CHemical Kinetics
Introducion:
Chemical Kinetics is the branch of
chemistry which deals with the study of
the rate of chemical reaction, factors
affecting rate of reaction and the
mechanism by which the reaction
occurs.
Rate of Reaction:
Rate of reaction is defined as the change in concentration of a
reactant or product per unit time. For a general reaction,
A→ B, the rate of reaction may be expressed as,
Rate of reaction= - decrease in concentration of A/time taken
= increase in concentration of B/time taken
Rate of reaction=-Δ[A]/Δt = Δ[B]/Δt
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Let [A1], [A2], and [B1] and [B2] be the concentration of A
and B at time t1 and t2 respectively.
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Rate of consumption of A= -[A2]-[A1]/t2-t1=-Δ[A]/Δt
Rate of formation of B =[B2]-[B1]/t2-t1 = Δ[B]/Δt
Negative sign indicates that concentration of reactant is
decreasing and positive sign indicates that concentration
of product is increasing.
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The negative sign in the rate expression indicates the
decrease in the concentration of the reactant and gives
a positive value of the rate.
Units of rate are mol L-1s-1 or atm s-1 (in gaseous
reactions).
The above expression of rate gives us the average rate
of reaction.
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Types of rate of reaction:
Average Rate: Instantaneous rate:
Average rate of reaction is It is defined as the rate of
defined as the rate of change of change of any one of the
concentration per unit time. reactants or products at a
particular instant of time.
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Instantaneous rate of reaction:
It is the rate of reaction at a particular moment of time and
measured as a very small concentration change over a very small
interval of time.
Mathematically, instantaneous rate = (average rate) Δt→ 0
For a general reaction, R → P
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Instantaneous rate can be determined graphically by drawing a
tangent at time t on either side of the curve. The concentration of
A or B vs time and calculating its slope.
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General Expression For Rate Of Reaction:
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Factors Affecting The Rate Of A Chemical Reaction:
a) Nature of reactants: It has been observed that ionic substances react more
rapidly than the substances with covalent bonds. This is because ions are
immediately available in aqueous solution on dissociation hence react rapidly but
covalent molecules consume part of energy in breaking of bonds.
b) Concentration of reactants: Rate of reaction is directly proportional to the
concentration of reactants.
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c) Temperature: Rate of reaction increases with the increase in temperature.
d) Presence of catalyst: In the presence of catalyst the rate of reaction generally
increases and the equilibrium state is attained quickly in reversible reactions.
e) Surface area of the reactants: The smaller the particle size, the greater is the surface area
and faster is the reaction.
f) Radiations: There are many reactions which either do not take place at all or take place
quite slowly in the dark. But take place at a considerable speed when exposed to sunlight or
ultraviolet radiations. Such reactions are called photochemical reactions. Eg: Photosynthesis,
Photography etc.
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Rate law: In rate law , rate is expressed in concentration terms which
actually influences the rate of reaction.
It is an experimentally determined expression which relates the rate of reaction with
concentration of reactants.
For a hypothetical reaction,
aA + bB →Products
Rate ∝ [A]m[B]n
Rate = K [A]m[B]n
Here K is the constant known as specific rate of reaction or rate constant
If A = B=1 mol L-1 then Rate = K
Thus rate constant may be defined as the rate of the reaction when the concentration
each reactant in the reaction is unity.
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Rate= K[A]m [B]n
where value of m and n may or may not be same as stoichiometric
coefficient a and b.
m and n determine the order of reaction with respect to A and B,
which actually influence the rate of reaction, m + n is called overall
order of reaction.
Rate law 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.
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Order of reaction:
It may be defined as the sum of powers of concentration of the reactants in the rate law
expression
Order of reaction can be 0,1, 2 or 3 and even a fraction
For a hypothetical reaction,
aA + bB + cC → Products
Let rate=K[A]m[B]n[C]p
Where, m= order of reaction with respect to A
n= order of reaction with respect to B
p= order of reaction with respect to C
Overall order of the reaction is m+n+p
It is determined experimentally.
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Units of rate constant
For nth order reaction
A → Product,
Rate = K[A]n
Or, K=Rate/[A]n = concentration/timeX 1/(concentration)n
= (concentration)1-n time-1
a) Examples of 1st order reaction
● All the radioactive disintegrations are of the first order
● Decomposition of sulfuryl chloride
SO2Cl2 → SO2 + Cl2
● Characteristics of first order reactions
● All first order reactions obey the kinetic equation of first order reaction
● Unit of K is time-1. Therefore change in unit of concentration does not alter
the value of K
● t1/2 ∝ 1/K implies that the time taken for completion of any fraction of the
reactant into product is independent of initial concentration.
