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CHEMICAL KINETICS
Chemical kinetics is the study of the rate of chemical reaction and its factors
Rate of reaction: - It is defined as the change in concentration of any reactant and
product in unit time.
It can be expressed in terms of
a) The rate of decrease in concentration of any one of the reactant i,e.
−∆[𝑅] 𝑑𝑒𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 [𝑅]
Rate of reaction of R = =
∆𝑡 𝑡𝑖𝑚𝑒 𝑡𝑎𝑘𝑒𝑛
b) The rate of increase in concentration of any one of the products i,e.
+∆[𝑃] 𝑖𝑛𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 [𝑃]
Rate of reaction of P = =
∆𝑡 𝑡𝑖𝑚𝑒 𝑡𝑎𝑘𝑒𝑛
Unit of rate of reaction is mol/L/S. In case of gaseous reaction, the unit is atm/s.
Average rate and instantaneous rate of reaction :
Average rate: The change in concentration of reactants or products and time taken
for that change to occur.
𝐷[𝑅] 𝐷[𝑃]
Average rate of reaction, rav = – =+=
𝐷𝑡 𝐷𝑡
Instantaneous rate of reaction: The rate at a particular moment of time of
determination is instantaneous rate. It is obtained when the average rate of the
smallest time interval.
Δ[𝑅]
The instantaneous rate is given by rav = Δ𝑡
𝑑[𝑅] 𝑑[𝑃]
As ∆t → 0 rinst = =
𝑑𝑡 𝑑𝑡
Instantaneous rate can be determined by graphical method, the slope of the tangent
drawn to curve at any instant in the concentration v/s time.

Expression for rate of reaction in terms of reactant and product:-

Consider Hg𝐶𝑙2 → Hg𝐶𝑙2
Where stoichiometric co-efficient of both product and reactants are same.
Δ[𝐻𝑔] Δ[𝐶𝑙2 ] Δ[𝐻𝑔𝐶𝑙2 ]
Then rate of reaction = − =− =
Δ𝑡 Δ𝑡 Δ𝑡

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I.e. the rate of consumption of any of the reactants is same as the rate of formation
of products.But difficulty arises when the stoichiometric co-efficient of substance
involved are different.
e.g.: 𝐻2 + 𝐼2 → 2HI. In this reaction the rate of formation of hydrogen iodide is
2 times the rate of disappearance of either 𝐻2 or 𝐼2 .
To have the same value for rate of reaction, the rate of disappearance of any of the
reactants or the rate of appearance of the product divided by their respective
stoichiometric co-efficient thus,
1 ∆[𝐻𝐼] Δ[𝐻2 ] Δ[𝐼2 ]
The rate of reaction = 2 = =
∆𝑡 Δ𝑡 Δ𝑡
NOTE:- For a gaseous reaction at constant temperature, the concentration is directly
proportional to the partial pressure of the species and hence the rate can also be
expressed as rate of change in partial pressure of the reactants and products
Problem:

Factors influencing rate of reaction:-

• Dependence of rate on concentration
The representation of rate of 1mole in terms of concentration of the reactants is
known as rate law or rate equation or rate expression.
Consider a general equation:-
aA + bB → Cc + dD (a,b,c and d are stoichiometric co-efficient)
Rate ∝ [𝐴]a [𝐵]b
Rate= k[𝐴]a [𝐵]b (where k is called as the rate constant)

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−𝑑(𝑅)
= k[A]a[𝐵]𝑏 This equation is known as differential rate equation
𝑑𝑡
NOTE:- Rate law is a mathematical expression relating the rate of reaction with the
concentration of reaction.
Order of reaction
Order of chemical reaction is defined as “the sum of power of the concentration
terms in the experimentally determined rate equation for the reaction.
For a reaction A+B→C+D
If the experimental rate equation is rate (r) =k[𝐴]1 [𝐵]1
Hence the order is equal to 1+1=2.
• Zero order reaction: - The rate of reaction is independent of concentration of
reactants.
ℎ𝑣
• Example: i) H2 +Cl2 → 2HCl rate (r) =k[𝐻2 ]0 [𝐶𝑙2 ]0 Order = 0+0 =0
𝑃𝑡
ii) 2NH3 → N2 + 3H2 rate (r) =k[2𝑁𝐻3 ]0 Order = 0
• First order reaction:- A chemical reaction in which the rate is directly proportional
to the 1st power of the molar concentration of the reactants.
Example: i) 𝑁2 𝑂5 → 4𝑁𝑂2 + 𝑂2 rate (r) =k[ 𝑁2 𝑂5 ]1 Order = 1
ii) 𝑁𝐻4 𝑁𝑂2 → 2𝐻2 𝑂 + 𝑁2 rate (r) =k[𝑁𝐻4 𝑁𝑂2 ]1 Order = 1
• Second order reaction:- The rate of reaction is directly proportional to the 2nd power
of molar concentration of the reactants.

