Chemical Kinetics

Chemical Kinetics
Prepared by
K.Rajeswar Reddy. M.Sc, B.Ed.
Qualified in NET,GATE & SET.
Faculty in IIIT Srikakulam, RGUKT.

K.Rajeswara Reddy Faculty in RGUKT Chemical kinetics
CHEMICAL KINETICS
 Chemical Kinetics is a branch of chemistry that deals with the study of
the rate of reaction, factors influencing the rate of reactions and
reaction mechanism.
 It doesn’t deals with the spontaneity or feasibility of a chemical reaction
 Actually, thermodynamics deals with the feasibility of chemical
reactions.
Rate of reaction:
The decrease in the concentration of reactants or increase in the

concentration of products in a particular time interval is called “Rate of
reaction”.
𝑑𝑒𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 𝑡ℎ𝑒 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

Rate =
𝑇𝑖𝑚𝑒 𝑖𝑛𝑡𝑒𝑟𝑣𝑎𝑙
𝑖𝑛𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 𝑡ℎ𝑒 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠

=
𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑡ℎ𝑒 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 (𝑜𝑟) 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠

=
Rate = ∆𝑋
∆𝑇
[Average Rate of reaction]
𝑑𝑋
Rate = [instantaneous rate of reaction]
𝑑𝑡
2
Expressions of rate of reactions:
1) A −−→ B
−𝑑 [𝐴] 𝑑 [𝐵]
Rate (r) = =
𝑑𝑡 𝑑𝑡
2) A + B −−→ C
−𝑑 [𝐴] −𝑑 [𝐵] 𝑑 [𝐶]
Rate (r) = = =
𝑑𝑡 𝑑𝑡 𝑑𝑡
3) n1A + n2B −−→ m1C + m2D

1 −𝑑 [ 𝐴 ] 1 −𝑑 [𝐵] 1 𝑑 [𝐶 ] 1 𝑑 [𝐷]
Rate (r) = [ ] = [ ]= [ ]= [ ]
𝑛1 𝑑𝑡 𝑛2 𝑑𝑡 𝑚1 𝑑𝑡 𝑚2 𝑑𝑡
3
Here,
−𝑑 [𝐴]
= rate of disappearance of A
𝑑𝑡
−𝑑 [𝐵]
= rate of disappearance of B
𝑑𝑡
𝑑 [𝐶 ]
= rate of formation of C
𝑑𝑡
𝑑 [𝐷]
= rate of formation of D
𝑑𝑡
For example:
a) CO + NO2 −−→ CO2 + NO

−𝑑[𝐶𝑂] −𝑑[NO2] 𝑑[CO2] 𝑑[NO]
Rate (r) = = = =
𝑑𝑡 𝑑𝑡 𝑑𝑡 𝑑𝑡
b) 2H2O2−−→ 2H2O + O2
1 –𝑑[𝐻2 𝑂2 ] 1 𝑑[𝐻2 𝑂] 𝑑[𝑂2 ]

Rate (r) = [ ]= [ ]=
2 𝑑𝑡 2 𝑑𝑡 𝑑𝑡
c) H2 + I2 −−→ 2HI
–𝑑 [ 𝐻2 ] –𝑑 [ 𝐼2 ] 1 𝑑[HI]
Rate (r) = = =
𝑑𝑡 𝑑𝑡 2 𝑑𝑡
d) 2N2O5 −−→ 4NO2 + O2
1 –𝑑[𝑁2 𝑂5 ] 1 −𝑑[NO2] 𝑑[𝑂2 ]

Rate (r) = [ ]= [ ]=
2 𝑑𝑡 4 𝑑𝑡 𝑑𝑡
Units of rate:
Since,
𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑡ℎ𝑒 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛
Rate of reaction =
𝑇𝑖𝑚𝑒 𝑖𝑛𝑡𝑒𝑟𝑣𝑎𝑙 Units of concentration is “moles/liter”
Units of rate = [(moles/ liter) / (sec)]