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b) examples of second order reaction:
● 2HI(g) → H2(g) + I2(g)
● CH3COOC2H5 + NaOH → CH3COONa + C2H5OH
● NO(g) + O3(g) → NO2(g) + O2(g)
Unit of K= litre mole-1 second-1
c) examples of third order reaction:
● 2NO(g) + O2(g) → 2NO2(g)
● 2NO(g) + Br2(g) → 2NOBr(g)
Unit of K= L2mole-2 s-1
d) Example of fractional order reaction:
● CH3CHO → CH4 + CO; Rate= k[CH3CHO]3/2
Calculate the unit of K.
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Zero order reaction: Adsorption of ammonia on
the surface of platinum in unimolecular layer.
When total surface area of platinum is covered,
the rate of reaction remains unaffected even if
concentration of ammonia is increased or
decreased. Thus the order of reaction becomes
zero.
2NH3 Pt N2 + 3H2
Rate = K[NH3]0 , order = 0
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Elementary reaction:
A reaction which takes place in one step is called an elementary reaction. When a
sequence of elementary reactions gives the products, the reaction is called complex
reaction.
Molecularity:
The number of reacting species (molecules, atoms, ions) taking part in an elementary
reaction which must colloide simultaneously in order to bring about a chemical
reaction.
Reactions are classified as unimolecular, bimolecular and trimolecular for molecularity
1, 2 and 3 respectively
Examples:
● NH4NO2 → N2 + 2H2O (Unimolecular reaction)
● 2HI(g) → H2(g) + I2(g) ( Bimolecular reaction)
● 2NO(g) + O2(g) → 2NO2(g) (Trimolecular reaction)
The probability of more than three molecules colliding simultaneously is rare. Therefore
molecularity of a reaction does not extend beyond three. Molecularity can be defined
only for an elementary reaction and has no meaning for a complex reaction.
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Intermediates:
The species which are produced in one step and consumed in another are called intermediates.
Mechanism of reaction:
A series of elementary reactions proposed to account for the overall reaction is called mechanism
of reaction. The overall rate of reaction is controlled by the slowest step in a reaction and is called
the rate determining step.
Consider the reaction, 2H2O2 + I- → 2H2O + O2
The rate equation for this reaction is found to be
First step being slow is the rate determining step. Thus the rate of formation of intermediate IO-
will determine the rate of reaction. 28
Pseudo First Order Reaction:
The reaction which is not truly of first order but under certain conditions becomes reaction of the
first order is known as pseudo first order reaction. For example the inversion of cane sugar is a
bimolecular reaction but it is a first order reaction as concentration of H2O is quite large and does
not change appreciably
C6H12O11 + H2O → C6H12O6 + C6H12O6
Rate = K[C12H22O11]
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The molecularity of acidic hydrolysis of sucrose and ester is two, whereas its order is one.
So this is another example of pseudo first order reaction.
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The differential and integrated rate equations:
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The instantaneous rate is measured by determination of slope of the
tangent at suitable point 't' in "Concentration" versus "Time" Plot.
Determination of instantaneous rate by this method is not always
convenient. Thus, it is difficult to determine the rate law and hence
the order of the reaction.
On integration of the differential rate equation, we get
integrated rate equations. They give a relation between directly
measured experimental data, i.e., rate constant and concentrations
at different times.
For the reactions of different orders, the integrated rate
equations are different.
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Integrated rate equation for zero order reaction:
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Concentration [R] Vs. time(t) plot for a zero order reaction:
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Examples of zero order reactions.
(i) The thermal decomposition of HI or gold surface.
(ii) The decomposition of gaseous ammonia on a hot platinum surface at high
pressure.
(iii) Some enzyme catalysed reactions.
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Integrated rate equation for
rate constant of first order reaction:
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Examples of first order reaction:
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Relation between the half life period of a
reactant(t1/2) and its initial concentration [R]o
for the reaction of nth order
t1/2∝ ([R]o)1-n
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Temperature dependence of the rate of a reaction:
What is the effect of temperature on the rate of reaction
For the decomposition of N2O5 as per the following equation
N2O5(g) → 2NO2(g) + ½ O2(g)
The time taken for half of the original amount of N2O5 to decompose(t1/2) at different
temperatures is found to be as follows:
This means the reaction gets accelerated by increase in temperature.
It has been experimentally found that rate constant is nearly doubled for a chemical
reaction with rise in temperature by 100C
● Rise in temperature by 100C = 21 X rate constant
● Rise in temperature by 100CXn = 2n X rate constant
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Activation Energy
Activation energy is the energy required by reactants
to collide and form an unstable intermediate (known as
activated complex). This activated complex then
decomposes to form the product. Thus, activation
energy is the extra energy which must be supplied to
the reactants so that they can change into the
products after crossing the activation energy barrier,
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Arrhenius Equation:
Arrhenius (Swedish chemist) provided following mathematical equation for
explaining
the temperature dependence of the rate of a chemical reaction.
K=Aexp(-Ea/RT)
where A-The Arrhenius factor (or the frequency factor) (or the
pre-exponential factor). It is a constant specific to a particular chemical
reaction.
R- Universal gas constant
E = Activation energy measured in Joules per mole.
exp(-Ea/RT) = Fraction of molecules that have kinetic energy greater than
Ea.
