UNIT-II: Chemical Kinetics

Introduction to Chemical Kinetics – Theories of Reaction Rates – Collision Theory – Modified

Collision Theory –Arrhenius Theory –Brief note on Absolute Reaction Rate Theory (Transition
State Theory) – Reaction between Ions – Influence of Solvent (Double Sphere Activated
Complex and Single Sphere Activated Complex) – Lindamanns’ theory of unimolecular
reactions – Influence of Ionic Strength on the Rate of the Reactions – Steady State
Approximation in Chain Reactions – Hydrogen and Bromine, Hydrogen and Oxygen (Steady
State Treatment) – Explosion Limits.

Introduction to Chemical Kinetics:

 Chemical kinetics is the branch of physical chemistry which deals with the study of the rates
of chemical reactions and the factors which affect the reaction rates. Such studies also enable
us to understand the mechanism by which the reaction occurs.
Reaction Rates
 Rate of a chemical reaction = change in concentration (mol/L) of a reactant or product with
time (s, min, hr);
Change in Concentration
 Rate of Reaction = Change in Time

 Progress of a simple reaction, Reactant A → Product B

 Concentration of Reactant A (Blue) decreases with time and concentration of Product B

(Red) increases with time.
∆[A] ∆[B]
 For simple reactions, Rate = − =
∆t ∆t

∆[A] = change in concentration of A over time period ∆t.

∆[B] = change in concentration of B over time period ∆t.

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 For complex reactions, aA +bB…. → Cc + dD….
1 ∆[A] 1 ∆[B] 1 ∆[C] 1 ∆[D]
Rate = − = − = =
a ∆t b ∆t c ∆t d ∆t

 Unit of rate: mol L s -1 -1

 For gaseous reactants & products, conc. is usually expressed as partial pressures, so unit of
rate is atm s-1.
 The rate is a measure of the change in concentration of reactant or product with time.
 The change in concentration of any of the reactants or the products over a specified interval
of time is called the average rate of reaction (r).

Change in Concentration
Rate (r) = Time interval

 Average Rate of reaction decreases with time as concentration of reactants decreases.

 Rate of change of concentration of any of the reactants or products at a particular instant of
time is called the instantaneous rate of reaction, for that particular reaction at that instant of
time. The instantaneous rate is also known as differential rate.
 The instantaneous rate is the rate at a particular time.

 It is determined by finding the slope of the tangent to the concentration Vs time curve at that
time.
C2 − C1
Slope = t2 − t1

 The initial rate is the instantaneous rate at the very beginning of a reaction.

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  A tangent is drawn to the curve at the time t, at which the rate of reaction is to be
determined. The negative slope of the tangent to the reactant concentration versus time is
the instantaneous rate of consumption of the reactant at time t. The positive slope of the
tangent to the curve of product concentration versus time is the instantaneous rate of
formation of the product.
 Factors affecting the rate:
 Nature of reactants
 Concentration of reactants
 Temperature
 Surface area of reactants
 Catalyst
 Molecularity and order of a reaction:
Molecularity: Number of reacting species which collide to result in reaction. Only positive
integral values and never negative. Ex: 1, 2, 3….
Theoretical concept and the value is derived from mechanism of reaction.
Ex: N2O4 → 2NO2 Unimolecular
CO + NO3 → NO2 + CO2 Bimolecular
Order: Sum of powers to which concentrations are raised in the rate law expression. Zero,
fractional or even be negative. Experimental fact and derived from rate law.
Rate law: Expresses the relation between rate of reaction and concentration of reactants.
Rate = k [A]m [B]n
k is rate constant and over all order of the reaction = m+n

N2O5 → 2NO2 + ½ O2 Order = 1

2HI → H2 + I2 Order = 2
CHCl3 (1) + Cl2 (1/2) → CCl4 + HCl Order = 3/2
 A negative order indicates that the concentration of that species inversely affects the rate of a
reaction.
Ex: Decomposition of ozone to oxygen: 2O3(g) ⇌ 3O2(g)
 Zero-order reaction is a chemical reaction wherein the rate does not vary with the increase or
decrease in the concentration of the reactants. Therefore, the rate of these reactions is always

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 equal to the rate constant of the reactions, since the rate of these reactions is proportional to
the zeroth power of reactants concentration.

