1 1 .

3 FA C TO R S A F F E C T I N G R E A C T I O N R AT E

C H E M I S T RY U N I T
SK027
 CHAPTER 11: REACTION KINETICS
1 1 . 3 FA C TO R S A F F E C T I N G R E A C T I O N R AT E

OBJECTIVES:
1. Explain factors affecting reaction rate;
-Concentration / Pressure -Temperature
-Catalyst -Particle size

2. Explain the effect of temperature on reaction

rate using Maxwell-Boltzmann distribution
curve.

3. Explain the effect of catalyst on activation

energy based on energy profile diagram for
exothermic and endothermic reactions.
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 CHAPTER 11: REACTION KINETICS
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OBJECTIVES:

4. Relate rate constant to temperature and

activation energy using the Arrhenius equation.
k = Ae-Ea/RT or ln k = ln A –Ea/RT

5. Determine k, Ea, T and A using Arrhenius

equation by calculation and graphical method.

 k1  Ea  1 1 
ln  =  − 
 k 2  R  T2 T1 

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 CHAPTER 11: REACTION KINETICS
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Factors affecting Reaction Rate

a) Effect of Concentration
o When concentration of reactant increases, frequency
of collision also increases.
o More particles present in the same volume, they are
more likely to collide
o The probability of effective collisions increase
frequency of effective collision =
collision frequency × fraction of molecules with
sufficient energy
o Rate of reaction increases.
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 CHAPTER 11: REACTION KINETICS
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Effect of Concentration

[reactants] increases, the frequency of collision increases.

5 particle system
4 particle system
(3 and 2)
6 collision
(2 and 2)
4 collision

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 CHAPTER 11: REACTION KINETICS
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Effect of Concentration
o This observation correlates with the RATE LAW that
has been previously discussed…
x y
Reaction rate = k [ A ] [ B ] …
(A & B = reactants)
(x & y = rate order)
o Based upon this equation,
Reaction rate ∝ concentration of reactants
(depending on its rate order)
o REMINDER!
Only in zero order reactions, the rate of reaction is not
dependant upon the concentration of the reactants.
Reaction rate = k [ A ]0 = k (constant)
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 CHAPTER 11: REACTION KINETICS
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Effect of Temperature

o At a higher temperature, molecules have higher

kinetic energy and move at higher speed
o more collisions will occur in a given time
o Furthermore, the higher the KE, the higher the
energy of the collisions
o So more molecules will have energy greater than Ea
o effective collision also will be increased
o thus the reaction rate increases.

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CHAPTER 11: REACTION KINETICS
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Distribution of Kinetic Energies of Molecules
(Maxwel-Boltzmann Distributions)

The collision frequency

is higher at higher
temperature because
the fraction of
reactant molecules
with activation energy
is higher.

Ea
 CHAPTER 11: REACTION KINETICS
1 1 . 3 FA C TO R S A F F E C T I N G R E A C T I O N R AT E

Maxwel-Boltzmann Distributions

• The figure shows the distribution KE of gaseous

molecule at temperature T1 and T2.
• At higher temperature, the fraction of molecules
with energy greater than Ea increases.
• Thus, rate of reaction increase with increase of
temperature.

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 CHAPTER 11: REACTION KINETICS
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Maxwel-Boltzmann Distributions
Take note:
• Area under the curve ∝ to the total number of
molecules
area under the curve is the same, bcoz no. of molecules
is the same.
• There are a wide range of molecular energy
A few molecules have low and high KE, most have value
in the middle.
• The shape of the graph changes with temperature
At higher temperature the peak of the graph moves
towards the right to a higher KE value as the curve
broadens out.
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 CHAPTER 11: REACTION KINETICS
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Maxwel-Boltzmann Distributions
Take note:
• At higher temperatures, the fraction of molecules
with higher energy increase
Average energy increase at higher temperature, but
fraction of molecules with low energy decreases.
At higher temperature, fraction of molecules with energy
greater than Ea increase

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 CHAPTER 11: REACTION KINETICS
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Effect of Temperature
ARRHENIUS EQUATION
• the effect of temperature on the rate constant, k:
-Ea⁄
k = A e RT
Where…
k = rate constant
A = frequency factor
(is a measure of the probability of a favorable collision)
e = natural log exponent
Ea = activation energy for the reaction (kJ/mol)
R = universal gas constant (8.314 J mol-1 K-1)
T = absolute temperature (T in Kelvin)
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 CHAPTER 11: REACTION KINETICS
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Effect of Temperature

ARRHENIUS EQUATION The relationship between

-Ea⁄ k and T.
k = Ae RT

Rate constant, k
The equation shows;
k↑ ↑A

k↑ ↓ Ea
T
k↑ ↑T
T↑ k↑ rate ↑
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CHAPTER 11: REACTION KINETICS
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ARRHENIUS EQUATION - DERIVATION

−Ea
k = Ae RT Plot ln k vs 1/T
−Ea ln A
ln k = ln (A.e RT
)
ln k Slope = Ea/R
Ea
ln k = ln A -
RT