Units of time is “second”
= mole.lit-1. sec-1
4
 However, In gaseous reactions, when the concentration of gases is

expressed in terms of their partial pressures, then units of rate equation
will be atm.sec-1
 The units of rate of reaction may be expressed as,
mol. L-1 .sec-1,
mol.L-1 .min-1,
mol.L-1 .h-1,
mol.L-1 .day-1
mol.L-1 .year-1
Rate law (Rate Equation):
 Representation of rate of a reaction in terms of concentrations of

reactants is known as rate law. It is also called as rate equation or rate
expression.
 According to law of mass action, the rate of a chemical reaction is
directly proportional to the product of molar concentration of reactants.
 It is proposed by Gold burg and Waage.
Examples:
1) A−−→ B
Rate α [A]
Rate = k [A]
2) 2 A + B −−→ C + D
Rate α [A] 2[B]
Rate = k [A] 2 [B]
5
2) a A + b B−−→ c C + d D
Rate α [A] a [B] b
Rate = k [A] a [B] b
Units of rate constant:
n A  products
Rate = K [A]n
K = rate / [A]n
K = (dx/dt) / [A] n
K = {[(mol/lit)1.Sec-1 ]/ [(mol/lit)n]}
K = litn-1. Mol1-n.sec-1
Factors influencing the rate of reaction :

The rate of reaction depends on following factors. They are
1) Concentration of reactants
2) Nature of reactants
3) Temperature
4) Catalyst
5) Light
6
1.Concentration of reactants:
According to law of mass action, the rate of a reaction is directly

proportional to the product of molar concentration of reactants.
r αC
Where, C = molar concentration of reactants,
r = rate of reaction
So, the rate of a reaction generally increases with increase in the

concentration of reactants.
Example:
When Zn pieces are added to dil.HCl, chemical reaction takes place

slowly and liberates hydrogen gas. But, the same reaction is rapid by
concentration HCl.
Zn + dil.HCl −−→ ZnCl2 + H2 [slow]
Zn + conc.HCl −−→ ZnCl2 + H2 [fast]
2. Nature of Reactants:
(a) Physical State of reactants:
The decreasing order of rate of reaction based on the physical

state is
Gases>Liquids>Solids
7
(b) Physical size of the reactants:
Among the solids, rate increases with decreases in the particle

size. In powered state, rate of reaction is maximum. Because, in
powdered state, surface area is maximum.
The rate of reaction increases as surface area of the reactants

increases.
Example:
“Mg” powder reacts with dil.H2SO4 more rapidly than “Mg”

ribbon.
(c) Chemical nature of reactants:
Reactions between ionic substances take place much faster

than the reactions occurring between covalent substances. Because,
in ionic reactions, there is no breaking and forming of bonds.
NaCl + AgNO3−−→ NaNO3 + AgCl
The reactions between covalent molecules involving the

breaking and making of covalent bonds.
H+
C2H5OH + CH3COOH → CH3COOC2H5 + H2O
Reactions which involve lesser bond rearrangements are rapid at

room temperature than those which involves greater bond rearrangements.
8
Here,
Reaction A involves breakage of 6 bonds and formation of 6 bonds. Reaction B

involves breakage of 8 bonds and formation of 8 bonds. So, reaction A is faster
than Reaction B.
3. Effect of temperature:
 The rate of a reaction increases with increase in the temperature.

 For most of the reactions for every 10 0c rise of temperature, generally
doubles the rate of the reaction.
 With the increase of temperature the average kinetic energy of
molecules increases, therefore velocity of the molecules increases.
Hence number of collisions between the molecules increases and then
rate of reaction increases.
9
Example:
The reaction between Zn and HCl can be performed at two different

temperatures 293 K and 308 k. It will be found that the volume of hydrogen
formed during the same interval of time will be more at 308 K than at 293 K.
The rate of reaction is directly proportional to the temperature. Arrhenius

