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UNIT : 4
CHEMICAL KINETICS
1. Define rate of a chemical reaction? Rate of a
chemical reaction can be defined as the change in concentration of a reactant or product in unit time.
Average rate, rav = Decrease in concentration of reactant
Time taken

= ─ ∆[R] = ─ ([R2] ─ [R1])

∆t t2 ─ t1
= Increase in concentration of products
Time taken
= +∆ [P] = [P2] ─ [P1]
∆t t2 ─ t1
NOTE: For finding the instantaneous rate draw a tangent at time t on either of the curve for
concentration [R] and [P] VS t and find out the slope.
rinst = ─d[R] = ─slope (Reactants)
dt
rinst = d[P] = +slope (Products)
dt
2. Representation of rate from equation :
Hg(l) + Cl2(g) → HgCl2(s)
(Stoichiometric coefficient of reactants and
products are same)
Rate of reaction = ─∆ [Hg] = ─∆[Cl2] = ∆[HgCl2]
∆t ∆t ∆t
NOTE: For expressing rate of reaction where stoichiometric coefficients are not equal to one, rate
of disappearance of any of the reactants or rate of appearance of products divided by respective
stoichiometric coefficients.
2HI(g) → H2(g) + I2(g)
Rate of reaction = ─ 1 ∆[HI] = ∆[H2] = ∆[I2]
2 ∆t ∆t ∆t
3. Rate law or rate equation or rate expression.
The representation of rate of reaction in terms of concentration of the reactants is known as rate
law or rate equation or rate expression.
aA + bB → cC + dD
( a, b, c, d are the stoichiometric coefficients of reactants and products .)
Rate expression,
Rate α [A]x [B]y (x and y may or may not be equal to the stoichiometric
coefficients a and b of the reactants)
x y
Rate = K[A] [B] , k = rate constant
Differential rate equation:
─d[R] = k[A]x [B]y
dt
4. Rate law:
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It is the expression in which reaction rate is given in terms of molar concentration of reactants with
each term raised to some power, which may or may not be same as the stoichiometric coefficient of
the reacting species in a balanced chemical equation.
Unit of rate:
rate = Change in concentration = mol /L = mol L-1 s-1
Change in time s
Unit of rate constant(k):
rate = K [R]n
K = rate = (mol/L)1s-1
[R]n (mol/L)n
K = (mol/L)1-n s-1
Units of rate constant :
Zero order (n=0)
K = (mol/L)1-0s-1 = mol/L s-1
First order (n=1)
K = (mol/L)1-1s-1 = (mol/L)0s-1
= S-1
Second order(n=2)
K = (mol/L)1-2s-1= (mol/L)-1s-1
= mol-1 L s-1
NOTE: Rate law for any reaction cannot be predicted by merely looking at the balanced chemical
equation. ie., theoretically but must be determined experimentally.
Theoretical Experimental rate
CHCl3 + Cl2 → CCl4 + HCl Rate = K [CHCl3] [Cl2]½

5. Define order of a reaction?

The sum of the powers of the concentration of reactants in the rate law expression is called the
order of that chemical reaction. Order can be 0, 1, 2, 3 and even a fraction.
r = K [A]x [B]y order (n) = x+y
6. Define Elementary reaction?
The reactions taking place in one step are called elementary reactions.
7. Define Complex reactions?
The reactions which give the products in a sequence of elementary reactions are called complex
reactions.
eg: Halogenation of methane
8. Define molecularity of reaction?
The 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 is called molecularity
of a reaction.
eg: NH4 NO2 → N2 + 2H2O
Molecularity = Uni molecular
2HI → H2 + I2 , Molecularity = 2 or Bimolecular
NOTE: Complex reactions involving more than three molecules in the stoichiometric equation must
take place in more than one step. Reactions with molecularity three are very rare and slow.
9. Rate determining step:
In a complex reaction, the overall rate of the reaction is controlled by the slowest step, which is
called the rate determining step.
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eg: 2H202 + I─ 2H2O + O2

Alkaline medium

Rate = ─d [H2O2] = K [H2O2]1 [ I-]1

Dt
The reaction is first order with respect to H2O2 and I- .
Mechanism:
i) H2O2 + I- → H2 O + I O- (slow step, rate determining step)
ii) H2O2 + I O- → H2O + I- + O2
Both steps are bimolecular elementary reactions. Species IO- is the intermediate since it is
formed in the course of the reaction but not in the balanced equation. First step is the slow or
rate determining step
10. Distinguish between Order and Molecularity?
ORDER MOLECULARITY
Order is the sum of the powers of the Molecularity is the no: of reacting species
concentration of reactants in the rate law which must collide simultaneously in
expression. order to bring about a chemical reaction.

Order of a reaction is an experimental Molecularity is a theoretical concept. It

quantity. It can be zero and even a
fraction.
Order is applicable to elementary as well
as complex reactions.
cannot be zero or a non-integer.
Molecularity is applicable only for
elementary reactions. For complex
reaction, molecularity has no meaning.

