Kinetics of Homogeneous Reactions

• Chemical Kinetics:
- It is a study of rate of reaction and effect of various parameters like temperature,
pressure, concentration and presence of catalyst on it.
- Suppose a single-phase reaction aA + bB  rR + sS. The rate of reaction is given
by

- Similarly for reactant B, -rB = (-1/V)*(dNB/dt)= dCB/dt

- Similarly for product R, rC = (1/V)*(dNR/dt)= dCR/dt
- Similarly for product D, rS = (1/V)*(dNS/dt)= dCS/dt
• The rates of reaction of all materials are related by
• Temperature and concentration dependent term of Rate equation:

Rate = f(temperature and concentration)

= kCAa ,
k is the function of temperature. CAa is the concentration dependent term
k = k0e-E/RT
1. Temperature-dependent term of a rate equation
- The temperature dependency of reactions is determined by the activation energy and temperature
level of the reaction
- Arrhenius law: k = k0e-E/RT
where k = rate constant
k0 = frequency factor
E = activation energy
R = Gas constant
T = Temperature
- At same concentration, but at two different temperatures,

- From this equation, activation energy can be find out.

- Activation energy can also be found out from plot of lnk vs 1/T.
- Do experiment and find value of k at different temperature.
- Take ln on both side of Arrhenius equation, plot of lnk vs 1/T. Slope of curve will give – E/R. By
choosing proper value of R, we can find value of E.
• Activation energy: Minimum amount of energy is required for reaction to takes
place. If reactant is not have an energy equal to activation energy, reaction will not
be started.
- This amount of energy is required to break bonds between reactant and to form
bond between product.
• Theories of reaction rates:
1. Collision theory:
- According to this theory, atoms, molecules or ions must colloid to form product.
- Atoms, molecules or ions must have sufficient energy (Activation Energy) when
collision takes place.
- Collision must be effective. i.e. molecules must be properly oriented when
collision takes place.
2. Concentration dependent term of rate equation
• Single reactions: single rate equation is used to represent progress of the reaction.
E.g. AB
• Multiple reaction: more than one rate equation are used to represent progress of
the reaction. They may be series, parallel or combination of series parallel,
reversible etc. E.g
Series:

Parallel:

Series-parallel:

Reversible:
• Rate equations of various types of reactions:
Series:

Parallel:

Series-parallel:

Reversible:
Molecularity of reaction: It is the number of molecules involved in the
elementary reaction only.
- It may be one, two or three. Molecularity more than three is not possible.
- It has always integer value. Never be a fraction.
Order of reaction: It is the power of concentration in rate equation. E.g. for
rate equation the reaction is,

and where n is the overall order of reaction.

- Order of reaction may be fractional or integer and can be found from
experiment.
Rate constant K: Proportionality constant of rate. For nth order reaction,
dimension or rate constant becomes
• Elementary reactions: Elementary reactions are those in which stoichiometry
coefficient of reactant is same as order of that particular reactant in rate equation. E.g.
for reaction
rate equation becomes,

- This happens when single molecule of A interact with single molecule of B and
directly gives product without forming intermediates. The number of collisions is
proportional to concentration of reactant so rate is proportional to concentration.
• Nonelementary reactions: Nonelementary reactions are those in which
stoichiometry coefficient of reactant is not same as order of that particular reactant in
rate equation. E.g. for reaction , rate equation becomes

- This happens when single molecule of H2 interact with single molecule of Br2 and
forms intermediates.
- The intermediates may be free radicals, ions, polar substances or molecules.
- Nonelementary reactions are the sequence of elementary reactions.
• Representation of Elementary reactions:
- For reaction, the rate equation can be written as

- Here order with respect to reactant A is same as stoichiometry coefficient of

reactant A in reaction
- This reaction is not considered as by cancelling 2 on both sides for
which rate equation becomes
- Consider reaction
- The rate with respected to B is
- The rate with respect to D is
- The rate with respect to T is
- All the rates are related as
- All the rate constants are related as
• Representation of non elementary reactions:
A Nonelementary reaction is one whose stoichiometry does not match its kinetics.
For example,

- This confirms when experimental data do not follows rate equation.

- For example consider equation for which rate equation becomes,

- Lets assume that k = 6 lit/mol.s, CA0 = 0.1 mol/lit, CB0=0.1 mol/lit. Substituting in
above equation, Rate becomes 0.06 mol/lit.s as per equation and reaction is
elementary
- But when you carry experiment, actual rate is not 0.06 mol/lit.s i.e. rate do not
follow the rate equation. It means reaction is Nonelementary and intermediates are
formed.