10.

3 Factors Affecting Rate of Reactions

Objectives
At the end of the lesson the students should be able
to:
1. Explain reaction rates in terms of collision
theory.
2. Identify factors affecting the effectiveness of
collision.
3. Define activation energy.
4. Define and state the characteristics of an
activated complex
 Medications

Why do you think

that certain pills are
found as small
spheres of the
medication inside a
soluble capsule?
 Medications

The more surface

area the medication
has, the faster it will
react. These small
spheres allows more
surface area and a
faster reaction.
 Why do we refrigerator our foods in terms
of the collision theory?

If we lower the temperature

of the food, then the decay
reactions will slow down.
The colder the molecules
are, the less energy they
have to collide and thus
the less effective collisions
are.
 Dangerous Habit
What is especially
dangerous about this
smoking situation?
The man has an
oxygen mask (30%)
over his nose and
mouth. Describe the
dangers in terms of
the collision theory.
 Dangerous Habit
The man is breathing in
more concentrated
oxygen. Since oxygen
is needed for
combustion, combustion
will proceed faster with
a higher concentration
of O2. This could cause
a serious fire with the lit
cigarette.
Factors Affecting Rate of Reactions
1. Nature of the reactants complexity of
the molecules; states of matter
2. surface area
3. temperature
4. concentration
5. catalysts
 Effect of concentration on the rate of
reaction
Change in the [ ] of reactants change the number
of particles per unit volume and increase the
number of collisions per unit time in that volume.

If [ ] is doubled the number of collisions would

also doubled, because in any given volume there
would be twice as many molecules that could
collide.

Consequently the rate would increase by a factor

of 2.
 According to the collision theory, an
increase in the number of collisions will
bring an increase in the rate of reaction.

Number of molecular collisions is

proportional to the concentration.
 Example:

Magnesium reacts with dilute hydrochloric acid

according to the equation:
Mg(s) + 2HCl(aq) MgCl2(aq) + H2(g)
When the concentration of hydrochloric acid
increases, the rate of reaction also increases.
 When the concentration of hydrochloric acid
increases, the number of particles per unit
volume also increases and the particles are
closer together.

Same
volume

When the number of particles increases, the

frequency of collisions also increases. As a result,
the frequency of effective collisions increases. This
causes the rate of reaction to increase.
Effect of pressure on the rate of reaction
 Effect of pressure on the rate of reaction

Example: N2(g) + O2(g) 2NO(g)

The rate of reaction between nitrogen and
oxygen to produce nitrogen monoxide can be
increased by increasing the pressure.

Number of particles
same
At high pressures,
the number of gaseous molecules per unit volume
is increased and the gaseous molecules are
packed closer together.
causes the gaseous molecules to collide more
frequently.
Consequently, the frequency of effective
collisions increases and the rate of reaction also
increases.

Number of particles
same
Effect of temperature on the rate of reaction
The higher the temperature the higher the rate
of reaction
Example: Calcium carbonate reacts with
hydrochloric acid to form carbon dioxide
according to the following equation:
CaCO3(s) + 2HCl(aq) CaCl2(aq) + H2O(l) +
CO2(g)
 When the temperature is increased, the particles
absorb the heat energy. As a result, the kinetic
energy of the particles increases. Hence,
(a) the reacting particles move faster, and
(b) the number of reacting particles with the
activation energy required increases.
Consequently, the frequency of effective
collisions increases and hence, the rate of
reaction also increases.
 Kinetic energy distributions for a reaction mixture at
two different temperatures.

Ea
Maxwell-Boltzmann speed distribution for a gas at temperature
T1 and temperature T2,
 Maxwell-Boltzmann distribution defines the
distribution of the different kinetic energies of
particles in a system.

Note that the curve flatten at the higher

temperature.

The shaded areas represent the number of

molecules traveling at a speed equal to or greater
than activation energy, Ea.
 The higher the temperature, the greater
the number of molecules moving at high
speed.