e.g.: CH3COOCH3 +NaOH→CH3COONa +CH3OH

Rate = K [CH3COOCH3]1[NaOH]1, Order = 1+1 =2
Unit of rate reactant:-
Consider aA + bB → cC + dD
Rate = k [A]a[B]b = a + b = n(Order of reaction)

𝑅𝐴𝑇𝐸 (𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛) 1 𝑚𝑜𝑙/𝐿 1

k =[𝐴] [𝐵]
= ˟ (𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛)𝑛 = = (𝑚𝑜𝑙/𝐿) 𝑛
𝑡𝑖𝑚𝑒 𝑠

Unit of rate constant:-

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Molecularity of a reaction.
“Number of reactants of species,(atoms, ions molecules) taking part in
elementary reaction which must collide simultaneously in order to bring about
a chemical reaction’’ is called as molecularity of a reaction.
Note: Elementary reaction takes place very slowly. And also known as known as
Rate determining step.
Type of molecularity of a reaction:-
1) Unimolecular reaction:- The reaction in which only one reactant species is involved.
e.g.: NH4NO2 → N2 + 2H2O
2) Bimolecular reaction:- The reaction in which simultaneous reaction between two
species. e.g.: 2HI → H2 + I2
3) Trimolecular reaction:- The reaction which involves simultaneous reaction between
three reacting species. e.g.: 2NO + O2 → 2NO2

NOTE: mechanism of reaction:

Decomposition of 𝐻2 𝑂2 catalysed by iodide ion
in alkaline medium.
𝑎𝑙𝑘𝑎𝑙𝑖𝑛𝑒
𝑚𝑒𝑑𝑖𝑢𝑚(𝐼 − )
2H2O2→ 2H2O +O2
The rate equation found to be rate=k[𝐻2 𝑂2 ] is 1st order reaction.
It takes place in two steps:
1. H2O2 +I–→H2O +IO– (slow)
2. H2O2 +IO⁻ →H2O +I +O⁻ (fast)
2H2O2 → 2H2O + O2
In the above mechanism IO‾ is an intermediate. It does not appear in the overall
balanced equation .Thus rate of formation of the intermediate determines the rate of
the reaction
Problems:-
For a reaction, A + B → Product; the rate law is given by, r = k [ A]1/2 [B]2.
What is the order of the reaction?

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1 5
Order of reaction: + 2 = 2 or 2.5 (fractional order)
2
1) The conversation of molecule X to Y second order kinetics if the concentration
(x) is increased to 3 times. How will it affect the rate of formation of Y?
X → Y follows 2nd order reaction
i.e. Rate = k [X]2
If the concentration of X increased 3 times i.e. [X] =3mol/l
Rate = k [3X]2 =9kX2
Thus the rate of reaction increases 9 times, Hence the rate of formation of Y Will be
increased by 9 times

Difference between order of reaction and molecularity of reaction:-

Order of reaction Molecularity of reaction
1) It is the sum of powers of It is the number of reacting species
concentration terms in the rate taking part in an elementary
equation. reaction that collides
simultaneously to bring about the
reaction.
2)It is applicable for both It is applicable only to the
elementary and complex reaction. elementary reaction.

Integrated rate equation:-

I. Integrated rate equation for zero order reaction:
Consider a general zero order reaction
R → 𝑃
Rate = k[R] 0
−𝑑[𝑅]
= 𝑘[𝑅]0
𝑑𝑡
−𝑑[𝑅]
=k 1
𝑑𝑡
d[R]= –kdt
Integrated on both sides,
∫ 1𝑑[𝑅] = − ∫ 𝑘𝑑𝑡
[𝑅] = −𝑘 ∫ 𝑑𝑡
[R]= – kt + C--------------------- (1) [where C is constant of integration]
When t=0 [R] = [[𝑅]0 (where [R]O is initial concentration)
Substitute the above value to equation (1)
[𝑅]0 = – k(0) + C

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[𝑅]0 = C
Substitute the value of c to equation (1)
[R]=– kt + [R] 0 -----------------(2)
kt = [𝑅]0 – [R]
[𝑹]𝟎− [𝑹]
k= this is an expression for rate constant of zero order reaction.
𝒕