A → Products

Rate = k [A]n Here n = 0

where ‘k’ is the rate constant of the reaction.
The unit of the rate constant in a zero order reaction is mol L-1 time-1.

 First-order reaction can be defined as a chemical reaction in which the reaction rate is
linearly dependent on the concentration of only one reactant. Thus, the order of these
reactions is equal to 1.
Rate = k [A]

2.303 a
k1 = log 𝑎−𝑥
t

The unit of the rate constant in a first order reaction is time-1.

Ex: N2O5 → 2NO2 + ½ O2

H2O2 → H2O + ½ O2
 Second-order reactions can be defined as chemical reactions wherein the sum of the
exponents in the corresponding rate law of the chemical reaction is equal to two. The rate of
such a reaction can be: Rate = k[A]2 (or) k[A][B].
1 x
K2 = t 𝑎 (𝑎−𝑥)

The unit of the rate constant in a second order reaction is litre. mol-1. time-1.

Ex: N2O → 2N2 + O2

NO + O3 → NO2 + O2
2HI → H2 + I2

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 Pseudo-order reactions: An order of a chemical reaction that appears to be less than the true
order due to experimental conditions; when one reactant is in large excess.

Ex: CH3COOC2H5 + H2O → CH3COOH + C2H5OH

The concentration of water does not get altered much during the process (because it is in
excess), we can take it as constant.

Rate = k [CH3COOC2H5]

Theories of reaction rates:

Collision theory–Modified collision theory:
 Collision theory of chemical reactions is based on the kinetic theory of gases.
 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.
 Collisions must occur between reactant molecules during a chemical reaction, without
collisions between reactant molecules, no reaction takes place.
 They must collide with sufficient energy to break the original bonds and form new ones.
 As concentration increases, the number of collisions will increase, also increasing the rate.
 For a bimolecular elementary reaction: A + B → Products
The rate of reaction can be expressed as:

Where, ZAB represents the collision frequency of reactants, A and B.

The number of collisions per second per unit volume of the reaction mixture is known as
collision frequency (Z).
Ea = Activation Energy
R = Universal gas constant
T = Temperature in absolute scale
 The collision frequency between A and B is defined by:

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 where, NA and NB are the numbers of molecules A and B, and is directly related to the
concentrations of A and B.
σAB is the collision cross-sections of molecules A and B. The collision cross section
represents the collision region (collision diameter).
μ is the reduced mass and kB is Boltzmann constant.
 All collisions do not lead to form products. Only some collisions give products. These
collisions are called fruitful collisions.
 Threshold Energy (ET) is the minimum amount of energy which the reactant molecules must
possess for the effective collision in forming the products.
 Under ordinary conditions most of the molecules are having energy less than threshold
energy. These molecules are called normal molecules.
 The additional energy required to the normal molecules to attain threshold energy is called
Activation energy (Ea).The term activation energy was given by Arrhenius.
 As per the Arrhenius equation, all the molecules that have energy greater than or equal to
activation energy will collide to form products.
 Activation energy = Threshold energy – Average kinetic energy of molecules.
Ea= ET-ER

 Some molecules having sufficient energy (activation energy) did not collide to form the
product. Only a few of them made effective collisions (formation of products). The scientists
found that the kinetic energy of the molecules is not the only parameter that directs the
reaction.
 They concluded that only those molecules that have the threshold energy (activation energy)
and proper orientation during the collision will form products.

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 Ex:

 They introduced a probability factor P to account for the effective collisions. So now the rate
of a reaction is given by:

 The activation energy and proper orientation of the reacting molecules together determine the
condition for a collision that will result in the formation of products (an effective collision).
So in collision theory, both activation energy and effective collision direct the rate of a
reaction.

