CHEMICAL KINETICS

Learning points:
- Introduction
- Rate of a chemical reaction
- Types of chemical reaction on the basis of rate
- Average and instantaneous rate of reaction
- Factors affecting rate of reaction
- Concentration dependent rate
- Order of reaction
- Integrated rate equation
- Molecularity of reaction
- Temperature dependent rate of reaction
- Collision theory of chemical reaction
Chemical Kinetics - It is the branch of chemistry which deals
about the rate of a chemical reaction and its mechanism (The
path of a chemical reaction)
Rate of a Chemical reaction - It is the change in molar
concentration of reactant or Product with respect to time
𝐶ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑚𝑜𝑙𝑎𝑟 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡
Rate = 𝐶ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑇𝑖𝑚𝑒

𝐶ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑚𝑜𝑙𝑎𝑟 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡

= 𝐶ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑇𝑖𝑚𝑒
R ----------→ P
∆[𝑅] ∆[𝑃]
Rate = - =
∆𝑇 ∆𝑇

- In above equation the rate expression with respect to

reactant is multiplied by -1 because the final concentration of
reactant is less than initial concentration hence ∆[𝑅] is
negative but rate of reaction never be negative

S.I. Unit of rate of a chemical reaction is MolL-1/Time

Types of Chemical reaction on the basis of rate –
i. Very Fast or Instantaneous reaction- Such type of
reaction completes in fraction of seconds so for such
type reaction the rate not important for us.
- Instantaneous reaction are of ionic nature.
ii. Very Slow reaction – Those reactions which completes in
a very long period of time, their rate is also not
important for us . Rusting of Iron
 iii. Moderate reaction – Such type of reaction completes in a
measurable time interval and the rate of such reaction is
important for us for the industrial as well as biochemical
process
Rate expression for the reactions involving stoichiometry
coefficients:
aA + bB -------→ cC
1∆[𝐴] 1∆[𝐵] 1∆[𝐶]
Rate = - =- =+
𝑎∆𝑇 𝑏∆𝑇 𝑐∆𝑇

Write the rate expression for the following reaction

N2(g) + 3H2(g) -----→ 2NH3(g)

∆[𝑁2] 1∆[𝐻2] 1∆[𝑁𝐻3]

Rate = - =- =+
∆𝑇 3∆𝑇 2∆𝑇

Average Rate and instantaneous rate – The rate of reaction

determined in a measurable time interval is called Average
rate of reaction
R ----------→ P
∆[𝑅] ∆[𝑃]
R ave = - =
∆𝑇 ∆𝑇

Instantaneous rate – The average rate of reaction is called to be

instantaneous rate when 𝜕𝑡 → 0
 R ave = Rint 𝑤ℎ𝑒𝑛 𝜕𝑡 → 0
- To determine the instantaneous rate a tangent is drawn on
concentration time graph and the slope of the graph gives
instantaneous rate
𝜕[𝑅] 𝜕[𝑃]
Slope = - = +
𝜕𝑡 𝜕𝑡

Factors affecting rate of reaction –

i. Concentration of reactant
ii. Pressure (for Gaseous Reactant)
iii. Temperature
iv. Presence of Catalyst
v. Exposer to radiation
 Dependence of rate on Concentration - The concentration
dependent rate law is given as
Rate law – The rate of a chemical reaction is directly
proportional to the concentration of reactant raised to the
power experimentally determined stoichiometry coefficients
For a reaction
A + B ------→ C
Rate α [A]a[B]b => rate = K [A]a[B]b
𝜕[𝑅]
- = K [A]a[B]b
𝜕𝑡

Where K is called rate constant.