Consider the equation( 2) [R] = – kt + [𝑅]0

This is in the form of y=mx+c so a plot [R] / time is a
straight line with
Slope = –k and intercept=[𝑅]0 as follows

II. Integrated rate equation for first order reaction

Consider a general 1st order reaction
R→𝑃
Rate=K[R]1
−𝑑[𝑅]
= 𝑘[𝑅]
𝑑𝑡
−𝑑[𝑅]
=k
𝑑𝑡
𝑑[𝑅]
= – kdt
[𝑅]
Integrated on both sides,
𝑑[𝑅]
∫ = − ∫ 𝑘𝑑𝑡
[𝑅]
𝑙𝑛[𝑅] = −𝑘𝑡 + 𝐶 -------------- (1)
When t=0, [R]=[𝑅]0 (where [R]O is initial concentration)
Substitute the above value to equation 1
𝑙𝑛[𝑅]0 = – k (0) + C
𝑙𝑛[𝑅]0 = C
Substitute the value of c in equation (1)
ln[R] = ―kt + ln [R]0------------(2)
kt = ln[R] ―ln[R]o
[𝑅]
kt = ln [𝑅]𝑜
[𝑅]
kt =2.303log[𝑅]𝑜 [because ln = 2.303log]
𝟐.𝟑𝟎𝟑 [𝑹]
k= log[𝑹]𝒐 ------------- (3) this is 1st order integrated rate equation
𝒕

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If [R]1 and [R]2 are the concentration of the reactants at t1 and t2 respectively then
equation 2 becomes ln[R]1=―kt +ln[R]0-----------------(4)
and ln[R]2=―kt + ln [R]0---------------(5)
(5) – (4) ⇒ ln[R]1−ln[R]2= −kt 1– (−kt2)
[𝑅]
ln [𝑅]1 = k (t2 − t1)
2
1 [𝑅]
k=𝑡 ln [𝑅]1 --------------- (6)
2 −𝑡1 2
But the equation 2 can be written as
ln [R]= −kt + ln[R]0
[𝑅]
ln[𝑅]0 = −kt
Taking log on both sides
[R] = [R]0 e‐kt
From the equation (2)
ln[R] =−kt + ln[R]0

it is clear that a plot of ln[R]/t is a straight line

with a slope = −kt and intercept = ln[R]0

2.303 [𝑅]0 [𝑅]0 𝑘𝑡

Similarly equation (3) k = log or log =2.303
𝑡 [𝑅] [𝑅]

[𝑹]𝟎
it is clear that a plot of log [𝑹] /t is a straight line
𝒌
with slope =
𝟐.𝟑𝟎𝟑

1) Problems:The rate constant of a reaction of zero order in A is 0.0030 mol/l/s.How

long will it take for the initial concentration of A to fall from 0.1m to 0.075m?
[𝑅]0−[𝑅] (0.1−0.075)𝑚𝑜𝑙/𝑙
For zero order reaction t = = =8.3 s
𝑘 0.003𝑚𝑜𝑙/𝑙 𝑠
1
2) The initial concentration of 𝑁2 𝑂5 → 2 𝑁𝑂2 + 𝑂 was1.24×10−2 mol/l a318k.
2 2
The concentration of 𝑁2 𝑂5 after 60 mins was 0.20×10 −2 mol/l. Calculate the rate
constant of the reaction at 318k.

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3).A first order reaction is 80% complete in 90 mins. Calculate the rate constant of
the reaction.
2.303 [𝑅]
[R]0=100 k= log[𝑅]𝑜
𝑡
2.303 100
[R] =100-80=20 = log 20
90𝑚𝑖𝑛
k =? = 0.02558×0.6990
=0.01789min-1
4).A first order reaction is 10% complete in 10 mins. Calculate the time taken for
90% completion of reaction.
2.303 [𝑅 ]0
For 10% k= log [𝑅]
𝑡
2.303 100
[R]0 = 100 k = 10𝑚𝑖𝑛log 90 = 0.0105 min-1
[R] = 100-10 = 90
t = 10min
2.303 [𝑅]0
For 90% k= log
𝑡 [𝑅]
2.303 100
[R] = 100–90 =10 t = 0.0105log 10 = 219.33 min-1
k = 0.0105min-1
5) A 1st order reaction has a rate constant 1.15×10 −3 /s. How long will 5gms of the
reactant take to reduce to 3gms?
2.303 [𝑅]0
t= 𝑘
log [𝑅]
2.303 5𝑔
t = 1.15×10−3log3𝑔
t =2.00× 103 × 0.2219 =443.8s
6) A reaction A products with k=2×10 −2 /s. Calculate the concentration of A
remaining after 100s if the initial concentration of A is mol/l.
2.303 0 [𝐴]
k= log
100𝑠 [𝐴]
2.303 1
2 × 10−2 = log[𝐴]
100𝑠
1 2×10−2 ×100
log[𝐴] = 2.303