Ea  1 
ln k = ln A −  
R T
1/T
y = C + mx
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 CHAPTER 11: REACTION KINETICS
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Example:
The table below gives the rate constants, k for the
reaction between potassium hydroxide and
bromoethane at different temperatures.

a) Using a graphical method, calculate

k(M-1s-1) T (K)
the activation energy (kJmol-1) for this
0.63 322 reaction.
2.50 331 b) What is the overall order of reaction?
Explain
10.0 347
c) Calculate the initial rate of reaction
22.6 353 at 330 K when the concentrations for
both KOH and CH3CH2Br are 0.1M
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Solution: 1/T 0.0031 0.0030 0.0029 0.0028

ln k -0.46 0.92 2.30 3.12
Plot ln k vs 1/T

3.5
3
a) Slope = Ea/R
y = -12492x + 38.45
2.5 = 12492
Ea = 12492 × 8.314
2
1.5
ln k

1
0.5
= 1.04 ×105 Jmol-1
0 = 104 kJmol-1
-0.5
0.0028 0.0029 0.003 0.0031 0.0032
-1 b) Second order,
1/T
unit of k = M-1s-1
− Ea 1
c) ln k = ( ) + ln A
Rate = k [KOH][CH3CH2Br]
R T
1
ln k = − 12492 ( ) + 38 . 45 = 1.81 x 0.1 x 0.1
330
-1
k = 1.81 M s -1 = 1.81 x 10-2 Ms-1
 CHAPTER 11: REACTION KINETICS
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ARRHENIUS EQUATION – FURTHER DERIVATION

Rate constant, k varies with T.
The ratio of rate constant at two different T can be calculated.
Ea
ln k 1 = ln A − (1)
RT 1
Ea
ln k 2 = ln A − (2)
RT 2
Equation (1) minus (2) gives;

 k1  E a  1 1 
ln   =  − 
 k2  R  T 2 T1 

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 CHAPTER 11: REACTION KINETICS
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Exercise
1. For the reaction NO2Cl + NO → NO2 + NOCl, the
frequency factor is 8.3 ×108 dm3mol-1s-1 and Ea is 28.9
kJmol-1. At 25°C the reaction is first-order with respect to
NO2Cl and first-order with respect to NO, what is the rate
constant for the reaction. (7.13 ×103dm3mol-1s-1)
2. For the reaction HI + CH3I →CH4 + I2, the rate constant is
1.7 × 10-5 mol-1dm3 s-1 at 430 K and 9.6 × 10-5 dm3mol-1s-1 at
450 K. Calculate the activation energy for the reaction.
(139 kJmol-1)
3. The rate constant for the reaction C4H8(g) →2C2H4(g) is
3.2 × 10-2 s-1 at 527oC. Calculate the rate constant at 577oC
if the activation energy for the reaction is 260 kJmol-1.
(3.2 x 10-1 s-1)
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 CHAPTER 11: REACTION KINETICS
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Exercise
4. In the presence of platinum as a catalyst, hydrogen iodide
decomposes to form hydrogen and iodine. The activation
energy for this reaction is 58 kJ mol-1. Calculate the ratio
of the rate constant at 30oC and 20oC. k 1 = 0.46
k2
5. Hydrogen iodide decomposes on heating according to the
equation ; 2HI(g) → H2(g) + I2(g)
At 227oC, the rate constant of the reaction is 5.71 ×10-7
dm3mol-1min-1. At 327oC, the rate constant is 6.6 ×10-4
dm3mol-1min-1. (176 kJ/mol)
a) Calculate the activation energy, Ea for this reaction.
b) The Ea of a certain reaction is 148 kJ mol-1. How many
times does the rate of reaction increases when the temp.
changes from 37oC to 47oC? (6X)
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Effect of Catalyst

• A catalyst is a substance that increases the

rate of a chemical reaction without itself being
consumed.
• It increases the reaction rate by providing an
alternative reaction pathway of which having
lower activation energy.
• A catalyst provides a different reaction
mechanism

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 CHAPTER 11: REACTION KINETICS
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A catalyst provides an alternative pathway for the reaction

to occur (----curve) which has a lower activation energy.

Ea (without catalyst)
Potential energy

Ea (with catalyst)

Reaction progress
When Ea decreases, k increases, reaction rate increases
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Effect of Surface Area

• For reactions that occur on a surface that is

for solid, the rate increases as the surface
area is increased.
• A larger surface area increases the contact
area between the reactants thus increases
the frequency of collision and the probability
of effective collision between the molecules
of the reactants.

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 CHAPTER 11: REACTION KINETICS
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Exercise
6. The results of the decomposition of N2O5 at two different
temperature were recorded as;
Temperature(K) rate constant, k (s-1)
298 1.74 × 10-5
308 6.61 × 10-5
a) Base on the unit of the rate constant, k, determine the
order of the reaction. (1st)
b) Find the value of Ea and A for the reaction (102 kJmol-1)
c) What would happen to the reaction if a catalyst were
added? (Rate increases)
d) How does a catalyst work?

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