provided its physical justification and interpretation.
Where,
K = rate constant
A = Arrhenius factor or frequency factor
e = exponential factor
Ea = Activation energy
R = gas constant
T = Temperature
Now,
Apply ln on both sides
10
ln K = -Ea/RT + ln A
𝐸𝑎
log k = − + log A
2.303 R T
At temperature T1
Ea
log k1 = − + log A  equation 1
2.303 R T1
At temperature T2
Ea
log k2 = − + log A  equation 2
2.303 R T2
Equation 2 – equation 1
Ea Ea
log K2 – log K1 =[− + log A ]−[− + log A ]
2.303 R T2 2.303 R T1
Ea 1 1
=[ ][ – ]
2.303 R T1 T2
K2 Ea T2 – T1
log = [ ]
K1 2.303 R T1T2
Logarithmic Arrhenius equation is
Ea
log10K = log10A –
2.303 R T
Ea
log K = – + log A
2.303 R T
Ea
log K = – (1/T)+ log A
2.303 R
The above equation is in the form of y = mx + C.
11
If we draw a graph between log K verses 1/T, we will get the graph shown
below.
4. Effect of catalyst:
 Catalysts are substances which alter the rate of reaction without

themselves undergoing any overall chemical change.
 Some catalysts are used to Speed up the reaction.
 Some catalysts are used to slow down the reaction
Presence of positive catalyst:
Positive catalyst increases the rate of reaction by decreasing the activation

energy.
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Example:
In the Habour process i.e, manufacture of ammonia, iron(Fe) is used as a

catalyst and it enhances the rate of this reaction.
𝐹𝑒
N2 + 3 H2 → 2 NH3
Presence of negative catalyst:
Negative catalyst decreases the rate of reaction by increasing the activation

energy.
Example:
In the decomposition of hydrogen peroxide, glycerol is used as negative

catalyst.
13
5. Effect of light:
The chemical reactions which are influenced by light are called photochemical
reactions. In photochemical reactions, rate is directly proportional to the
intensity of absorbed light.
r α I absorption
ℎѵ
Ex: A → B
rαI
Examples are photosynthesis and photography.
 Other examples are:

𝑆𝑢𝑛𝑙𝑖𝑔ℎ𝑡
H2 + Cl2→ 2HCl
𝑙𝑖𝑔ℎ𝑡
2AgCl → 2Ag + Cl2 (used in photography)
CO2 + Cl2→ COCl2 (phosgene)
SO2 + Cl2→ SO2Cl2 (sulphuryl chloride)
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Elementary reactions:
The reactions which completes in a single step are called “Elementary
reactions”.
Ex: 1) A → B
2) A + B → Products
Complex reactions:
Those reactions which proceeds in more than one individual steps are
called “complex reactions”.
Ex: 1) A → Products
𝑘1
Mechanism: A → B
𝑘2
B → C
𝑘3
C → Products
Overall reaction: A → Products
Molecularity of a reaction:
 The number of reactant molecules that are involved in the elementary
reaction is called molecularity of the reaction.
 The number of molecules that are involved in the rate determining step
of complex reaction is called molecularity of the reaction.
 Rate determining step: The slowest step in the mechanism of complex
reaction is called Rate determining step.
 Molelcularity is always a +ve whole number (1,2,…). It is never negative
or fractional or zero.
 Molecularity can be determined from the reaction mechanism only. i.e,
theoretically.
 Molecularity cannot be greater than three because more than three
molecules may not mutually colloide with each other.
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16
Order of a reaction:
It is defined as the sum of powers of concentration terms in the Rate law.
Ex:
Order of such a reaction = x + y
Ex:
Order = 1 + 2 = 3
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 It can be determined experimentally

 Order may be a whole number or a fractional number
 It may become zero.
 From the study of the kinetics of many simple reactions, it is observed

that for a large number of reactions, the molecularity and order are
same.
Ex:
Difference between Molecularity and Order:
Molecularity Order
1. It is the number of molecules that 1. It is the sum of powers of conc.
are involved in the Rate determining terms in rate law.
step of the mechanism.
2. It can be determined from the 2. It can be determined
Reaction mechanism. i.e theretically. experimentally.
3. It is always a Positive whole 3. It may be a whole number or a
number. fractional number
4. It never becomes zero. 4. It may become zero.
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Pseudo order reactions:

Reactions whose actual order is different from that expected using rate law
expression are called “Pseudo-order reactions”.
Water is taken in excess; therefore, its concentration may be taken constant.