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1
log[𝐴] =86.8432× 10−2 = 0.8684
1
=antilog (0.8684)
[𝐴]
[A] = 0.1354mol/l

II. Integrated rate equation for first order reaction in gaseous phase
consider

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Problems:

Half-life of a reaction
Half-life of a reaction is the time in which the concentration of a reactant is reduced
to one half of its initial concentration. It is represented as 𝑡1/2
Half-life of a zero order reaction

Condition: 𝑡1/2 for zero order reaction it is directly proportional to the initial
concentration of the reactant and inversely proportional to the rate constant.

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Half-life of a frist order reaction

1
Condition: 𝑡1/2 for the 1st order reaction t2 is independent of initial concentration of
the reacting species.
Problems:-
1) A 1st order reaction is found to have a rate constant k = 5.5×10 −14 /s. Find the half
life reaction.
0.693 0.693
𝑡1/2 = = 5.5×10−14 /𝑠 = 1.26× 1013 s
𝑘
st
2) A 1 order reaction takes place in 40 mins for 30% decomposition. Calculate the
half-life period of the reaction.
2.303 [𝑅]
k= log [𝑅]0
𝑡
2.303 100
k =40𝑚𝑖𝑛 log 70
k =8.918× 10−3 𝑚𝑖𝑛−1
0.693 0.693
𝑡1/2 = =8.918×10−3 𝑚𝑖𝑛−1
𝑘
= 77.7min
3) Time required decomposing 𝑆𝑜2 𝐶𝑙2 to half of its initial amount in 60mins. If the
decomposition is a 1st order reaction. Calculate the rate constant (k) of the reaction.
0.693 0.693
k= =10𝑚𝑖𝑛
𝑡1/2
−2
= 1.15× 10 min-1
4) Show that in a 1st order reaction, time required for completion of 99.9% is 10
times of half-
life( 𝑡1/2 ) of the reaction

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For a 1st order reaction,

When the reaction is completed 99.9 %
2.303 100
𝑡1 = log100−50
2 𝑘
2.303
𝑡1 = log 2
2 𝑘
2.303
𝑡1 = × 0.3010 -------(1)
2 𝑘
2.303 100
When𝑡99.9% . 𝑡99.9% = log100−99.9
𝑘
2.303 100
𝑡99.9% = log
𝑘 0.1
2.303
𝑡99.9% = 𝑘
3 ----------- (2)

2.303
𝑡99.9% ×3 3
𝑘
= 2.303 = 0.3010 ≈ 10
𝑡1 ×0.3010
2 𝑘
𝒕𝟗𝟗.𝟗%
= 10 or 𝒕𝟗𝟗.𝟗% = 10𝒕𝟏
𝒕𝟏 𝟐
𝟐
Intigrated rate law for the Reactions of Zero and frist order

Pseudo first order reaction:-

A chemical reaction of higher order can be converted into first order reaction by
taking the other reactant except one in a large excess. Such reaction is called pseudo
first order reaction.
𝑑𝑖𝑙𝐻𝐶𝑙
Example: 1)C12H22O11 + H2O → C6H12O6 +C6H12O6
𝑑𝑖𝑙𝐻𝐶𝑙
2)CH3COOH +H2O → CH3COOH +CH3OH
Condition:-If one of the reactants in the reaction is taken in large excess, the order
with respect to that reactant becomes zero.
Problems:-
1) Hydrolysis of C𝐻3 𝐶𝑂𝑂𝐶𝐻3 in aqueous solution has been studied by titerating the
liberated C𝐻3 𝐶𝑂𝑂𝐻3 against NaOH. The concentration of ester at different times is
given below
t /min 0 30 60 90

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[R]mol/l 0.8500 0.8004 0.7538 0.7096

st
Show that it follows a pseudo 1 order reaction as the concentration of
𝐻2 𝑂 remains nearly constant (55 mol/l) during the course of reaction .What is the
value of k in this equation
Rate=k[CH 3 𝐶𝑂𝑂𝐶𝐻3 ] [𝐻2 𝑂]
2.303 [𝑅]
[R]0=0.8500 k= log [𝑅]0
𝑡