Arrhenius Theory:

 Temperature has a very significant effect on the rate of chemical reaction. In general the rate
of chemical reactions increases with the rise in temperature.
 The temperature dependence of the rate of a chemical reaction can be accurately explained
by Arrhenius.

Where, k = rate constant

A = Arrhenius factor or frequency factor
Ea= Activation energy, R = gas constant, T = Temperature.
 In the Arrhenius equation, the exponential factor corresponds to the fraction of molecules
that have kinetic energy greater than activation energy.
 Thus, it has been found from Arrhenius equation that increasing the temperature or
decreasing the activation energy will result in an increase in the rate of the reaction and an
exponential increase in the rate constant.
 Taking natural logarithms of both sides of Arrhenius equation,

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

Ea
 The plot of ln k vs 1/T gives a straight line according to the equation with slope = – and
R

intercept = ln A. So we can calculate Ea and A using these values.

 At temperature T1, Arrhenius equation is:

 At temperature T2, Arrhenius equation is:

k1 and k2 are the values of rate constants at temperatures T1 and T2 respectively.

 Subtracting the above equations, we get

 Thus activation energy of a reaction can be determined from the above equation by knowing
the values of constants k1 and k2 at temperaturesT1and T2.

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Brief note on Absolute Reaction Rate Theory (Transition State Theory):

 In 1935, Henry Eyring develop a new theory called the Transition State Theory (TST).
 According to TST, between reactants and the products, there is a state known as the
transition state.
 In the transition state, the reactants are combined in a species called the activated complex.
 The activated complex is clearly different than the reactants or the products.
 Three major factors that determine whether a reaction will occur:
 The concentration of the activated complex
 The rate at which the activated complex breaks apart
 The way in which the activated complex breaks apart: whether it breaks apart to reform
the reactants or whether it breaks apart to form a new complex, the products.

 Consider a bimolecular reaction. In the transition state model, the activated complex AB is
formed:

 A certain amount of energy is required for the reaction to occur. The transition state, AB‡, is
formed at maximum energy. This high-energy complex represents an unstable intermediate.
 Once the energy barrier is overcome, the reaction is able to proceed and product formation
occurs.

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 The rate of a reaction is equal to the number of activated complexes decomposing to form
products. Hence, it is the concentration of the high-energy complex multiplied by the
frequency of it overcoming the barrier.

…………….i
 The rate can be rewritten:

……………….ii
 From these two equations:

…………iii

where, v is the frequency of vibration, k is the rate constant and K‡ is the thermodynamic
equilibrium constant.

 Statistical mechanics provides that the frequency, v, is equivalent to:

………………iv
 Substituting equation (iv) into equation (iii),

…………….v
 The equilibrium constant K‡ can be expressed in terms of (∆Go)‡, called the standard Gibbs
free energy of activation.
 For the activated complex, we can write,
(∆Go)‡ = -RT ln K‡ and (∆Go)‡ = (∆Ho)‡ - T(∆So)‡
K‡ = e-(∆Go)‡/RT
K‡ = e-[(∆Ho)‡ - T(∆So)‡]/RT
K‡ = e(∆So)‡/R. e - (∆Ho)‡/RT
kBT
From equation (v), we get: k = e - (∆Go)‡/RT
ℎ
kBT
k= e (∆So)‡/R. e - (∆Ho)‡/RT
ℎ

 This equation is known as Eyring equation.

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Reaction between ions –Influence of solvent (Double sphere activated complex and single
sphere activated complex):
Double sphere model:
 Ionic reaction in solution is affected by electrostatic interactions among the reactive species.
 A solvent is considered as continuous surrounding medium with a ε as the dielectric constant.
 According to double sphere model, two ions, which can same or opposite charges, combine
together to form an activated complex.
 In the initial state, the ions are considered as separate; while in the final state, they assumed
to form a dumbbell like coordination with ʻrʼ as the distance of separation between their
centers.