The reaction is, therefore, Pseudo first order reaction.
19
Zero Order reactions:

A reaction in which the rate of reaction is independent of the concentration of the reactants is called
zero order reactions.
A → Products
r = k [A]0
r=k
A → Products
rate = dx/dt = -d[A]/dt = k0[A]0
rate = k0
Initial concentration of reactants = a
Concentration of reactants remaining after time ‘t’ = a – x
Concentration of reactants consumed in time ‘t’ = x
-d[A]/dt = k0
- d[A] = k0dt
On integration
- {(a-x) –a} = k0 (t-o)
a – (a-x) = k0 t
k0 = {a-(a-x)} / t
k0 = x / t
20
Characteristics of zero order reactions:

Units of zero order rate constant:
K0 = x / t
= [moles / lit] / time
= mole. lit-1.sec-1
Half life: (t1/2)
The time required to consume half of the initial concentration of reactants is called half life.
If t =t1/2 , then x = a/2
K0 = x / t
K0 = (a/2) / (t1/2)
t1/2 = a / 2K0
Evolution of K:
A plot of x against t will yield a straight line passing through the origin. The slope of this
straight line is K.
Ex:
All Photochemical reactions.
21
First order reaction:

A → products
r α [A] 1
r = k1[A]1
- d[A]/dt = k[A] 1
dx/dt = k1(a-x)
- d[A]/dt = k1[A]1
-d[A]/[A] = k1dt
On integration,
22
Units of first order rate constant (K 1):

According to first order rate equation
23
Examples:
1. Decomposition of H2O2 in aqueous solutions.
2. Inversion of cane sugar.
Half life:
24
Evaluation of K1:
The first order rate constant can be evaluated by two methods.

a) By means of first order reaction:
Since the initial concentration with which reaction is started is known, by

determining the conc. of the reactant at different time intervals (t), K1 can be
easily calculated by putting these values in first order reaction. The calculated
value of K1 at different times remains the same; (an average value is taken
from the final calculation of k1).
25
Note:
 All natural and artificial radioactive decay of unstable nuclei takes place
by first order kinetics.
26
Second order reactions:
a) When concentrations of both reactants are equal or two molecules of the

same reactants are involved in the change, i.e.,
A + B → Products (or) 2 A → Products
b) When the initial conc. of the two reactants are different, i.e,
A + B → Products
Units:
Half life:
27
Third Order reactions:
3A → products (or) A + B + C → Products
Units:
lit2.mol-2.sec-1
Half life:
Methods to Determine Order of a Reaction:

 Order of a reaction can be determined by the following methods.
1. Integration method (or) Hit and Trial method

2. Half life method
3. Graphical method
4. Initial Rate method
5. Van’t Hoff differential method
6. Ostawald’s method of isolation.
28
1. Integration method (or) Hit and Trial method:
The Values of a (initial concentration), a-x (concentration after t) are

determined for a number of values of t. These values are then substituted in
the different integrated rate equations (i.e, zero, first, second, third order
reactions). The equation which gives a constant value of “K” decides the order
of the reaction.
This is illustrated by the following example
Example:
The following results were obtained for the dissociation of H 2O2
Solution:
The initial concentration, a =46.5
29
The values of k are constant. Hence the reaction is first order.
2. Half life method:

For zero order reaction (t1/2) = [A0] / 2 K0
For first order reaction (t1/2) = 0.693 / K1

In general, for a reaction of order n,
30
Only for the first order reaction t1/2 is independent of the initial concentration
of the reactant. This relation can be used to determine the order of a reaction.
A reaction is carried out at two different initial concentrations of a reactant

