KENYATTA UNIVERSITY

KITUI CAMPUS
SCH 330
UNIT 3
Dr. Lilian Gatogo

1
Course Purpose:
• To introduce the concepts of reaction kinetics and
reaction mechanisms

Objectives:
By the end of the course, the learner should be able
to describe:
• Reaction rates, rate laws and rate constants
• Factors affecting the rate of a chemical reaction
• Reaction mechanism for a given chemical
reaction

2
 Outline
• Types of reactions
• Rate equations
• Order of reactions
• Methods of determining rates and orders of
reaction of chemical reactions
• Integrated rate law and half life
• Dependence of reaction rate on temperature
• Qualitative treatment of Boltzmann factor
• Reaction mechanisms
3
 Collision Theory of Reaction
Rates/Molecular Activation
• Uses kinetic molecular theory

• Applicable to gaseous reactions

• Collision model: reactants react because they

collide;
– A and B; must collide.
– A+B+C; must collide

4
 Collision Theory of Reaction
Rates
• Essential requirements for reactions to occur
– Collision between reactant molecules
– Activation of molecules; activated complex
– Proper orientation of the reacting
molecules at the time of collision
• Successive collision

5
 Cont,
– To increase reaction rate, increase collision
rate.
– Increasing the temperature increases
molecular velocities thus increasing
collisions
• The reaction rate therefore depends on
frequency of collisions and probability of
reaction occurring upon collision (orientation).

6
 Factors Affecting Rate
• Concentration of reactants:
– Number of molecules with minimum required
energy increases (activation energy)
– The higher the concentration the higher the
frequency of collisions which increases the
rate
• Energy of collisions (Temperature Effect)
– Energy is needed to break bonds in reactants,
leading to the formation of new bonds.
• Catalysts:
7
The Effect of Temperature on Reaction
Rate
• Lizards become lethargic when their body
temperature drops; the chemical reactions
that control muscle movement slow down
at low temperatures
• Rates of chemical reactions highly
sensitive to temperature
• At Room Temperature, a 10 oC increase in
temperature increases the rate of a typical
reaction by two or three times
8
Cont,
• Rate = k [A]n
• Rate constant is affected by changes in
temperature.
• An increase in temperature results in an
increase in k resulting in a faster rate
• This is quantified by Arrhenius equation

 Ea / RT
k = Ae
9
 Temperature Dependence
 In 1888, Arrhenius noted that the increase in rate
with temperature fitted the Arrhenius equation
 Ea / RT
k = Ae
Where:
• k rate constant
• R: universal gas constant (8.314 J/mol.K)
• T: temperature (K)
• Ea activation energy/energy barrier
• A: collisional frequency factor; pre-
exponential factor; Arrhenius factor
• The parameter A(/s) and Ea(kJ/mol); are referred
to as Arrhenius parameters 10
 Cont,
• The activation energy Ea energy barrier or a
hump that must be overcome for the reactants
to be transformed into products.

11
 Cont
• To get to the products, the reactant must go
through an activated complex or transition state.
• The energy required to create the activated
complex is the activation energy
• Activation Energy (Ea):
– Ea is the minimum energy of molecular collisions
required to break bonds in reactants, resulting in
formation of products.
• The higher the activation energy, the higher the
energy barrier, the slower the rate of the reaction
(at a given temperature)
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 Cont,
 The temperature dependence can be explained by
assuming the existence of an energy barrier

Reactants
Products

 For two reacting molecules to react when they collide, they

must have sufficient energy to overcome the energy barrier
and pass through the TS.
 Ea; minimum kinetic energy that reactants must have in
order to form products 13
 Cont,
• Holds well nearly for all elementary
homogeneous reactions and for most
composite reactions
• Two colliding molecules require a certain
minimum kinetic energy to initiate breaking of
bonds; activation energy
– A low activation energy means a fast reaction
– A high activation energy means a slower
reaction
• Note; as the magnitude of Ea increases, k
becomes smaller, thus reaction rates
decrease as the energy barrier increases 14
 Cont,
• The rate constant increases as the temperature
is raised e.g. for methyl ethanoate; k at 35 oC is
1.82 times that at 25 oC
• Ea is given by the slope for a log form of
equation
• Therefore the higher the activation energy, the
stronger the temperature dependence of the
rate constant
• Zero activation energy; rate is independent of T
• Negative activation energy, rate decreases as T
is raised (complex mechanisms)
15
 Temperature Dependence of
Reaction Rates
– Increased temperature increases kinetic
energy of molecules and molecules with
minimum energy to react

– This increases the velocity & therefore the

probability of molecular collisions.