a and b are experimentally determined stoichiometry
coefficient that may or may not be equal to the coefficient of
a balance chemical equation.
2A + B2 -------→ 2AB
- Stoichiometry of balanced equation only for reactant – 2 and
1
Rate = k [A][B]1/2
From the rate law – stoichiometry of reaction are 1 and ½ are
experimentally determined
Order of reaction(n) – The sum of the stoichiometry
coefficients used in rate law of a reaction is called order of
reaction .
If rate = K [A]a[B]b order of reaction(n) = (a +b)
Some important facts about order of reaction -
i. Same reaction may have different order with respect to
two reactants but overall order be always same
e.g for the A2 + B2 -------→ 2AB
H2 + Cl2---------→ 2HCl
Rate = K [H2][Cl2]0
- The reaction is of first order with respect to H2
- The reaction is of Zero order with respect to Cl2
- Overall order of the reaction = 1+0 =1
ii. The order of reaction may have negative, positive, Zero
and a fractional value
Q. For a reaction the rate expression is K [A]-1/2 [B] 2/3
What is the order of reaction with respect to A and B
respectively? Also find the overall order of reaction?
Rate Constant (K) – The rate constant K is equal to the rate of
reaction when molar concentration of all the reactant is
unity.
Rate = K when conc. Of all reactant is unity.
 Types of chemical reaction on the basis of order-
i. Zero order reaction – A reaction is said to be of zero
order if its rate is independent from the concentration of
reactant
R ---------→ P
Rate = k[R]o
- That is the quantity of reactant does not affect the rate of
reaction for the zero order reaction
ii. First order reaction – The rate of first order reaction
depends upon the concentration of only one reactant
A + B ---------→ C
Rate = K[A]0[B]
iii. Second order reaction – If the rate of reaction depends
upon the concentration of two reactant then it is of
second order
2R --------→ P
Rate = K[R]2
iv. nth order reaction – If the rate of reaction depends upon
the conc. Of n molecules
nR ---------→ P
rate = k[R]n
Unit of rate constant k :
Rate = k (conc)n k = rate/(conc)n
Unit of K = MolL-1s-1 / (MolL-1)n = Mol1-nLn-1 s-1
Order of reaction Unit of rate constant K
Zero Order Reaction MolL-1s-1
Firs order s-1
Second Order Mol-1Ls-1
Third Order Mol-2L2s-1
4.2
Sol. For the reaction 2A + B ---------→ A2B Rate = K[A][B]2
K = 2.0 x10-6 mol-2L2s-1 [A]int = 0.1 [B] int = 0.2
[A]fin= 0.06 d[A] = 0.06-0.10 = -0.04
Rate = -1/2 d[A]/dt = -d[B]/dt
-1/2 (-0.04)/dt = -d[B]/dt = d[B]= 0.02
[B]fin =0.20-0.02 = 0.18
Rate = K[A][B]2 = 2.0x 10-6 (0.06) (0.18)2 molL-1s-1
= 0.00388 x 10-6 = 3.88 x 10-9 molL-1s-1
4.3
2NH3---------→ N2 + 3H2 rate = k[NH3]0
K = 2.5 x 10-4 mol-1Ls-1 what are the rate of production of N2 and
H2 gas
Rate of decomposition of NH3 = K
Rate = -1/2 d[NH3]/dt = d[N2]/dt = 1/3 d[H2]/dt
d[N2]/dt = K = 2.5 x 10-4 mol-1Ls-1
1/3 d[H2]/dt = K => d[H2]/dt = 3K = 3 x 2.5 x 10-4 molL-1s-1
 4.9 A reaction is first order in A and second order in B. (i)
Write the differential rate equation. (ii) How is the rate
affected on increasing the concentration of B three times?
(iii) How is the rate affected when the concentrations of both
A and B are doubled?
Sol – A + 2B ---------→ Procuct
Rate = k[A][B]2
i. diff. Rate = -d[A]/dt = -1/2 d[b]/dt
ii. if conc of b is increased three times
R1 = k[A][B]2 R2 = k[A][3B]2 = 9k[A][B]2 = 9R1
Determining the order of reaction by initial rate method –
To determine the order of reaction a series of reaction is carried
out keeping the concentration of one reactant constant for one
experiment and so on for the others
Exp [A] [B] R0
1 0.20 0.30 5.07 x 10-5
2 0.20 0.10 5.07 x 10-5
3 0.40 0.05 1.43 x 10-4