[A], that is [A] 0.1 and [A]0.2 and the respective t1/2 values (t1/2)1 and (t1/2)2 are
obtained . The order of the reaction can be calculated as follows.
Applying log on both sides
Where n is the order of reaction and thus can be calculated by knowing the
values of [A]1, [A]2, (t1/2)1, (t1/2)2.
31
3. Graphical Method:
The concentrations of the reactants are determined at different intervals of

time. Then, a graph is plotted between concentration and time. From the
resulting plot the instantaneous rates are determined by drawing tangents to
curve and then calculating their slopes.
The reaction rates so obtained are plotted against concentrations raised to

various powers. That is rates are plotted against [C] 1, [C]2, and [C]3 ….. [C]n, n
(n need not be intergral numbers). From the nature of the plots, the order of
the reaction can be judged.
32
For a zero order reaction the rate will not vary with concentration and the
plot will be a line parallel to the time axis.
If the reaction displays any other order, then the plot of rate against
concentration raised to the appropriate order will be linear which obeys the
relation, Y=mx. The slope m gives the rate constant K of the reaction.
4. Initial Rate Method:
This method is used for reactions where more than one reactant species are
involved. Initial rates of the reaction are determined by varying the
concentration of only one reactant while keeping the concentration of other
reactants constant. Initial rate of reaction corresponds to the rate at the start
of the reaction. The rate is calculated over the first smallest possible time
interval. This calculation is done by numerically.
The sum of the individual orders with respect to each reactant gives the order
of the reaction.
33
Illustration:
34
5. Van’t Hoff differential method:
In general, r α C n
r= kC n
For two different concentrations C 1 and C2, the rates r 1 and r 2 will be given by
r 1 = k C1 n
r 2 = k C2 n
on taking log, we get
log r1 = log k + n log c1
log r2 = log k + n log c2
log r2 – log r 1 = n log c2 – n log c1
n = (log r 2 – log r1) / (n log c2 – n log c1)
Where n = order.
The values of r 1 and r2 are evaluated by plotting concentration verses time graphs
corresponding to c1 and c2 concentrations.
6. Ostwald’s isolation method:
This method is applicable for reactions involving two more reactants. In this method, the
experiment is carried out for a number of times, each time taking all the reactants, except
one in excess. The reactant which is not taken in excess is said to be isolated. The kinetics of
the reaction then gives the order of the reaction with respect to the isolated reactant. The
orders found for the different reactants are then added up to get overall order of the
reaction.
Consider a general reaction;
Suppose we isolate A by taking B and C in large excess and get the order of the reaction
with respect to A (say p). similarly, we isolate B by taking A and C in excess and isolate C by
taking A and B in excess and get order with respect to B and (say q) and C (say r)
respectively. Overall order of the reaction n = p + q + r.
35
Collision theory:
 According to this theory, the reactant molecules are assumed to be hard
spheres and reaction is postulated to occur when molecules collide with
each other.
 The number of collisions per second per unit volume of the reaction
mixture is known as collision frequency (Z).
For a bimolecular elementary reaction
Rate of reaction can be expressed as
Here ZAB represents the collision frequency of reactants, A and B.

Comparing the above equation with Arrhenius equation, we can say that A is
related to collision frequency.
Postulates collision theory:

1. Collisions must occur between reactant molecules during a chemical
reaction, without collisions between reactant molecules, no reaction takes
place.
2. All collisions do not lead to form products. Only some collisions give
products. These collisions are called fruitful collisions.
3. In order to form products reactant molecules must possess some minimum

amount of energy called “Threshold energy” (ET).
36
4. Under ordinary conditions most of the molecules are having energy less than threshold
energy. These molecules are called Normal molecules.
5. The additional energy supplied to the normal molecules to attain threshold energy is
called Activation energy (Ea).
6. Activation energy Ea = Threshold energy – Average energy
Ea = ET - ER
7. Reactant molecules with energy equal to threshold energy (Activated molecules) form
products.
8. Greater the activation energy E a, lower is the rate of the reaction.
9. The fraction of the activated collisions amongst the total collisions is very small.
37
Activated complex theory (or) The transition state theory:

 According this theory the reactant molecules are not directly converted
into products but they are first transformed into activated complex or
transition state.
 The activated complex subsequently breaks up to produce the products.
 The formation of activated complex and the course of reaction can be
understood by considering the following reaction;
 The additional energy required by the reactant molecules to form the

activated complex is called activation energy.
 The life span of an activated complex is very small. Thus, the activated
complex breaks either into reactants again or new substances, i.e.,
products.
38
 The energy changes during exothermic and endothermic reactions

versus the progress of the reaction are shown in below figure.
Exothermic Reactions Endothermic Reaction
ΔH = Ep - ER ΔH = Ep - ER
ΔH = - Ve ΔH = + Ve
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 In reversible reactions,
40
Arrhenius equation: (Calculation of Activation Energy):

