CHEMICAL KINETICS

For any chemical reaction different properties are studied;

(a) the feasibility of a chemical reaction which can be predicted by thermodynamics ( as you
know that a reaction with ΔG < 0, at constant temperature and pressure is feasible);—-Tells if
reaction is possible or not!

(b) extent to which a reaction will proceed can be determined from chemical equilibrium;

(c) speed of a reaction i.e. time taken by a reaction to reach equilibrium, dealt by Chemical
kinetics.

The branch of chemistry, which deals with the study of reaction rates, factors affecting rate and
their mechanisms, called chemical kinetics.

The word kinetics is derived from the Greek word ‘kinesis’ meaning movement.

Rate of reaction:

Rate describes how rapidly(fast) the reactants are consumed (been used) and products are
formed.

This would differentiate the reaction in slow, fast and moderate reactions.

1. Fast reactions: precipitation of silver chloride (AgCl) on addition of NaCl to AgNO3.

2. Slow reactions: rusting of iron in presence of air and moisture.
3. Moderate speed: inversion of cane sugar, titration, hydrolysis of starch, etc.

The speed of a reaction or the rate of a reaction can be defined as the change in concentration of
a reactant or product in unit time.

4. Decrease in concentration of reactant per unit time is called rate of reaction

OR

2. increase in concentration of product per unit time is called rate of the reaction.

Consider for a reaction,

A+B C

A and B are reactants: Concentration of them is going to decrease with progress of reaction

C is the product: Concentration of it will increase with reaction progress.

The rate equation for it can be written as’

𝐷𝑒𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑟𝑒𝑎𝑐 tan 𝑡 𝑑[𝐴] 𝑑[𝐵]
Rate= =− =−
𝑇𝑖𝑚𝑒 𝑑𝑡 𝑑𝑡
 OR
𝐼𝑛𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑑[𝐶]
Rate= =+
𝑇𝑖𝑚𝑒 𝑑𝑡

Let’s consider a general reaction,

aA+ bB cC + dD

Rate equation can be written as

1 𝑑[𝐴] 1 𝑑[𝐵] 1 𝑑[𝐶] 1 𝑑[𝐷]

Rate= − 𝑎 =−𝑏 =+ 𝑐 =+ 𝑑
𝑑𝑡 𝑑𝑡 𝑑𝑡 𝑑𝑡

For example,

Consider a reaction

A + 3B 2C

𝑑[𝐴] 1 𝑑[𝐵] 1 𝑑[𝐶]

Rate=− =− 3 =− 2
𝑑𝑡 𝑑𝑡 𝑑𝑡

Dimensions/Unit of/for rate are concentration divided by time, that is mole dm-3 s-1

Rate law:

Consider a general reaction,

aA+ bB cC +dD

Rate of reaction at a given time is proportional to product of molar concentration of reactant

raised to some power, which may or may not be equal to geometric coefficient in a balanced
chemical equation

Rate ∝ [A]x[B]y

rate= k[A]x[B]y
Where, k is proportionality constant called the rate constant.

It is independent of concentration and varies with temperature.

• Rate constant is equal to rate of reaction when product of concentration of reactants is

unity.

The powers, X and Y tells us how the concentration change affects the rate of reaction,

1. For x=y=1,

Rate depends linearly on the concentration of A and B. that is, if concentration of a or B is

doubled, the rate would double.

2. For x=2, y=1

If the concentration of A is doubled, keeping B constant, the rate will increase by factor of four.

3. For, x=0, the rate is independent of concentration of A.

4. If X is less than 0(negative), the rate decreases as A increases.

Order of the reaction(n).

The sum of powers of the concentration of the reactants in the rate law expression is called
the order of that chemical reaction.

Denoted by “n”

n= x + y

x and y are powers of concentration of reactants expressed in rate equation.

1. 2H2O2(g) 2H2O(l) + O2(g) experimentally determined rate law is

rate = k[H2O2]

The reaction is of first order.

Molecularity= 2

2. If the experimentally determined rate law for the reaction

 H2 (g) + I2 (g) 2 HI(g)

rate = k[H2] [I2]

The reaction is of first order in H2 and I2 each and hence overall of second order.

Molecularity=2

Distinction between Order and Molecularity of the reaction

Order Molecularity
1. It is experimentally determined i. It is theoretical entity.
property.

2. It is the sum of powers of the It is the number of reactant molecules

concerntration terms of reactants taking part in an elementary reaction.
those appear in the rate equation.

It may be an integer, fraction or zero. It is integer.

Elementary reaction: The reactions that occur in single step and cannot be broken down into
simpler steps or reactions.

Example:

O3 O2 + O

C2H5I C2H4 + HI

Complex reactions: Reactions, those constitute a series of elementary reactions

Rate determining step: the slowest step in the complex reaction is the rate determining step.

Consider, 2NO2Cl(g) 2NO2(g) + Cl2(g).

The reaction takes place in two steps:

i. NO2Cl(g) NO2 (g) + Cl(g) (slow)

ii. NO2Cl(g) + Cl (g) NO2 (g) + Cl2 (g) (fast)

Overall

2NO2Cl(g) 2NO2(g) + Cl2(g)

The first step being slower than the second it is the rate determining step. The rate law is

rate = k[NO2Cl]

Reaction intermediate:

In the above reaction, Cl is formed in the first step and is consumed in the second step. such
species represent the reaction intermediate

Things to remember while writing rate law

1. Concentration of product is not represented in the rate law

2. Concentration of the intermediates are not represented in the rate law

3. Concentration of the excess reagent is not represented in the rate law

Collision theory of bimolecular reactions

Chemical reactions occur due to collisions between reactant species.

Rate of collision = Rate of reaction

Activation energy: molecules must possess minimum amount of energy so that the reaction can
occur is called activation energy (Ea)

The colliding molecules must possess kinetic energy equal to or greater than activation energy.

Orientation of reactant molecules:

Colliding molecules must have proper orientation along with Ea

Consider a reaction where,

A + B-C A-B + C
 1. The collision of A with C approaching toward A would not lead to reaction.

+ -

No reaction will take place. The reactant molecules would collide and separate owing to the
improper orientation of C - B.

2.

The reaction is successful as a result of proper orientation of C - B. A fraction of such collisions

brings forth conversion of reactants to products.

Potential energy barrier:

Consider again the reaction A+ C - B A- B + C
A configuration in which all the three atoms are weakly connected together is called activated
complex.

A+ C - B A⋅⋅⋅⋅ B⋅⋅⋅⋅ C A- B + C

To attain the configuration A⋅⋅⋅ B⋅⋅⋅ C atoms need to gain energy, which comes from the kinetic
energy of colliding molecules.
The energy difference between reactants and activated complex/transition state is activation
energy.

Whereas, Energy difference between products and reactants is the change in enthalpy (Δ H)

For endothermic (where energy is absorbed) reaction, the product formed has more energy as
compared to that of reactants.
For exothermic reactions (energy is released), the product has less energy as compared to that of
reactants as depicted in figure. The excess energy is released which is change in enthalpy.