate of reaction and increased
influence of temperature change on the rate constant.
PROBLEM. The rate of the chemical reaction doubles for an increase of 10 K in absolute
temperature from 298 K. Calculate ESolution.

SOLUTION. It is given that T1 = 298 K

∴T2 = (298 + 10) K

= 308 K

We also know that the rate of the reaction doubles when temperature is increased by 10°.

Therefore, let us take the value of k1 = k and that of k2 = 2k

Also, R = 8.314 J K - 1 mol - 1

Now, substituting these values in the equation:

Log k2/k1 = Ea/2.303R [T2-T1/T1T2]

Log 2k/k = Ea/2.303 X 8.314 [10/298 X 308]

Ea= 2.303 X 8.314 X 298 X 308 X log2/10

= 52897.78 J mol - 1

= 52.9 kJ mol - 1

Arrhenius equation

 The formula used to calculate the energy of activation and justify the effect of temperature
on rate of reaction is called Arrhenius Equation.

 It is given by the formula,

K = A e-Ea/RT

Where,

k = Rate constant

A= Frequency factor
e = mathematical quantity

Ea= activation energy

R = gas constant

T = kelvin temperature

ln K = ln A – Ea/(2.303RT)

Equation of a straight line with slope = –Ea /R.

 When Ea = 0 , Temperature = Infinity

K = Ae0 = A

e-Ea/RT =Boltzmann factor.

 For a chemical reaction the rate constant gets doubled for a rise of 10° temperature. This is
because according to Arrhenius Equation,

K = Ae-Ea/RT

Taking log on both sides of the equation

Ln k = ln A – Ea/RT

Comparing with the equation of a straight line

y= mx+c,

[m= slope of the line

c= y-intercept]

So we have:

y = ln k

x = 1/T

m = -Ea / R

c = ln A

Plotting k Vs (1/T)

PROBLEM. Find the activation energy (in kJ/mol) of the reaction if the rate constant at 600K is 3.4
M-1 s-1 and 31.0 at 750K.
SOLUTION. Ln k = ln A – Ea/RT

To find Ea, subtract ln A from both sides and multiply by -RT.

Ea = (ln A - ln k)RT

Collision theory

 It states that:

 According to collision theory the molecules collides with great kinetic energy in order to
bring about a chemical reaction.

The molecules of the reacting species collide through the space in a rectilinear motion.

Rate of a chemical reaction is proportional to the number of collisions between the molecules of
the reacting species.

The molecules must be properly oriented.

 Rate of successful collisions ∝ Fraction of successful collisions X Overall collision frequency.

 The number of collisions per second per unit volume of the molecules in a chemical reaction
is called collision frequency (Z).

Let A+B --> C + D

Rate = ZABe-Ea/RT

Here ZAB = collision frequency of A and B.

 In many reactions Rate = P ZABe-Ea/RT

Where p= steric factor which takes into account the proper orientation of the molecules participating
in a chemical reaction.

PROBLEM. The activation energy for the reaction 2HI(g) → H2 + I2(g) is 209.5 kJ mol-1 at 581 K.
Calculate the fraction of molecules of reactants having energy equal to or greater than activation
energy?

SOLUTION. Ea = 209.5 kJ mol - 1 = 209500 J mol - 1

T = 581 K
R = 8.314 JK - 1 mol - 1

Fraction of molecules of reactants having energy equal to or greater than activation energy is as
follows:

x = e-Ea/RT

ln x = -Ea/RT

log x = Ea/2.303RT

log x = 209500 J mol-1/2.303 X 8.314 J K-1 mol-1 X 581 = 18.8323

x = antilog (18.323)

= antilog 19.1977

= 1.471 X 10-19