 Arrhenius proposed one equation which gives relation among rate
constant (k), T and Ea.
Taking log on both sides
 The value of Ea can be evaluated by plotting a graph between log K and

1/T. The graph will be a straight line whose slope is equal to –
Ea/2.303R. From the slope Ea values can be determined.
Now let K1 and K2 are the rate constants at temperatures T1 and T2

respectively,
Subtract equation 3 from 4
41
Thus activation energy of a reaction can be determined from the above

equation by knowing the values of the constants K 1 and K2 at temperatures
T1and T2.
42
Catalyst:
Catalyst is a chemical substance that increases or decreases the rate of a
reaction by providing an alternate path of lower or higher activation energy.
Catalysis:
Catalysis is a process in which the rate of a chemical reaction is either
increased or decreased by means of a catalyst.
Ex: When oxygen is prepared by heating potassium chlorate the reaction needs strong
heating and even then it is slow. On the other hand, if potassium chlorate is mixed with a
small amount of manganese dioxide and then heated, oxygen starts evolving at a lower
temperature and with a rapid speed. After the reaction, manganese dioxide is recovered in
almost the same amount in which it is added. Such substance, like manganese dioxide in the
present case, which increases the rate of a chemical reaction without itself being
permanently changed is called a catalyst or a catalytic agent. The catalyst is written over
the arrow in the chemical equation, example
Characteristics of Catalyst:
 A small quantity of catalyst in milligrams is sufficient to maintain the reaction at
proper rate.
 The composition of the catalyst remains same at the end of the chemical reaction.
 A catalyst cannot initiate an impossible reaction, it just increases or decreases the
rate of reaction.
 Catalysts that fast up the reaction are called Positive catalysts.
 Catalysts that slow down the reaction are called negative catalysts.
 Substances that increase the activity of catalysts are called promoters.
 Substances that decrease the activity of catalysts are called inhibitors.
 Substances that deactivate catalysts are called catalytic poisons.
Ex: For instance, in the reduction of ethyne to ethene, the catalyst is

palladium (Pd) partly “Poisoned” with lead (II) acetate [Pb(CH3COO)2]. If the
deactivation of the catalyst is not done the ethene produced will be further
reduced to ethane.
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Types of Catalysis:
 Catalysis can be broadly classified into two types.
1. Homogeneous catalysis
2. Heterogeneous catalysis
Homogeneous catalysis:
In this catalysis the reactants & catalyst are in the same phase.
Ex:
1. Oxidation of SO2 in presence of NO catalyst
2. Hydrolysis of sugarcane solution in the presence of dilute sulphuric acid.
3. Formation of diethyl ether from ethyl alcohol using concentrated sulphuric

acid as catalyst.
4. Hydrolysis of esters in the presence of H 2SO4 catalyst.
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Heterogeneous catalysis:
In this catalysis the reactants & catalyst are present in different phase.
Ex:
1.
2.
 There are two important aspects of solid catalysts are (i) activity and
(ii) selectivity.
(i) Catalytic activity:

The catalytic activity of the catalyst depends on the strength of binding of the
reactant on the surface of the catalyst. It is observed that the metals of group
7,8 and 9 of the periodic table have maximum activity.
(ii) Selectivity:
The catalyst is specific in its reactivity
Ex: 1. the reaction of CO with H2 yields different products when different

catalysts are used i.e.
45
Ex: 2. the reaction of acetylene C2H2 with H2 results in different products,

ethane and ethylene, when different catalysts are used.
Zeolites:
46
Enzyme Catalysis:
 Enzymes are macromolecules, usually proteins, produced in living

