2.

0 THEORIES OF CHEMICAL KINETICS

2.1 Collision Theory

 Assumes that chemical reactions occur as a result of collisions between reacting molecules.
 Thus the rate of reaction will be directly proportional to the number of molecular collisions
per second or to the frequency of collisions:

𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑐𝑜𝑙𝑙𝑖𝑠𝑖𝑜𝑛𝑠
𝑟𝑎𝑡𝑒 ∝
𝑠

 Not all collisions are effective. Only a small fraction of the collisions produce a reaction.
 The two main conditions for a collision between the reacting molecules to be productive
are:
(1) The colliding molecules must possess sufficient kinetic energy to cause a reaction.
(2) The reacting molecules must collide with proper orientation.

(1) The molecules must collide with sufficient kinetic energy

 Consider the general reaction:

 A chemical reaction occurs by breaking bonds between the atoms of the reacting molecules
and forming new bonds in the product molecules.
 The energy for the breaking of bonds comes from the kinetic energy possessed by the
reacting molecules before the collision. Fig. 2.1 shows the energy of molecules A2 and B2
as the reaction A2 + B2 → 2AB progresses.

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Figure 2.1: The energy of the colliding molecules as the reaction A2 + B2 AB proceeds.
The activation energy provides the energy barrier.

 The activation energy, Ea is the minimum energy necessary to cause a reaction between
the colliding molecules. Only the molecules that collide with a kinetic energy greater than
Ea, are able to get over the barrier and react.
 Molecules colliding with kinetic energies less that Ea fail to surmount the barrier.
 The collisions between them are unproductive and the molecules simply bounce off one
another.

(2) The molecules must collide with correct orientation

 The reactant molecules must collide with favourable orientation (relative position). The
correct orientation is that which ensure direct contact between the atoms involved in the
breaking and forming of bonds. (Figure 2.2)
Bottom-line: only the molecules colliding with kinetic energy greater that Ea and with
correct orientation can cause reaction.

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Figure 2.2: Orientation of colliding molecules (a) Effective collision leading to formation of
products and b) ineffective collision – reaction occurs

2.1.1 Collision Theory and Reaction Rate Expression

 Taking into account the two postulates of the collision theory, the reaction rate for the
elementary process.

A + B ⎯⎯→ C + D

 Is given by the expression

Rate = f × p × z

Where: f = fraction of molecules which possess sufficient energy to react;

p = probable fraction of collisions with effective orientations

z = collision frequency.

Effect of increase of temperature on reaction rate

 Generally, increasing temperature increases the rate of reaction. As a rule, an increase of

temperature by 10°C doubles the reaction rate.
 The ratio of rate constants of a reaction at two different temperatures differing by 10
degrees is known as Temperature Coefficient.

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2.1.2 Arrhenius Equation: Activation energy, the temperature dependence of rate
constants

 The kinetic energy of a gas is directly proportional to its temperature. Thus as the
temperature of a system is increased, more and more molecules will acquire necessary
energy greater than Ea to cause productive collisions. This increases the rate of the reaction.
 The rate constants of most reactions increase as the temperature is raised. Many reactions
in solution fall somewhere in the range spanned by the hydrolysis of methyl ethanoate
(where the rate constant at 35°C is 1.82 times that at 25°C) and the hydrolysis of sucrose
(where the factor is 4.13).
 Arrhenius suggested as simple relationship between the rate constant, k, for a reaction and
the temperature of the system.

k = Ae–Ea/RT ...(1) Arrhenius equation

Where Ea is the activation energy (in kJ/mol), R is the gas constant (8.314 J/K. mol) T is
the absolute temperature and e is the base of natural logarithm scale. The quantity A is an
experimentally determined quantity called the frequency factor and represents the collision
frequency.

 Due to the negative sign on the exponent, rate constant decreases with increasing activation
energy and increases with increasing temperature.
 The equation can made useful by introducing natural logarithm on both sides Equation

Calculation of Ea Using Arrhenius Equation

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a) Calculation of Ea from the Values of k at Two Temperatures
 An equation relating the rate constants k1 and k2 at temperatures T1 and T2 can be used to
calculate the activation energy or to find the rate constant at another temperature if the
activation energy is known.
 The rate constant, k, is measured at two temperatures. Starting with Equation 2, at
temperature T1, where the rate constant is k1, and temperature T2, where the rate constant
is k2, we have

 Subtracting ln k2 from ln k1 gives:

OR

 From Equation 4, we calculate the activation energy, Ea if the experimental value of the
rate constant, k, is known.