– Increase in molecular collisions increases

the reaction rate
16
  Ea / RT
k = Ae
• The Frequency Factor (A)
– The number of approaches to the activation barrier
per unit time
– Any time a bond begins to rotate or vibrate, it
approaches the activation barrier
– With each vibration, the reactant approaches the
activation barrier
• Remember; the approach will require enough energy to
make it over the energy barrier

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 The Exponential Factor
• Exponential factor (e -Ea/RT) a number btn 0-1
• Represents the fraction of molecules that have
enough energy to make it over the activation
barrier on a given approach
• Fraction of approaches that are actually
successful and result in the product
• E.g. if A = 109/s and exponential factor is 10-7 at
T, overall rate constant = 102/s. only 1 in 10 7
molecules have sufficient energy to make it over
the activation barrier (=A e -Ea/RT)
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 Cont,
• The exp factor depends on T and Ea
• A low activation energy and a high temperature
make the negative exp small
• If Ea = 0, then Exp is zero, the factor = 1
• By contrast, a large activation energy and a low
T, makes the exponent a very large number, and
the exponent becomes very small
• Example; at T = 0, exponent approaches
infinitely large number, exponential factor
approaches zero
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• As the temperature increases, the number of molecules
having enough thermal energy to surmount the
activation barrier increases
• At any given temperature, a sample of molecules of
molecules will have a distribution of energies

Step 1
T(lower) = 25 oC; lower KE
T(higher) = 35 oC; higher KE
T lower; normal/gaussian
distribution
Step 2; relation of molecules with
temperatures/activation energy
Ea = 50 kJ/mol
Step 3; identify the number of
molecules with activation energy

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21
• Under common circumstances, only a small
fraction of the molecules have enough energy to
make it over the activation barrier
• But, a small change in temperature will result in
a large difference in the number of molecules
having enough energy to overcome the barrier

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 Cont,
 The fraction of collissions with a kinetic energy in
excess of Ea is given by Boltzmann distribution
as e -Ea /RT
 Hence -Ea /RT is the fraction of collissions that have
enough kinetic energy to lead to reaction
 A = empirical frequency factor (preexponential
factor); measure of rate at which collissions occur
irrespective of their energy
 Hence A and the exponential factor e -Ea /RT gives
the rate of successful collisions
 Ea / RT
Ae
23
Cont,
• Boltzmann statistics tell us; An increase in
temperature increases the probability of
molecules having enough energy to cross
the transition state. Fraction of collisions
that have Ea or greater

24
 Conclusion
• The frequency factor is the number of times
that the reactants approach the activation
barrier per time
• The exponential factor is the fraction of
approaches that are successful in surmounting
the activation barrier and forming products
• The exponential factor increases with
increasing temperature but decreases with an
increasing value for the activation energy
25
 Arrhenius Plots
• Enables experimental measurements of the
frequency factor (A) and the activation energy
(Ea)
• k = Ae -Ea/RT
• lnk = lnA + ln (e -Ea/RT)
• lnk = - (Ea/R) (1/T) + ln A
• y = mx + c
• Plot of ln k versus (1/T) yields a straight line
– Slope ; - Ea /R
– Intercept; ln A
• Such a plot is called an Arrhenius plot 26
 Arrhenius Plots
• lnk = - (Ea/R) (1/T) + ln A

• Log k = – Ea / (2.303 RT) + log A

• Plot of Log k versus (1/T) is a straight line

– Slope; – Ea / 2.303R
– Intercept; log10 A

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Graphical Determination of Ea
 Ea 1
ln k     ln A
R T 