Late Rate = K[A]x[B]y

R1= k(0.20)x(0.30)y = 5.07 x 10-5
R2= k(0.20)x(0.10)y = 5.07 x 10-5
R3 = k(0.40)x (0.05)y = 1.43 x 10-4
R1/R2 = (0.30/0.10)y =1
3y = 1 y= 0
R4/R1 = (0.40/0.20)x = 1.43 x 10-4/ 5.07 x 10-5
= (2)x = 0.28 x 10 = 2.8
Xlog2 = log 2.8 => x 0.30 = 0.45
X = 45/30 = 3/2 =1.5
Molecularity – The no. of chemical
species(atoms/molecules/ions) which collide together to
form intermediat/Product is known as molecularity of
reaction
H2 + I2 -------→ 2HI Molecularity = 2
N2 + 3H2 -------→ 2NH3 Molecularity = 4(x)
4HBr + O2 ----------→ 2H2O + 2Br2 Molecularity = 5 (x)
Important points regarding Molecularity of reaction –
i. It helps in understanding the path (mechanism ) of a
chemical reaction
ii. Molecularity never be zero or a fractional no.
iii. The molecularity is a theoretically assigned.
iv. The molecularity of a reaction more than three is not
possible
 Elementary reaction – A reaction which completes in one step
is known as elementary reaction. During elementary reaction
no intermediate is form
N2 + O2 -------→ 2NO
- For elementary reaction both molecularity and order are
same
Complex reaction – A reaction which completes in many
intermediate step is known as complex reaction.
- The molecularity of each intermediate step is different
- The slowest step will be rate determining step. and the order
of the slowest step will be the order of whole reaction.
𝐼−
2H2O2 > 2H2O + O2
Step 1 – H2O2 + I- ------→ H2O + IO- (slow)
Step 2- H2O2 + IO- ----------→ H2O + I- + O2 (fast)
Rate = k[H2O2] [I-]
Both the steps are bimolecular elementary reactions. Species IO-
is called as an intermediate since it is formed during the course of
the reaction but not in the overall balanced equation. The first
step, being slow, is the rate determining step. Thus, the rate of
formation of intermediate will determine the rate of this reaction.
Thus, from the discussion, till now, we conclude the following: (i)
Order of a reaction is an experimental quantity. It can be zero and
even a fraction but molecularity cannot be zero or a non integer.
(ii) Order is applicable to elementary as well as complex reactions
Integrated Rate Equation –
1. Zero Order reaction – A zero order reaction is that whose rate
is independendent from the concentration of reactant.
R ---------→ P
Rate = K[R]0
𝜕[𝑅]
Also Rate = - 𝜕𝑡
𝜕[𝑅]
- = k => 𝜕[𝑅] = −𝑘𝜕𝑡
𝜕𝑡
Integrating both side
∫ 𝜕 [𝑅] = −𝐾 ∫ 𝜕𝑡 => [R] = -kt + C --------(1)
C is called integration constant
At t= 0 , [R] =[R]0 => [R]0 = -kx 0 +C => C = [R]0
Substituting the value of C in equ 1
[𝑅 ]0−[𝑅]
[R] = -kt + [R]0 => k= 𝑡
2. First Order Reaction – For a first order reaction
R -----------→P
Rate = k[R]
𝜕[𝑅] 𝜕[𝑅]
Also Rate = - => =−𝑘𝜕𝑡
𝜕𝑡 [𝑅]
Integrating both side
𝜕[𝑅]
∫ [𝑅] = -k∫ 𝜕𝑡 => ln[R] = -kt + C ------------(i)
𝐴𝑡 = 0 [R] = [R]0
C = ln[R]0 Substituting the value of C in equ(i) We have
 1 [𝑅 ]0 2.303 [𝑅 ]0
ln[R] = -kt + ln[R]0 => k = 𝑡 ln = log
[𝑅] 𝑡 [𝑅]
2.303 [𝑅 ]0
( k= log )
𝑡 [𝑅]
Rate Constant K for the first order decomposition of Gas is
expressed in terms of pressure change as follow
A(g) --------→ B(g) + C(g)
𝜕𝑝𝐴 𝜕𝑝𝐵 𝜕𝑝𝐶
Rate = - = =
𝑑𝑡 𝑑𝑡 𝑑𝑡

Initial pressure P1 0 0
At Time t P1- x x x
Total pressure at time t (Pt) = P1-x +x +x = P1 + x x = Pt-P1
Pressure of A At time t= P1-x = P1- (Pt-P1 ) = 2P1 - Pt
2.303 𝑃1
(K = log )
𝑡 2𝑃1−𝑃𝑡