2.303 0.8500
When t =30min k= log0.8004 =2.004× 10−3 min-1
30

2.303 0.8500
When t =60 min k= log = 2.002 × 10−3 𝑚𝑖𝑛−1
60 0.7538
2.303 0.8500
When t=90min k= log0.7096 = 2.005 × 10−3 𝑚𝑖𝑛 −1
90
Average value of k = 2.004× 10−3 min–1
But rate = k [CH3COCH3] [H2O]
i,e. r = k[CH3COCH3] where k = k1 [H2O] (because constant)
𝑘 2.004×10−3 𝑚𝑖𝑛−1
k1 = = = 3.64× 10−5 𝐿𝑚𝑖𝑛−1 /𝑚𝑖𝑛
[𝐻2 𝑂] 55 𝑚𝑜𝑙/𝑙
Temperature dependence of the rate of the reaction:-
“The ratio of rate constant of a reaction at a particular temperature to the rate constant
of the reaction at a temperature 10 degree lower is called temperature co-efficient
of the reaction”.
𝑘𝑇 +10
i.e. Temperature co-efficient of the reaction = 𝑘𝑇
The rate of a reaction doubles to triples for every 100 lower in temperature.
The physical justification for the effect of temperature on the rate of reaction was
given by Arrhenius. According to Arrhenius,
H 2 + I 2 → 2HI
Reaction is possible only if a molecule of hydrogen collides with molecule of
iodine i.e.

This collision leads to the formation of an unstable intermediate called activated

complex. It exists for a very short time and then breaks up to form two molecules of
HI and the energy required to form this intermediate (activated complex ) is called
activation energy(Ea.). During the decomposition of activated complex some energy
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is released. Thus heat of reaction (∆H = HP – HR) depends on the nature of reactants
and products.
From the graph it is evident that all the reacting
molecules do not have the same kinetic energy at a
particular temperature. However fraction of
molecules having a particular kinetic energy remains
constant at a particular temperature.

The peak of the curve represents the kinetic energy

possess by the fraction of molecules.
Kinetic energy corresponding to this peak is called
most probable kinetic energy. i.e. kinetic energy of
maximum fraction of molecules

Increasing the temperature of the

substance increases the fraction of
molecules which collide with energies
greater than Ea. So it is clear that, in the
curve at (t+10) the area showing the
friction of molecules having energy
equal to or greater than Ea. gets doubled
leading to doubling the rate of reaction.
Quantitatively the effect of temperature on the rate of reaction is given by
Where A is Arrhenius factor or frequency factor
also called pre-exponential factor, R is gas constant, Ea is energy of activation
measured in joule /mole
𝐸𝑎
The factor 𝑒 −𝑅𝑇 corresponds to the fraction of molecules that have
Kinetic energy > Ea
Taking log on both sides to equation 1
𝐸𝑎
lnk = ln[A,𝑒 −𝑅𝑇 ]
𝐸𝑎
lnk = lnA + ln𝑒 − 𝑅𝑇
𝐸𝑎
ln k = lnA – lne
𝑅𝑇

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𝐸𝑎
ln k = – + lnA
𝑅𝑇
The plot of lnk verses 1/t gives a straight line,

Thus it has been found from Arrhenius equation that

increasing the temperature or decreasing the Ea will
result in an increase in the rate of reaction and an
exponential
increase in the rate constant
𝐸𝑎
Slope = – and intercept = lnA
𝑅
𝐸𝑎
At temperature T1, ln k1 = – + lnA --------------(3)
𝑅𝑇1
𝐸𝑎
At temperature T2, , ln k2 = – + lnA --------------(4)
𝑅𝑇2
k1 and k2 are the value of rate constant at temperature T1 and T2

Note: Fraction of molecule having energy equal or greater than Ea is given by

𝑬𝒂
ln x= – 𝑹𝑻
1) Problem: The rate of chemical reaction doubles for an increase in 10K in absolute
temperature from 298K. Calculate the Ea.
𝑘 𝐸 1 1
Solution: log 𝑘1 = 2.303𝑅
𝑎
[𝑇 – 𝑇 ]
2 1 2
2 𝐸𝑎 𝑇2 −𝑇1
log 1 = 2.303×8.314 [ 𝑇 𝑇 ]
1 2