For complex reaction order is given by Molecularity of the slowest step is same
the slowest step. as the order of the overall reaction.

11. Give some examples for zero order reactions?

i) The decomposition of gaseous NH3 on a hot platinum surface
2NH3 (g) 1130 K N2(g) + 3H2(g)
Pt catalyst
Rate = K [NH3]0 = K
NOTE: At high temperature the metal surface get saturated with gas molecules. So a further
change in reaction conditions is unable to alter the amount of ammonia on the surface of the
catalyst making rate of the reaction independent of its concentration.
ii) The thermal decomposition of HI on gold surface
iii)Enzyme catalysed reactions
12. Derive integrated rate equation for zero order?
Integrated rate equation:
Zero order:
For zero order reactions, the rate of the reactions is proportional to zero power of the
concentrations of reactants.
R→P
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Rate = ─d[R] = K[R]0

dt
─ d[R] = K × 1 = K
dt
d[R] = ─ Kdt
Integrating on both sides,
∫d[R] = ─ K∫dt [ ∫dx=x ]
[R] = ─ Kt + C (1)
At t = 0, [R] = [R]0
Substitute in eqn: (1)
[R]0 = ─ K × 0 + C = C
[R]0 = C
[R] = ─ Kt + [R]0
K = [R]0 ─ [R]
t
Zero order - Graphical representation

[R]0
Slope = _K Zero order
Rate
[R]

t Concentration
13. Derive integrated rate equation for first order?
First order reaction:
The rate of the reaction is proportional to the first power of the concentration of the
reactant R.
R→P
Rate = ─ d[R] = K[R]
dt
d[R] = ─ K [R]
dt
Integrating this equation, we get

ln [R] = ─ Kt + C (1)
When t = 0, [R] = [R]0
ln [R]0 = ─ K × 0 + C = C (Substitute this in the above eqn 1)
ln [R] = ─ Kt + ln [R]0
Kt = ln [R]0 - ln [R]
ln [R]0 = Kt
[R]
K = 1 ln [R]0 = K = 2.303 log [R]0
t [R] t [R]

Graphical representation for first order reaction:

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i) ln[R] = ─ Kt + ln[R]0
ln [R]0
K = ─ Slope Rate
ln [R] First order

0
t concentration

ii) K = 2.303 log [R]0

t [R]
log [R]0 Slope = K
log [R]0 = K t [R] 2.303
[R] 2.303
t

14. Give some examples for first order reactions?

i) Hydrogenation of ethene
C2H4 (g) + H2 (g) → C2H6 (g)
Rate = K [C2H4]
ii) Natural and artificial radioactive decay of unstable nuclei.
15.Derive the equation for rate constant of a first order gas phase equation?
First order gas phase reaction:
A(g) → B(g) + C(g)
Let Pi be the initial pressure of A and Pt the total pressure at time ‘t’. Integrated rate equation
for such a reaction can be derived as
Total pressure Pt = PA + PB + PC
If PA, PB and PC are the partial pressures of A, B and C respectively. If x atm decrease in pressure
of A at time t and one mole each of B and C is being formed , the increase in pressure of B and C
will be x atm each.
A (g) → B (g) + C (g)
At time=0 Pi atm 0 atm 0 atm
At time=t (Pi─x) x atm x atm
Pi be the initial pressure at t=0
Pt = (Pi─x) + x + x = Pi + x
x = Pt ─ Pi
PA = Pi ─ x = Pi ─ (Pt ─ Pi) = 2Pi ─ Pt
K = 2.303 log Pi
t 2Pi ─ Pt

16. Define half life period? Derive the relation between half life period and rate constant for a zero order
reaction?
Half life of a reaction:
The time in which the concentration of reactants is reduced to one half of its initial concentration is
called half life of a reaction.
For zero order:
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K = [R]0 ─ [R]
t
When t = t½ , [R] = [R]0
2
K = [R]0 ─ [R]0
2 , t½ = [R]0
t½ 2K
t1/2 for a zero order reaction is directly proportional to the initial concentration of reactants and
inversely proportional to rate constant.
17. Derive the relation between half life period and rate constant for a first order reaction?
For first order:
K = 2.303 log [R]0
t [R]
When t = t½ , [R] = [R]0
2
K = 2.303 log [R]0
t½ [R]0/2
t½ = 2.303 log 2
k
= 2.303 × 0.3010 = 0.693
K k