Only fast-moving molecules have sufficient

kinetic energy to overcome the activation
energy.
 Effect of catalysts on reaction rates
A catalyst is substance that increases the rate of
a chemical reaction without itself being
consumed.
Increase the rate of a chemical reaction by
providing an alternative reaction pathway with a
lower activation energy.
 Effect of catalysts on reaction rates
Example: The decomposition of hydrogen
peroxide to water and oxygen occurs very slowly
at room temperature.
2H2O2(aq) 2H2O(l) +O2(g).
In the presence of a catalyst, the decomposition
of hydrogen peroxide occurs rapidly.
 A catalyst provides an alternative reaction route
(or pathway) for the reaction to occur.
An alternative route has a lower activation
energy.
As a result, more reacting particles possess
sufficient energy to overcome the lower
activation energy required for effective collisions.

Hence, the
frequency of
effective collisions
increases and the
rate of reaction
increases
Addition of a catalyst increases the reaction rate
by increasing the frequency of effective collision.
That is by
Decreasing the Ea, and
Correct orientation

Example : surface-catalyzed reaction

Adsorption of Diffusion of reactants Formation of

reactants along the surface product
In a surface-catalyzed reaction, almost all the
catalysts surface is covered by adsorbed
molecules.
Molecules that are adsorbed on a surface are
thus closer to each other.
Its easier for the electron clouds of these
molecules to interact and bonds to form or
break.
The molecules need not possess a minimum
kinetic energy for an effective collision to take
place.
Comparison of the activation energy of the catalyzed and
uncatalyzed reactions
 Effect of surface area on the reaction rate
The smaller the size of reacting particles, the
greater is the total surface area exposed for
reaction and consequently the faster the
reaction.

In the case of heterogeneous systems, in which

the reactants are in different phases, the area of
contact between the reacting substances will
influence the reaction rate
 Effect of surface area on the reaction rate
The sodium chloride crystal as shown in Figure (a) has a
surface area of 16 cm2. Surface area of the NaCl crystal
=(1 x 2) x 4 + (2 x 2) x 2 =16cm2
When this crystal is divided into smaller crystals as shown
in (b), the total surface area is increased to 24 cm2.
The greater the surface area of a solid, the higher the reaction
rate.
A greater area causes a greater frequency of collisions, thus
increasing the reaction rate.
 Example:
In the reaction between hydrochloric acid and marble chips
(calcium carbonate),
CaCO3(s) + 2HCl(aq) CaCl2(aq) + H2O(l) + CO2(g)
The rate of reaction will increase if powdered marble is
used instead of marble chips.
 The total surface area is larger in powdered
marble.
With greater surface area exposed for reaction
with the acid collisions between reacting
molecules become more frequent.
This means that the frequency of effective
collisions (that is, collisions with the correct
orientation and with energy equal to or greater
than activation energy) between reacting
particles will increase.
As a result, the rate of reaction also increases.
Relating the frequency of effective collisions
with factors influencing the rate of reaction
According to the collision theory, two important
factors that determine the rate of a chemical
reaction are:
(a) the frequency of effective collisions and
(b) the magnitude of the activation energy

In general, any factor that increases the rate

of effective collisions will also increase the
rate of reaction.
Relating the frequency of effective collisions
with factors influencing the rate of reaction
1 Frequency of effective collisions
For a given reaction, if the frequency of
collisions between reactant molecules is high,
it follows that the frequency of effective
collisions that causes a reaction to occur will
also be high.
As a result, the rate of reaction increases.
 Relating the frequency of effective collisions
with factors influencing the rate of reaction
2 Magnitude of activation energy
Reactions that have high activation energy will
occur at a slow rate. This is because only a
small fraction of the molecules possess
sufficient energy to overcome the activation
energy for the reaction to occur.
 Relating the frequency of effective collisions
with factors influencing the rate of reaction
2 Magnitude of activation energy
In contrast, reactions that possess low
activation energy will occur at a fast rate.
This is because most of the molecules have
sufficient energy to overcome the activation
energy.
The frequency of effective collisions that
causes a reaction to occur will also be high.
 The Arrhenius Equation