𝑎 𝐸 308−208
log 2 = 19.147 [ (298)(308)]
𝑎 𝐸 10
0.3010 = 19.147 [ 91784]
0.3010×19.147×91784
Ea = = 52.6 kJ / mol
10
2) The Ea for the reaction 2H𝐼(𝑔) → 𝐻2 (𝑔) + 𝐼2 (𝑔) is 209.5 kj/mol at 581K.
Calculate the fraction of molecules of reactants having energy equal to or
greater than Ea.
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Fraction of molecules having energy equal to or greater than Ea

𝑬𝒂
lnx = – 𝑹𝑻
209.5×103
log x = – 2.303×8.314×581
log x = – 18.8323
x = antilog (– 18.8323)
x = 1.471 × 10−19
3) The rate constant of a reaction at 500K and 700Kare 0.02s-1 and 0.07s-1 calculate
the Ea and A
𝐾 𝐸 𝑇2 −𝑇1
log 𝑘2 = 2.303×𝑅
𝑎
[ ]
1 𝑇1 𝑇2
0.07 𝑎𝐸 700−500
log 0.02 = 19.147 [(700)(500) ]
𝐸 200
log (7× 10−2 ) –log (2× 10−2 ) =19.147
𝑎
[350000]
𝐸𝑎× 200
1.1549 –1.6989 = 6701450
6701450×0.544
Ea = = 18230.8J
200
𝐸𝑎
k = A 𝑒 − 𝑅𝑇
18230.8
0.02 = A 𝑒 − 8.314×500
0.02
A = 0.012 = 1.61

4) The 1st order rate constant for the decomposition of C2H5I by the reaction
C2H5(g) → C2H4(g) + HI(g) at 600K is 1.60 × 10−5 s-1 its energy of activation
of 209 kj/mol .calculate the rate constant of the reaction at 700K

𝐾 𝐸 𝑇2 −𝑇1
log 𝑘2 = 2.303×𝑅
𝑎
[ ]
1 𝑇1 𝑇2
𝐸𝑎 700−600
log k2 = log k1+ 2.303×8.314 [ (600)(700)]
209000
log k2 = log (1.60 × 10−5 )+ 2.303×8.314
log k2 = – 4.796 + 2.599 = – 2.197
k2 = antilog (–2.197) =6.36 × 10−3 s-1

Effect of catalyst:-
A catalyst is a substance which alters the rate of reaction without itself undergoing
any change in mass and chemical composition.
𝑚𝑛𝑜2
e, g. 2KClO3 → 2KCl + 3O2

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According to intermediate complex theory, a catalyst participates in a chemical

reaction forming temporary bonds with the reactants resulting in an intermediate
complex. This has a stationary existence and decomposes to yield products and the
catalyst.
It is believed that catalysis provides an reaction mechanism by reducing the E a
between reactants and products and hence lowering the potential energy.
A catalyst does not alter Gibbs energy of
reaction.
It catalysis the spontaneous reaction but
does not catalyse the non-spontaneous
reactions. Catalyst also does not change
the equilibrium constant of a reaction
rather it helps in attaining the equilibrium
faster
Collision theory of chemical reactions:-
. According to the kinetic theory of gases, a chemical reaction taking place , the
reactant molecules must collide with each other.
“The number of collisions per second, per unit volume of the reaction mixture’’
is known as collisions frequency (Z).
Consider bimolecular elementary reaction,
A + B → Products

(Where Z 𝐴𝐵 is the collision frequency of reactants)A and B and 𝑒 −𝐸𝑎/𝑅𝑇 𝑖𝑠 Fraction

of molecules with energies equal or greater than Ea )
For effective collisions, the normal reacting molecules must possess enough energy
to overcome the intermolecular repulsion i.e. “the minimum energy that the reacting
molecules must possess in order to form products is called as threshold energy of
reaction and the molecules possessing the required threshold energy called
activated molecules”.
For example: Formation of 𝐶𝐻3 𝑂𝐻 from bromo-ethane depends upon the orientation
of reactant molecules.

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The proper orientation of reactants molecules lead to bond formation. Whereas

improper orientation makes them to simply bounce back and no products are formed
to take into consideration orientation factor a new factor probability or steric or
orientation factor P.

Limitations of collision theory:-

1) Collision theory takes into consideration when both activation energy and proper
orientation of the reacting molecules for effective collisions and hence the rate of
reaction.
2) The collision theory treats reacting particles as hard sphere and does not consider
the structural aspects of the particle.

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