For first order reaction t½ is independent of [R]0

18. What is meant by pseudo first order reaction? Give examples of it?
Pseudo first order reaction:
A chemical reaction between two substances when one reactant is present in large excess, the
reaction behaves as first order reaction. Such reactions are called pseudo first order reactions.
i) eg; Hydrolysis of ester:
H+
CH3COOC2H5 + H2O CH3COOH + C 2H5OH
t=0 0.01 mol 10 mol 0 mol 0 mol
t 0 mol 9.9 mol 0.01 mol 0.01 mol
The concentration of H2O does not get altered much during the course of the reaction.
Rate = K1 [ CH3COOC2H5 ] [H2O]
the term [H2O] = Constant where k 1[H2O] =K
= K [ CH3COOC2H5 ]
ii) Inversion of cane sugar:
C12H22O11 + H2O H+ C6 H12 O6 + C6H12O6
Glucose Fructose
Rate = K [ C12H22O11 ]
19. What is the effect of temperature in the rate of a chemical reaction?
Temperature dependence and rate of a reaction:
For a chemical reaction with rise in temperature by 100C, the rate constant is nearly doubled. The
temperature dependence of the rate of a chemical reaction can be explained by Arrhenius
equation;
K = Ae –Ea/R T
A = Arrhenius equation ,Ea = Energy of activation
R = 8.314 J/K/mol , T = Temperature in K scale
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fraction
of
molecules

most probable K.E K.E

All the molecules of reactants do not have same kinetic energy. The number of molecules
possessing very low K.E are very less and very high kinetic energy are also very less. Most of the
molecules have average K.E. When temperature is increased, the maximum of the curve to the
higher energy value and the curves broadens out. Increasing the temperature of the substance
increases the fraction of molecules, which collide with energies greater than Ea. It is clear from
the graph that the curve at (t+10), the area showing the fraction of molecules having energy
equal to or greater than A.E gets doubled leading to doubling the rate of the reaction.
Graph
t

Fraction Energy of activation

of molecules t+10
Fraction of additional
molecules which react at (t+10)

This area shows

Kinetic energy fraction of molecules
Arrhenius equation: reacting at t
log K2 = Ea [ T2 ─ T1 ]
K1 2.303 [ T1 T2 ]
K1 and K2 are the values of rate constants at temperature T1 and T2 respectively.
20. Explain collision theory?
Collision theory:
It is based on kinetic theory of gases. According to this theory, reaction takes place as a
result of collision between reacting molecules. The no. of collisions per second per unit volume of
the reaction mixture is known as collision frequency (Z).
A + B → Products
Rate = ZAB e-Ea/R T (1)
-Ea/R T
e represents the fraction of molecules with energy equal or greater than Ea. Using eqn: (1)
, we can calculate the value of rate constant accurately for the reactions involving atomic species
or simple molecules. For complex reaction, deviations are observed because all collisions do not
lead to the formation of products. The molecules which possess sufficient K.E. (threshold
energy) and proper orientation can undergo effective collision.
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The proper orientation leads to formation of chemical bond whereas improper collision do not
lead to bond formation.
The rate of reaction depends upon the no. of effective collisions. Greater the no. of effective
collisions, more will be the rate of reaction.
Rate = PZAB e-Ea/R T ,P- Steric or probability factor
Eg: Nucleophilic substitution of OH─ with CH3Br
CH3Br + OH─ → CH3OH + Br ─
H
H Proper orientation [ HO----C----Br
H C Br + OH- H H
H improper orientation No products

21. What is the effect of catalyst in the rate of a chemical reaction?

A catalyst is a substance which alter the rate of a chemical reaction itself without undergoing a
permanent chemical change.
Catalyst takes part in a chemical reaction by forming an intermediate complex. This is not stable
which decomposes to give products and catalyst. A catalyst provides an alternate pathway or
reaction mechanism by reducing the A.E between reactants and products and hence lowering the
potential energy barrier.
A catalyst does not alter Gibb’s energy, ∆G of a reaction. A catalyst does not change the
equilibrium constant but helps in attaining the equilibrium faster.
--------------------------------------
Ea without catalyst

Potential
energy Ea with catalyst

---------------------------------------------------
reactants
Products

Reaction coordinate

22. Define Activation energy?

The extra energy given to the reactants to enable them to cross over the energy barrier between
reactants and products is called activation energy.
Activation energy = Threshold energy ─ average energy of the reactants.
OR
The energy required to form the intermediate, called activated complex is called activation
energy
23. Define threshold energy?
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The minimum energy that the reacting molecules must possess in order to undergo effective
collision to form the product is called threshold energy.
24. For a reaction A B ,the rate of the reaction becomes twenty seven times when the
concentration of A is increased 3 times. What is the order of the reaction?
R =k [A]n (1)
When A= 3A
27R =k [3A]n = k3n [A]n (2)
Eqn 2/1
27R = k3n [A]n
R = k [A]n
27 = 3n
33 = 3n ,n=3 (order=3)
25. When could order and molecularity of a reaction i) be the same and ii) different?
i) For elementary reaction order and molecularity of a reaction will be the same
ii) For complex reactions order and molecularity of a reaction will be different.
26. A reaction is 50% complete in 2 hours and 75% complete in 4 hours. What is the order of the
reaction?
First order (proof below)
27. Show that the time required for completion of three fourth of a first order reaction is twice the
required for the completion of half reaction?
t=2.303 log a [a= initial conc: , x=amount of substance reacted]
k a-x
t 3/4=2.303 log 1
k 1- 3/4
t 1/2=2.303 log 1
k 1- 1/2
t¾ = log 4 [log22 =2log2 = log 4]
t½ = log 2
t ¾ /t1/2 = 2
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