The dependence of the rate constant of a reaction on

temperature can be expressed by the following
equation known as Arrhenius equation.
Ea = activation energy
Ea k = rate constant
k=A e RT R = gas constant
T = absolute temperature
e = the base of the natural
logarithm scale
A = quantity represents the collision
frequency (frequency factor)
By taking the natural logarithm of both sides.
ln k = ln Ae -Ea/RT
ln k = ln A Ea/RT
The equation can take the form of a linear equation

ln k =(
E a
1
) ( ) + ln A
R T
y x c
m
1
A plot of ln k versus gives a straight line
T
Slope m =
Ea and intercept c with the y axis is ln A.
R
 Example
The rate constants for decomposition of acetaldehyde
2HI(g) H2(g) + I2(g)
were measured at five different temperatures. The data
are shown below. Plot ln k versus 1/T, and determine
the activation energy (in kJ/mole) for the reaction.

k (1/M s) T (K)
3.52 x 10-7 283
3.02 x 10-5 356
2.19 x 10-4 393
1.16 x 10-3 427
3.95 x 10-2 508
 Solution
We need to plot ln k on the y-axis versus 1/T
on the x-axis. From the given data we obtain
ln k 1/T (K-1)
14.860 3.53 x 10-3
10.408 2.81 x 10-3
8.426 2.54 x 10-3
6.759 2.34 x 10-3
3.231 1.97 x 10-3
 ln k

-2

-4

-6

-8 y

-10

-12

-14
x
-16
x 10-3
1.0 2.0 3.0
1/T(K-1)

Plot of ln k versus 1/T. The slope of the line is

calculated from two pairs of coordinates.
 Slope = (-14.860) (-3.231) = -7454.5 K
(3.53-1.97) x 10-3 K-1

Finally, calculate the activation energy from the

slope:

The slope, m = Ea/R.

Ea = R (m)
= (8.314 J K-1 mol-1) (-7454.5 K)
= 61976.6 J mol-1
= 61.976 kJ mol-1
 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.

Ea 1 Ea 1
ln k1 ( ) ln A and ln k 2 ( ) ln A
R T1 R T2

Rearranging the equations would give

Ea 1 Ea 1
ln k1 ( ) ln A ln k 2 ( ) ln A
R T1 R T2
Since A is a constant
Ea 1 Ea 1
ln k1 ( ) ln k2 ( )
R T1 R T2

Ea 1 Ea 1
ln k1 ln k2 ( ) ( )
R T2 R T1

k1 Ea 1 1
ln ( )
k2 R T2 T1
 Example
The rate constant of a first-order reaction is 3.46 x
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/mole?
Solution
Given
k1 = 3.46 x 10-2 s-1 k2 = ?
T1 = 298 K T2 = 350 K

Substituting in equation
k1
= Ea 1 1
ln
k2 R T2 T1
ln 3.46 x 10-2 = 50.2 x 103 J/mol 298K 350K
k2 8.314 J/K mol (298K)(350K)

Solving the equation gives

ln 3.46 x 10 -2 = 3.01
k2
3.46 x 10 -2 = 0.0493
k2
k2 = 0.702 s 1
 Exercise: the Activation energy
The decomposition of hydrogen iodide,
2 HI (g) H2(g) + I2(g)
has rate constants of 9.51 x 10-9 L mol-1 s-1
at 500 K and 1.10x10-5 L mol-1 s-1 at 600 K.
Find Ea.

( Ea = 1.76 x 105 J/mol = 176 kJ/mol )

 Arrhenius Equation

The ratio of rate constant at 2 different

temperatures
Conclusion : Factors affecting rate of reaction
CONCENTRATIONS OR PRESSURE OF
REACTANTS:
Reaction rates generally increase as the
concentrations of the reactants are increased.
TEMPERATURE:
Reaction rates generally increase rapidly as the
temperature is increased.

CATALYSTS:
Catalysts speed up reactions.

PARTICLE SIZE:
The rate increases as the smaller the size of
reacting particles .
 change Effect of the Effect on the
rate of reaction rate constant
Increasing [ ] Increases No effect
Decreasing [ ] Decreases No effect
Increasing P Increases No effect
Decreasing P Decreases No effect
Increasing T Increases Increases
Decreasing T Decreases Decreases
Addition of catalyst Increases Increases