CHAPTER

4 Chemical Kinetics

Chemical Kinetics In Collision Theory Activation Energy

Chemical Kinetics is the study of chemical reactions with respect In collision theory activation energy and proper orientation of the
to reaction rates, effect of various variables rearrangement of molecules together determine the criteria for an effective collision
atoms and formation of intermediates. and hence rate of a reaction.
The rate of a reaction
Nuclear Chemistry
The rate of a reaction is concerned with decrease in concentration
Nuclear chemistry is the study of chemical reactions involving
of reactants or increase in concentration of products per unit time.
changes in nuclei of atoms. It provides information about kinetic
It can be expressed as an instantaneous rate at a particular instant
of radioactive decay and time period (unaffected by temperature,
of time and average rate over a large period of time.
pressure catalyst).
Factors affecting rate of reaction
A number of factors such as nature of reactants and products, Formulae Chart
exposure to radiations, temperature, concentration of reactants, (i) For a general chemical transformation
catalyst and surface area of solid reactants effect the rate of a nA + mB → pC + qD
reaction.
1 d[A] 1 d[B] 1 d[C] 1 d[D]
Rate =    

Rate Law n dt m dt p dt q dt
Rate law is the mathematical representation for rate of reaction, it (ii) For general chemical changes
can be determined experimentally and cannot be predicted.
mA + nB → Products
Order of a reaction
dx
Order of a reaction with respect to a reactant is the power of Theoretical rate 
= k[A]m  [B]n
dt
its concentration term which appears in the rate law, it is an
(iii) For a general reaction:
experimentally determined quantity.
aA + bB → Products
Molecularity dx
Rate 
= k[A]m  [B]n
Molecularity of a reaction is the number of reacting species taking dt
part in an elementary reaction, which must collide simultaneously Order of reaction w.r.t. A = m
in order to bring about a chemical reaction. Molecularity of Order of reaction w.r.t. B = n
a reactant greater than 3 are rare, order and molecularity of
(iv) Unit of rate constant = (mole litre–1)1–n (time–1)
elementary reactions are same.
where, n = order of reaction
Rate Constant (v) For a zero order reaction: A → B
Rate constant is the proprotionality constant in rate law. d[A] 0
Rate =  k[A]  k(constant)
dt
Integrated Rate
(vi) For a first order reaction A → B
Integrated rate equations can be determined by integrating the
d[A]
differential rate equations. Rate =  k[A]
dt
Half Life 2.303 [A]0 2.303  a 
= k = log10 log10 
Half life is the time, in which half of the initial amount of reactants t [A]t t  a − x 
is converted into products. (Time taken for 50% completion of
reactions) (vii) For a first order reaction, A → B
 −k k T +10
log=
10 [A]t t + log10 [A]0 (xii) Temperature coefficient = = 2 to 3
2.303 kT
[A]0 Arrhenius equation, k = Ae − Ea / RT
(viii) For a zero order reaction t1/ 2 =
2k
0.693 k Ea  T2 − T1 
log10 2 =
For a first order reaction t1/ 2 =
k k [2.303R]  T1T2 
1
1 (A = Arrhenius’s constant Ea = Activation energy)
For an nth order reaction, t1/ 2 = (for n ≥ 2)
[A]0n −1
(ix) For a parallel reaction Ea
log
= 10 k log10 A −
2.303RT

(xiii) Binding energy, B.E. = ∆m×931.5 MeV

−d[A]
∆m = mass defect = calculated At. mass – observed At mass
= (k1 + k 2 )[A]
dt B.E.(total)
(x) For a first order reaction: A→B+C a reactant reacts with as B.E. per nucleon =
mass number
A, B and C
1 Mev = 9.6 × 1010 joule mol–1
2.303  V − V0 
k=
log10  ∞
t  V∞ − Vt  (xiv) Packing fraction, P.F.

(V = vol. of reagent) isotopic atomic mass − mass number

= × 104
mass number
(xi) For hydrolysis of sucrose, S 
+
H
→G + F (xv) In a radioactive decay, Nt = N0e–λt
2.303  r − r 
k= log10  0 ∞  . Amount of radioactive substance after ‘n’ half life periods
t  rt − r∞ 
n
 1
(r = rotation due to all S, G and F) N =   N0
 2

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