Half Life of Reaction –(t1/2 ) - The half life of a reaction is the

time where the half of the reactant are consumed or converted to
product .
[𝑅 ]0
At t ½ [R] = 2

Half life of Zero Order reaction

For Zero order reaction
[𝑅 ]0−[𝑅] [𝑅 ]0−[𝑅]
K= t= at t1/2 [R] = [R]0/2
𝑡 𝐾
 [𝑅 ]0
(T1/2 = )
2𝐾

Half life of first order reaction

For first order reaction
2.303 [𝑅]0 2.303 [𝑅]0
K= log t= log at t1/2 [R] = [R]0/ 2
𝑡 [𝑅] 𝐾 [𝑅]
2.303 0.693
T1/2 = log2 = > t1/2 =
𝐾 𝐾

- The half life of first order reaction is independent from

concentration of the reactant.
Q4.8 Show that in a first order reaction, time required for
completion of 99.9% is 10 times of half-life (t1/2) of the reaction.
Solution –
2.303 [𝑅 ]0 2.303 [𝑅 ]0
k= log t= log
𝑡 [𝑅] 𝐾 [𝑅]

At t99.9% [R] = 100-99.9 = 0.1 [R]0 = 100

2.303 [100] 2.303
t99.9% = log [0.1]
= 𝑥 3 (logam = mloga)
𝐾 𝐾

t1/2 = 0.693/K
Now t1/2/t99.9 = (0.693/k) / (2.030x3)/k = 1/10
 t99.9 = 10 x t1/2
4.6 2N2O5(g) ----------→ 2NO2(g) + O2(g)
Exp Total pressure Time (s)
 1 0.5 0
2 0.512 100

2N2O5(g) ----------→ 2NO2(g) + O2(g)

P1 0.5 0 0
Pt 0.5-2x 2x x
Ptotal = 0.5-2x +2x+x = 0.512 => 0.5+x = 0.512 x = 0.512 –
0.500 = 0.01
PN2O5 = 0.5- 2 x 0.012 = 0.476

P1 = 0.5 Pt = 0.512
2.303 𝑃1 2.303 0.5
K= log 2𝑃1−𝑃𝑡 = log
𝑡 100 0.476

=2.303 x 10-2 x log (0.5/ 0.488) = 2.303 x 10-2 (log500- log476)

2.303 x 10-2 (2.6990 – 2.6776) = 2.303 x 10-2 x 0.0214
= 0.0492 x 10-2 = 4.9 x 10-4 s-1.
 Pseudo First order reaction – A reaction which appears to be
bimolecular i.e. of second order but actually follow the firs
order kinetics is called pseudo first order reaction
- In pseudo first order reaction one of the reactant is present in
excess large quantity so as practically its concentration
remains constant throughout the reaction
- During acidic hydrolysis of ester the water is present in large
quantity hence the rate of the reaction depends upon the
concentration of ester only
RCOOR’ + H2O/H+ -----------→ RCOOH + R’OH
Rate = k [RCOOR’]

4.17 During nuclear explosion, one of the products is 90Sr with

half-life of 28.1 years. If 1µg of 90Sr was absorbed in the
bones of a newly born baby instead of calcium, how much of
it will remain after 10 years and 60 years if it is not lost
metabolically.
Sol - All radioactive decomposition follow first ord order
decomposition.
t1/2 = 28.1 yr
[R]0 = 1um [R]10 = ? [R]60 = ?

T1/2 = 0.693/K K = 0.693/ t1/2 = 0.693/28.1 yr-1

= 24.66 x 10-3 yr-1
 K = 2.303/t log [R]0 /[R]
Log[R]0/[R] = k x t / 2.303 = 24.66 x 10-3 x 10 /2.303 =
10.70 x 10-2 = 0.107
Log[R]0 /[R] = 0.107 => [R]0/ [R] = antilog 0.107
= 0.1279 x 101 => 1/[R] = 1.279
[R] = 1/1.279 = 0.78ug
Again Log[R]0/[R] = k x t / 2.303 = 24.66 x 10-3 x 60 / 2.303
= 642.46 x 10-3 = 0.6424
[R]0 /[R] = antilog 0.6424 = 0.4389 x 101 =4.389
[R] = [R]0 1/ 4.389 = 0.227ug