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How does Arrhenius calcuation help in the calculation of activation energy of a
reaction ?
Taking natural logarithm of both sides of equation:
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The plot of Ink along y-axis, and
along 1/T x-axis gives a straight line according to the
equation (1).
As m= Slope=-Ea/R and intercept = In A,
using these values, Ea and A can be calculated.
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Derive:
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Arrhenius equation at two temperatures T1 and T2,
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For a given reaction, A is constant.
At temperatures T₁ and T₂; k, and k₂ are the values of rate constants, respectively.
Subtracting equation (1) from equation (2), we get
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Some important of concepts:
1. Activated complex
2. Reaction Coordinate
3. Activation energy
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Consider a simple reaction:
H2(g) + I2(g) → 2HI (g)
For a reaction to take place, following steps are generally involved:
1. Collision between the reactants.
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Formation of an unstable intermediate also known as activated complex:
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When reactants collide, they
form an unstable activated complex and
finally change into products, the energy
profile also changes simultaneously at
each step.
The profile of energy change when
reactants change into products is
represented by reaction coordinate.
When potential energy is plotted
vs. reaction coordinate, we get Fig. 4.9(a)
Activation energy (E,) is the energy
required to form the activated complex.
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Unstable intermediate exists
for a very short time and
then breaks up to form
products along with release
of some energy. The nature
of reactants and products
govern the total enthalpy
change (or heat change) of
reaction, whether reaction
will be exothermic (A)
or endothermic (B).
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In the reacting system, all the
molecules have different kinetic energies.
Energies among gaseous molecules can
be statistically (as per Ludwig Boltzmann
and James Clark Maxwell) shown in the
distribution curve (Fig. 4.10). Statistics is
useful for predicting the behaviour of large
number of molecules when it is difficult to
predict the behaviour of any one molecule
with precision.
The peak of the distribution curve
corresponds to the kinetic energy of
maximum fraction of molecules. It is
known as the most probable kinetic energy.
There are decreasing number of mole-
cules with energies higher or lower than
most probable kinetic energy.
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Catalyst:
A substance which increases or decreases the rate of a reaction without itself
undergoing any permanent chemical change is known as a catalyst.
Negative catalyst decreases reaction rate while positive catalyst increases reaction rate.
Consider the decomposition of KCIO3, for the production of O₂ as per following reaction :
MnO₂
2 KClO3 2 KCl +30₂
For this reaction, MnO₂ acts as a positive catalyst and considerably increase the rate of
reaction.
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Intermediate Compound Formation Theory. This theory is useful for explaining the
action of the catalyst. This theory explains reaction as per following two steps
Step 1. A catalyst and a reactant interact, form temporary bonds resulting in the
formation of an intermediate complex
R + C → [RC]
Reactant Catalyst Intermediate complex
Step 2. Unstable intermediate complex decomposes to make product and the
catalyst gets regenerated.
[RC] → P + C
Intermediate Product Catalyst
Complex
Transitory existence
Thus the catalyst provides an alternate pathway or reaction mechanism.
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Characteristics of a catalyst:
(i) Catalyst is required in less amount. This is because a small amount of the catalyst can
catalyse conversion of a large amount of reactants into products as catalyst gets
regenerated after every conversion.
(ii) A catalyst does not alter Gibbs energy (AG) of a reaction. A catalyst alters rate of only the
spontaneous reactions. There is no effect of catalyst on non-spontaneous reactions.
(iii) A catalyst does not change the equilibrium constant of a reaction. Catalyst alters the
forward as well as the backward reactions to the same extent. The equilibrium is
attained faster but the equilibrium state remains same.
(iv) The catalyst provides an alternate pathway or reaction mechanism. In the presence of
positive
catalyst, alternative path has reduced activation energy barrier so the rate of reaction
increases. In the presence of negative catalyst, alternative path has increased
activation energy barrier (in comparison to uncatalyzed reaction) so the rate of
reaction decreases.
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Collision Theory of Chemical Reactions
According to Max Trautz and Willian Lewis, reaction is postulated to meet
following three criteria:
(i) The reactants must collide before the reaction can occur. Assuming the
reactant molecules as hard spheres, then for a bimolecular elementary
reaction between two reactants A + B → Products
The Collision frequency (ZAB) of reactants A and B is the number of collisions
per second Per unit volume of the reaction mixture
(ii) The rate of the reaction is directly proportional to the fraction of molecules
having energy greater than activation energy.
The fraction of molecules with energies equal to or greater than E, is
represented by e-Ea/RT
There must be proper orientation of the reactant molecules in a collision.
Consider biomolecular nucleophilic substitution (SN2) reaction between
bromomethane (CH3Br) and hydroxide ions (HO-) leading to the formation of
methanol (CH3OH).
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To take into account this proper orientation between reactants , a factor P is introduced in
rate expression. It is known as probability or steric factor.
To sum up the criteria for effective collision and hence the rate of a chemical reaction can be
mathematically expressed as :
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