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Example:
The gas-phase reaction between methane (CH4) and diatomic sulphur (S2) is given by the equation
CH4 (g) + 2S2 (g) ⎯⎯→ CS2 (g) + 2H2S (g)
At 550°C the rate constant for this reaction is 1.1 l mol–1 sec and at 625°C the rate constant is
6.4 1 mol–1 sec. Calculate Ea for this reaction.
Solution
Here k1 = 1.1 1itre mol–1 sec. T1 = 550 + 273 = 823 K
k2 = 6.4 1itre mol–1 sec. T2 = 625 + 273 = 898 K
Substituting the values in the equation

Exercise
1. The rate constant of a first-order reaction is 3.46 × 10-2s-1 at 298 K. What is the rate constant at
350 K if the activation energy for the reaction is 50.2 kJ/mol?
2. The first-order rate constant for the reaction of methyl chloride (CH3Cl) with water to produce
methanol (CH3OH) and hydrochloric acid (HCl) is 3.32 × 10-10 s-1 at 25°C. Calculate the rate
constant at 40°C if the activation energy is 116 kJ/mol.

b) Graphical method for determining the activation energy Ea of a reaction

 Equation (2) can be rearranged to a linear equation:

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  Equation 5 is that of a straight line, y = mx + b. The two variables in this equation are 1n
k and 1/T.
 Thus if we plot the natural logarithm of k against 1/T, we get a straight line (Fig. 2.3). From
the slope of the line, we can calculate the value of Ea.

Figure 2.3: The plot of In k versus I/T is a straight line when the reaction follows the behaviour
described by the Arrhenius equation (Equation 5). The slope gives −Ea/R and the
intercept at 1/T = 0 gives ln A..

 The quantity ‘A’ can be treated as a constant for a given system over a fairly wide range of
temperature. The rate constant is directly proportional to A, and thus the collision
frequency.
 In Figure. 2.3, the parameter A, corresponds to the intercept of the line at 1/T = 0 (at infinite
temperature,), and is called the pre-exponential factor or the ‘frequency factor’.
 The pre-exponential factor A is a measure of the rate at which collisions occur irrespective
of their energy.
 The parameter Ea (activation energy), is obtained from the slope of the line (−Ea/R).
 Collectively the two quantities Ea and A are called the Arrhenius parameters.

Example:

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The values of the rate constant (k) for the reaction 2N2O5(g) ⎯→ 4NO2(g) + O2(g) were determined
at several temperatures. A plot of 1n k versus 1/T gave a straight line of which the slope was found
to be – 1.2 × 104 K. What is the activation energy of the reaction?
Solution

Determining Arrhenius parameters

The rate of the second-order decomposition of acetaldehyde (ethanal, CH3CHO) was measured
over the temperature range 700–1000 K, and the rate constants are reported below. Find Ea and A.

T/K 700 730 760 790 810 840 910 1000

k /(dm3 mol-1 s-1 0.011 0.035 0.105 0.343 0.789 2.17 20 145

Method According to Equation 5, the data can be analysed by plotting ln (k/dm3 mol−1 s−1) against
1/(T/K), or more conveniently (103 K)/T, and getting a straight line, we obtain the activation energy
from the dimensionless slope by writing −Ea/R = slope/units, where in this case ‘units’ = 1/(103
K), so Ea=−slope × R × 103 K. The intercept at 1/T = 0 is ln(A/dm3 mol−1 s−1).

Answer

We draw up the following table:

(103 K)/T 1.43 1.37 1.32 1.27 1.23 1.19 1.10 1.00
ln k /(dm3 mol-1 s-1 -4.51 -3.35 -2.25 -1.07 -0.24 0.77 3.00 4.98

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Figure 2.4: The Arrhenius plot using the data in Example

Exercise:
Determine A and Ea from the following data:

 The fact that Ea is given by the slope of the plot of ln k against 1/T means that, the higher
the activation energy, the stronger the temperature dependence of the rate constant (that is,
the steeper the slope). A high activation energy signifies that the rate constant depends
strongly on temperature. If a reaction has zero activation energy, its rate is independent of
temperature. In some cases the activation energy is negative, which indicates that the rate
decreases as the temperature is raised. We shall see that such behaviour is a signal that the
reaction has a complex mechanism.

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 The temperature dependence of some reactions is non-Arrhenius, in the sense that a straight
line is not obtained when ln k is plotted against 1/T. However, it is still possible to define
an activation energy at any temperature.

 This definition reduces to the earlier one (as the slope of a straight line) for a temperature-
independent activation energy. However, the definition in Equation 6 is more general than
Equation 5, because it allows Ea to be obtained from the slope (at the temperature of
interest) of a plot of ln kr against 1/T even if the Arrhenius plot is not a straight line.
 For simple reactions (for example, reactions between atoms), we can equate the frequency
factor (A) in the Arrhenius equation with the frequency of collision between the reacting
species.
 For more complex reactions, we must also consider the “orientation factor,” i.e., how
reacting molecules are oriented relative to each other.
Illustration: consider the reaction between carbon monoxide (CO) and nitrogen dioxide
(NO2) to form carbon dioxide (CO2) and nitric oxide (NO):
CO(g) + NO2(g) CO2(g) + NO(g)
 This reaction is most favourable when the reacting molecules approach each other
according to that shown in Figure 2.5(a). Otherwise, few or no products are formed
[Figure 2.5(b)].