 Now, if ZA and ZB are the charge numbers of the participating ions and x as the distance of
separation, the force of electrostatic interaction (FAB) between them can be given from the
Coulomb’s law as:

The symbol e represents the elementary charge and has a value equal to 1.6 × 10 −19C. The
value of parameter varies from ∞ to r with the mutual approach of two ions. The amount of
work done in moving the two ions closer by an extant dx will be

Work = Force × Displacement

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 The negative sign is an indicator of decreasing separation. The total amount of work done in
moving the two ions from x = ∞ to x = r will be

 The work given the above equation is actually the potential energy of the system which
would have a negative sign for oppositely charged ions and positive sign if the ions have
same charges.
 Furthermore, this work is the free energy change due to electrostatic interactions, therefore,
multiplying it by Avogadro number (N) would give the value of the corresponding molar free
∗
energy change (ΔG𝐸𝑙 ), i.e.,

∗
 Correcting the above equation for non-electrostatic contribution (ΔG𝑁𝐸𝑙 ), the total molar free
energy change for the whole process can be given by the following relation.

 Also, from the activated complex theory, we know that

 After putting the value of ΔG*, we get

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 Taking natural logarithm both side of equation, we get

 Which can also be expressed as

where k0 represents the magnitude of the rate constant for the ionic reaction carried out in a
solvent of infinite dielectric constant so that the electrostatic interactions become zero.

Single sphere model:

 As the double-sphere model, a solvent is considered as continuous surrounding medium with

a ε as the dielectric constant.
 According to single sphere model, two ions, which can same or opposite charges, combine to
form a single-sphere activated complex.

 In the initial state, the ions are considered as separate; while in the final state, they assumed
to form a single-sphere activated complex with ʻr*ʼ as the overall radius.
 The rate law for this case was derived by Born by considering the energy required to charge
an ion in solution.

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 Born’s expression is derived as follows: Consider the process of charging a conducting
sphere of radius r from an initial charge of ‘0’ to final charge ‘Ze’.
 This process is carried out by transporting, from an infinite distance, small increments of
charge equal to edλ, where λ is a parameter that varies from ‘0’ to ‘Z’.
 At any time the charge on the sphere may be written as λe, and if at a given instant the
increment of charge (edλ) is at a distance x from the ion, the force acting on it is

 The work of moving the increment from x to x-dx is

𝑑𝑤 = 𝑑𝐹 × 𝑑𝑥

The negative sign is an indicator of decreasing separation.

 The total amount of work done can be obtained by carrying out the double integration with
respect to x = ∞ –r and λ = 0 – Z.

 The work given the above equation is actually the contribution of the electrostatic
interactions to the Gibbs free energy of the ion.

 From the above correlation, the electrostatic contribution to the Gibbs free energy of distinct
ions and activated complex can be written as
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 Hence, the change in electrostatic contribution can be obtained simply by subtracting the
sum of individual contributions from the overall contribution i.e.,

∗
 Correcting the above equation for non-electrostatic contribution (ΔG𝑁𝐸𝑙 ), the total molar
free energy change for the whole process can be given by the following relation.

 Also, from the activated complex theory, we know that

 After putting the value of ΔG* in the above equation, we get,

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 Taking natural logarithm both side of the above equation and rearranging, we get,

 Which can also be expressed as

where k0 represents the magnitude of the rate constant for the ionic reaction carried out in a
solvent of infinite dielectric constant so that the electrostatic interactions become zero.

Lindemann’s’ theory of unimolecular reactions:

 The first successful explanation for unimolecular reactions was provided by Lindemann in
1921 and therefore known as Lindemann theory.
 This is the simplest theory of unimolecular reaction rates and was successfully explained
first order kinetics of many unimolecular reactions.
 Lindemann assumed that there is time lag between activation and reaction during which the
activated molecules may either react to give products or deactivated to ordinary molecules.
 Lindemann assumed a situation where “A reactant molecule A becomes energetically
excited by collision with another molecule of reactant A”.

where A represents inactive molecule while 𝐴∗ represents activated molecule.