Slope = −Ea/R
Intercept = ln A

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 Graphical Determination of Ea
Log10 k = log10 A – Ea/ (2.303RT)
log10 A Plot of Log10 k versus (1/T)
Slope = −Ea/2.303 R
Intercept = log10 A
log10 k

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 Mathematical Determination of Ea
• Need to know rate constant (k) values at 2
different temperatures:

ln k1 ln A  E a / RT1 ln k 2 ln A  E a / RT2

ln k1  ln k 2 (ln A  E a / RT1 )  (ln A  E a / RT2 )

ln (k1/k2) = Ea/R (1/T2 – 1/T1)

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 Application
1. The value of rate constant for the
decomposition of nitrogen pentoxide (N2O5 →
N2O4 + ½ O2 ) is 3.46 x 10 -5 at 25 oC and 4.87 x
10 -3 at 65 oC. Calculate the energy of
activation for the reaction
2. A second-order reaction in solution has a rate
constant of 5.7 x 10 -5 dm3 mol-1 s-1 at 25 oC and
of 1.64 x10-4 dm3 mol-1 s-1 at 40 oC. Calculate
the activation energy and the preexponetial
factor, assuming the Arrhenius equation apply
3. Calculate Ea for a reaction whose rate constant
at room temperature is doubled by a 10- oC
increase in T.
31
4.The rate of a second order decomposition of
acetaldehyde (ethanal) was measured over
temperature range 700-1000K, and the rate
constants are reported below. Find Ea and A.
T/K 700 730 760 790 810 840 910 1000
k/(L mol -1 s-1) 0.01 0.03 0.105 0.343 0.789 2.17 20.0 145
• 1 5

• Graph lnk vs 1/T

• Slope; =-Ea /R = -2.27 x 104
• Ea = slope x R= -2.27 x 104 K x 8.314 TK-1mol-1 =
188 kJmol-1 (same as those for RT)
• lnA = intercept = 27.7 (least square analysis)
• A = e 27.7 L mol -1 s-1 (units of k) 32
Cont,
• A can also be calculated from
 Ea 1
ln k     ln A
R T 

• If extrapolation can not be achieved (use a

mid range figure)

33
5.For the reaction C2H5I + OH- → C2H5OH + I-
The rate constant data versus T are
10 4k/(L 0.503 3.68 67.1 1190
Mol 1 s-1)
lnk 8.5 10.5 15.01 16.2
1/T 3.46 x 10 - 3.27 3.00 2.7
3
T/k 289.0 305.2 332.9 363.8

Use a graph to find Ea and A for this reaction. 34

 Transition State Theory
Review:
An activated complex forms between
reactants as they collide and begin to
assume the nuclear and electronic
configurations characteristic of products.

The change in potential energy associated

with formation of the activated complex
accounts for the activation energy of the
reaction.
35
 Transition State Theory
• Its an attempt to identify the principal features
governing the size of a rate constant in terms
of a model of the events that take place
during the reaction.
• Postulates that a hypothetical transition state
occurs between reactants and products
• The hypothetical distance between the reactants
and products is known as the Transition State
• Activated complex; high-energy species that is
formed during the transition state of a chemical
reaction 36
 Transition State Theory
• Postulates 3 major factors for a reaction to
occur
– Concentration of the activated complex
– The rate at which the activated complex
breaks apart
– Mechanism by which the complex breaks
apart
• It can be used to calculate
– Standard enthalpy of activation
– Standard entropy of activation
– Gibbs energy of activation
37
38
 Cont,
• Transition state AB*;
– State with highest energy during reaction;
– Chemicals bonds are cleaved and rearranged.
– Rate limiting step = product formation with k*
– Equilibrium constant K*

39
 Application in Biochemistry
• Useful in modelling reactions catalysed by
enzymes in the body
• By knowing the possible transition states that
can form in a given reaction and the various
activation energies for each transition state,
one can predict the course of a biochemical
reaction
– Reaction rate
– Rate constant

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