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 Figure 2.5: The orientations of the molecules shown in (a) are effective and will likely
lead to formation of products. The orientations shown in (b) are ineffective
and no products will be formed.
 The quantitative treatment of orientation factor is to modify Arrhenius Equation (1) as
follows:
k = pAe-Ea /RT 7
 Where p is the orientation factor. The orientation factor is a unit-less quantity; its value
ranges from 1 for reactions involving atoms such as I + I I2 to 10-6 or smaller for
reactions involving molecules.
2.1.3 Limitations of the Collision Theory

(1) The theory applies to simple gaseous reactions only and for solutions in which the reacting
species exist as simple molecules.

(2) The values of rate constant calculated from the collision theory expression (Arrhenius equation)
are in agreement with the experimental values only for simple bimolecular reactions. For
reactions involving complex molecules, the experimental rate constants are quite different
from the calculated values.

(3) There is no method for determining the steric effect (p) for a reaction whose rate constant has
not been determined experimentally.

(4) In the collision theory it is supposed that only the kinetic energy of the colliding molecules
contributes to the energy required for surmounting the energy barrier. There is no reason why
the rotational and vibrational energies of molecules should be ignored.

(5) The collision theory is silent on the cleavage and formation of bonds involved in a reaction.

These drawbacks are not a concern in the modern transition-state theory.

2.2 Transition state theory/Activated complex theory

 Also called the absolute rate theory because with its help it is possible to get the absolute
value of the rate constant.
 Assumptions:

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 o Simple collision between the reactant molecules does not really causes a reaction.
During the collision, the reactant molecules form a transition state or activated
complex which decomposes to give the products. Thus,

 The climax of the reaction is at the peak of the potential energy, which corresponds to the
activation energy Ea. Here two reactant molecules have come to such a degree of closeness
and distortion that a small further distortion will send them in the direction of products.
This crucial configuration is called the transition state of the reaction.
 Some molecules entering the transition state might revert to reactants. However, if they
pass through this configuration then it is inevitable that products will emerge from the
encounter.
 Therefore, as stated earlier, a reaction involving the collision of two molecules, the
activation energy is the minimum kinetic energy that reactants must have in order
to form products.
 For example, in a gas-phase reaction there are numerous collisions each second, but only
a tiny proportion are sufficiently energetic to lead to reaction. The fraction of collisions
with a kinetic energy in excess of an energy Ea is given by the Boltzmann distribution as
e−Ea/RT.
 The transition state theory may be summarised as follows:

(1) In a collision, the fast approaching reactant molecules (A and BC) slow down due to gradual
repulsion between their electron clouds. In the process the kinetic energy of the two
molecules is converted into potential energy.
(2) As the molecules come close, the interpenetration of their electron clouds occurs which
allows the rearrangement of valence electrons.
(3) A partial bond is formed between the atoms A and B with corresponding weakening of B
– C bond. This leads to formation of an activated complex or transition state. The
activated complex is momentary and decomposes to give the products (A–B + C)

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  The activated complex theory may be illustrated by the reaction energy diagram (Figure
2.5).

Figure 2.6: Change of potential energy during a collision between the reactant molecules for an
exothermic reaction.

 The potential energy of the system undergoing reaction is plotted against the reaction
coordinate (the progress of the reaction). The difference in the potential energy between
the reactants and the activated complex is the activation energy, Ea. The reactants must
have this minimum energy to undergo the reaction through the transition state.
 From the energy diagram, energy is required by the reactants to reach the transition state.
Also, the energy is obtained in passing from the transition state to the products. If the
potential energy of the products is less than that of the reactants (Figure 2.6) the energy

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 obtained in going from the activated complex to products will be more than the activation
energy (Ea). Thus such a reaction will be exothermic.
 On the other hand, if the potential energy of the products is greater than that of the reactants,
the energy released in going from the activated complex to products will be less than the
activation energy and the reaction will be endothermic, Figure 2.7.

Figure 2.7: A potential energy diagram for an endothermic reaction.

2.2.1 Activation energy and catalysis

 We know that for each reaction a certain energy barrier must be surmounted. As shown in
the energy diagram shown in Figure 2.8, the reactant molecules must possess the activation
energy, Ea, for the reaction to occur.

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Figure 2.8: Energy diagram for a catalysed and uncatalysed reaction showing a lowering of
activation energy by a catalyst.

 The catalyst functions by providing another pathway with lower activation energy, E cat.
Thus a much large number of collisions becomes effective at a given temperature. Since
the rate of reaction is proportional to effective collisions, the presence of a catalyst makes
the reaction go faster, other conditions remaining the same.
 Note, from the above diagram that although a catalyst lowers the activation energy, the
energy difference, ΔE, between products and reactants remains the same.

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