 The rate for the reaction becomes,

 The energized molecule 𝐴∗ can lead to two situations:

 Situation I: The energized molecule 𝐴∗ might lose its energy by colliding with another
molecule of A.

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 Situation II: The energized molecule 𝐴∗ might lead to product formation.

The rate for reaction becomes,

…………(i)
 Steady state approximation/Principle: This principle states that when a short lived reaction
intermediate such as 𝐴∗ exists in a system, the rate of formation of the intermediate can be
considered to be equal to its rate of disappearance. Applying this to [𝐴∗] gives,

On rearranging the equation gives,

 Substituting the value of [𝐴∗] in the equation (i),

 This is the rate law expression for unimolecular reaction based on Lindemann theory. The
rate law as given by above equation is not first order.
 Case I: 𝑘−1[𝐴] ≫>>𝑘2

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 So the reaction becomes first order with respect to reactant A.

 When the pressure of the gas is very high then there will be more number of collisions
between the molecules. So the energized molecule will be de-energized more by collisions
rather than decomposing into products.
 Case II: 𝑘−1[𝐴] ≪<<𝑘2

So, the reaction becomes second order with respect to A.

 Using ideal gas equation condition as,

 When the pressure of gas is so low, then the molecule will be very far apart and hence
instead of getting de-energized by collision with another molecule, the energized molecule
A* will decomposed into products.
 So, “at low pressures the rate is of second order whereas at high pressure conditions, the rate
becomes of first order”.

Influence of ionic strength on the rate of reactions:

 The ionic strength of the solution is a measure of the concentration of ions in that solution.
Ionic strength of a solution can significantly affect the rates of reactions.
 The influence of ionic strength (I) on the rate of ionic reactions is:

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 where ci is the concentration of each ion present in the solution and zi is its charge number.
(Ex: +2 for Ca2+ and –1 for Cl–).
 Consider a reaction,

where zA and zB are the charges on the reactants A and B and the charge on the activated
complex is equal to zA+zB.
 The rate of the reaction is proportional to the concentration of the activated complex, hence
R = k [X]
 The equilibrium between the activated complex and the reactants is written as

….(i)
where γA, γB and γ# are the activity coefficients for the reactant A, B and the activated
complex X, respectively.
 Now, rearranging equation (i), we get

 Since the left-hand side simply equals to a second-order rate constant, the above equation
takes the form

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 Taking logarithm both side, we get

……….(ii)
 According to Debye-Huckel theory, the activity coefficient of an ion is related to the ionic
strength by the equation,

……….(iii)
where B is the Debye-Huckel constant.
 From (ii) and (iii) equations, we get

which is clearly the equation of straight line (y = mx + c) with a positive slope (2𝐵𝑧𝐴𝑧𝐵) and
positive intercept (log 𝑘0).
 For aqueous solutions at 25°C, this equation becomes,

……(iv)
where k0 is the rate constant at zero ionic strength and can be obtained by the extrapolation of
log k vs square root of the ionic strength.
 According to the equation (iv), A plot of log (k/k0) versus I1/2 gives a straight line with slope
1.02 zAzB.
 The plot for different ionic reactions in aqueous solution at 25°C is as shown in Figure.

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 It has been found that an increase the ionic strength increases the rate of reaction if charges
on the reacting species are of the same sign.
 On the other hand, the reaction rate has been found to follow a declining trend with
increasing ionic strength if reaction ions are of opposite sign.
 It has been seen that, if one of the reactants is a neutral molecule, the product of zAzB=0 and
therefore the rate constant will become independent of the ionic strength. This is true for the
base-catalyzed hydrolysis of ethyl acetate.

Steady state approximation in chain reactions:

 The steady state approximation is a method used to derive the overall reaction rate of a
multi-step reaction.
 It assumes that the rate of change of intermediate concentration in a multi-step reaction is
constant.
 The reactive intermediate (Int) will be consumed as soon as it is formed.
 In other words, Rate of formation of intermediate = Rate of disappearance of intermediate

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Hydrogen and Bromine:
 The overall reaction between hydrogen and bromine is:

H2 + Br2⟶ 2HBr

 The chain mechanism for the hydrogen-bromine reaction can be proposed as:

 The net rate of formation of HBr must be equal to:

 In order to obtain the overall rate expression, the steady-state approximation must be applied
to the two intermediates H and Br.
𝑑[𝐻]
 The steady state equation for hydrogen radical is = 0 (or)
𝑑𝑡

Rate of formation of H radical = Rate of disappearance of H radical

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 𝑑[𝐵𝑟]
 Similarly, the steady state equation for bromine radical is =0 (or)
𝑑𝑡

Rate of formation of Br radical = Rate of disappearance of Br radical

 Now substitute the value of [Br] from equation (iv), in the equation (iii), we have,

……….(v)
 Substitute the value of equation (ii) in equation (i), we have,

 Taking k3[Br2] as common in the denominator and then canceling out the same form
numerator, we get,

 Now consider two new constants as

This is the rate expression of hydrogen and bromine reaction.

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  The initial reaction rate expression can be obtained by considering [HBr] ≈ 0, i.e.,
𝑑[𝐻𝐵𝑟]
1 + 𝑘’’ ≈1
𝐵𝑟2

 Hence, the order of the hydrogen-bromine reaction in the initial stage will be 1.5 only.

Hydrogen and Oxygen (Steady State Treatment)–Explosion Limits:

 An explosion occurs when a reaction rate accelerates out of control. Some reactions proceeds
explosively.
 The explosions are of two types:
(i)Thermal explosion, (ii) Explosion depends on chain reaction
 Thermal explosion: If the energy of an exothermic reaction cannot escape, the temperature of
the system rises and the reaction goes faster and it leads to explosion.
 In some chain reactions, each chain carrier produces more than one free radical in
propagation steps resulting in a rapid increase in the concentration of active species. This in
turn further increase the production of free radicals. The reaction thus occurs rapidly and an
explosion takes place.
Ex: 2H2 (g) + O2 (g) → 2H2O (g)
 Though this may appear to be a very simple reaction, and is still not fully understood.
Involving carriers such as H, O and OH radicals.

 Each of reactions 2 and 3 produce two radical chain carriers from one chain carrier.
 When such chain branching occurs, the number of free radicals in the system can increase
extremely rapidly, and an explosion may result.
 The free radicals may also be destroyed mainly by colliding with walls of the container.

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 Between 460 and 6000C, a stoichiometric mixture explodes spontaneously at certain
pressures.
 Below a certain pressure, the reaction takes place slowly and smoothly (steady reaction rate).
 At low pressure, the radicals reach the surface easily and get destroyed. The rate destruction
of radicals counter balances the formation of radicals from branching of the chain. Hence,
reaction proceeds smoothly.
 On increasing the pressure, the rate of diffusion of radicals to the walls decreases and
therefore the rate of destruction of radicals slows down while the rate of propagation and
branching increases.
 Thus due to a considerable increase in concentration of radicals, the rate of reaction increases
enormously leading to an explosion. This is called lower explosion limit.
 On further increasing the pressure, the radicals more readily destroy internally in the gas than
at the walls. This results in the removal of radicals and any increase in the production of
radicals is again counter balanced. The reaction, therefore proceeds smoothly. This is the
second explosion limit.

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 Thus, at this temperature, there is a pressure region within which there is explosion but above
and below which there is smooth (steady) reaction. The two explosion limits are referred to
as the first and second limits.
 There is also a third limit, at still higher pressures. For some reactions the explosion that
occurs beyond this limit is due to the fact that the rate of heat production by a reaction
mixture exceeds the rate of heat loss to the surroundings. This is the third explosion limit.
 In exothermic reactions when the reaction is carried out in closed space, the heat generated
cannot be dissipated. The reaction rate suddenly becomes very rapid and a thermal explosion
occurs.
 In the hydrogen-oxygen system, the explosion is due to an increase in the concentration of
free radicals.

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