systems, which act as catalyst in physiological reactions.
 The striking characteristics of enzymes are their catalytic power and
specificity.
 Enzymes have immense catalytic power; they accelerate reactions by
factors of at least a million.
 Most reactions in living systems do not occur at perceptible rates in the
absence of enzymes.
 A simple reaction like hydration of CO2 is catalyzed by the enzyme
carbonic anhydrase.
 The transfer of CO2 from tissues into the blood would be very slow in
the absence of this enzyme.
 The enzyme can hydrate 105 molecules of CO2 per second, which is 10 7
times faster than the uncatlysed one.
 Enzymes are highly specific. An enzyme usually catalyses a single
chemical reaction or a set of closely related reaction.
Ex: Urease catalyses the hydrolysis of urea only.
Other examples of enzyme catalyzed reactions are as follows:
47
Catalysts in industry:
The phenomenon of catalysis has made tremendous revolution in chemical

industries. Some of the important industrial processes catalyzed by different
catalysts are summarized below.
48

Chemical Kinetics

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Chemical Kinetics

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Chemical Kinetics

K.Rajeswar Reddy. M.Sc, B.Ed.

Qualified in NET,GATE & SET.

Faculty in IIIT Srikakulam, RGUKT.

The decrease in the concentration of reactants or increase in the

𝑑𝑒𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 𝑡ℎ𝑒 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

𝑖𝑛𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 𝑡ℎ𝑒 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠

𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑡ℎ𝑒 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 (𝑜𝑟) 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠

Expressions of rate of reactions:

3) n1A + n2B −−→ m1C + m2D

a) CO + NO2 −−→ CO2 + NO

1 –𝑑[𝐻2 𝑂2 ] 1 𝑑[𝐻2 𝑂] 𝑑[𝑂2 ]

d) 2N2O5 −−→ 4NO2 + O2

1 –𝑑[𝑁2 𝑂5 ] 1 −𝑑[NO2] 𝑑[𝑂2 ]

Units of rate = [(moles/ liter) / (sec)]

 However, In gaseous reactions, when the concentration of gases is

Rate law (Rate Equation):

 Representation of rate of a reaction in terms of concentrations of

Rate α [A] 2[B]

Rate = k [A] 2 [B]

Rate α [A] a [B] b

Rate = k [A] a [B] b

Units of rate constant:

Factors influencing the rate of reaction :

According to law of mass action, the rate of a reaction is directly

Where, C = molar concentration of reactants,

So, the rate of a reaction generally increases with increase in the

When Zn pieces are added to dil.HCl, chemical reaction takes place

Zn + dil.HCl −−→ ZnCl2 + H2 [slow]

Zn + conc.HCl −−→ ZnCl2 + H2 [fast]

(a) Physical State of reactants:

The decreasing order of rate of reaction based on the physical

(b) Physical size of the reactants:

Among the solids, rate increases with decreases in the particle

The rate of reaction increases as surface area of the reactants

“Mg” powder reacts with dil.H2SO4 more rapidly than “Mg”

(c) Chemical nature of reactants:

Reactions between ionic substances take place much faster

NaCl + AgNO3−−→ NaNO3 + AgCl

The reactions between covalent molecules involving the

Reactions which involve lesser bond rearrangements are rapid at

Reaction A involves breakage of 6 bonds and formation of 6 bonds. Reaction B

 The rate of a reaction increases with increase in the temperature.

The reaction between Zn and HCl can be performed at two different

The rate of reaction is directly proportional to the temperature. Arrhenius

A = Arrhenius factor or frequency factor

Apply ln on both sides

Logarithmic Arrhenius equation is

The above equation is in the form of y = mx + C.

 Catalysts are substances which alter the rate of reaction without

Presence of positive catalyst:

Positive catalyst increases the rate of reaction by decreasing the activation

In the Habour process i.e, manufacture of ammonia, iron(Fe) is used as a

Presence of negative catalyst:

Negative catalyst decreases the rate of reaction by increasing the activation

In the decomposition of hydrogen peroxide, glycerol is used as negative

Examples are photosynthesis and photography.

 Other examples are:

Order of such a reaction = x + y

 It can be determined experimentally

 From the study of the kinetics of many simple reactions, it is observed

Difference between Molecularity and Order:

Pseudo order reactions: