1 Reaction Kinetics

TOPIC 1: REACTION KINETICS
CHAPTER 1.0: REACTION KINETICS
MAPPING COGNITIVE
TOPIC SUBTOPIC LEARNING OUTCOMES DOMAINS
C1 C2 C3 C4
a) Define reaction rate √
b) Write differential rate equation √
c) Determine reaction rate based on differential rate equation of a
√
reaction
d) Define rate law, order of reaction and half life √
1.1 Reaction
e) Write rate law with respect to the order of reaction √
Rate f) Write the integrated rate equation for zero, first and second order
√
reactions
g) Determine the order of reaction involving single reactant using:
i. Initial rate method
ii. Half-life based on graph of concentration against time √ √
iii. Linear graph method based on the integrated rate equation
and rate law
h) Perform calculation using integrated rate equations √
a) Explain collision theory √
Reaction
Kinetics 1.2 Collision b) Define activation energy √
Theory c) Explain transition state theory √
d) Draw energy profile diagram of a reaction √
a) Explain the effect of the following factors on the reaction rate:
i. Concentration or pressure
ii. Temperature √
iii. Catalyst
iv. Particle size
b) Illustrate the effect of temperature on the reaction rate using Maxwell
1.3 Factors √ √
Boltzmann Distribution curve
Affecting c) Compare the curve of the energy profile diagram for a reaction with
Reaction Rate √
and without catalyst
d) State Arrhenius equation √
e) Explain the relationship between temperature and activation energy to
√
the rate constant based on Arrhenius equation
f) Determine k, Ea, T and A using Arrhenius equation by calculation and
√ √
graph
CHAPTER 1  REACTION KINETICS page 1

MAPPING COGNITIVE
SUBTOPIC LEARNING OUTCOMES DOMAINS
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a) Define reaction rate √
1.1 Reaction b) Write differential rate equation √
Rate c) Determine reaction rate based on differential rate equation of a
√
reaction
INTRODUCTION
 Chemical kinetics is the area of chemistry concerned with the speeds or

rates at which chemical reactions occur
 Kinetics refers to movement or change during a reaction
RATE OF REACTION
 Definition: Reaction rate is the change in the concentration of a reactant or

a product with time
 Besides concentration, reaction rates also studied by monitoring change in
 volume
 pressure
 pH
 colour intensity
 A reaction rate (r) is a positive quantity
rate = (final concentration) – (initial concentration)

time
= Δ (concentration) mol L-1

=
Δt time

Consider the following reaction:

A  B
 During the course of reaction, reactant molecules are consumed while
product molecules are formed
 As a result, [A] decreases and [B] increases with time
concentration
concentration of B
concentration of A
time
 reaction rate = concentration change

time
= + d[B] =  d[A]
dt dt
 unit of reaction rate is M time1
(time can be in second, minute etc.)
 Reaction rate is inversely proportional to time.

 The shorter the time taken for the reaction to progress, the higher the rate
of reaction.

The differential rate equation
Definition: The relationship between the rate of disappearance (or depletion) of

reactant(s) and the rate of appearance (or formation) of product(s).
For the reaction A  B
rate =  d[A] = + d[B]

dt dt
For the reaction 2C  D
rate =  1 d[C] = + d[D]

2 dt dt
Generally, for the reaction:

aA + bB  cC + dD
a, b, c and d are the stoichiometry coefficient
the rate expression is:
Exercise:
1. Write the differential rate equation
a) N2(g) + 3H2(g)  2NH3(g)
b) 2SO2(g)  2SO(g) + O2(g)

2. Consider the reaction between Zn and AgNO to form Zn(NO ) and Ag.
3 3 2
Zn(s) + 2AgNO (aq)  Zn(NO ) (aq) + 2Ag(s)
3 3 2
a) Write the differential rate equation for the above reaction.
2+ -1 +
b) When [Zn ] is increasing at 0.25 Ms , what is the rate of decrease of [Ag ]?
3. For the reaction 2HI(g)  H2(g) + I2(g), determine the rate of disappearance of
HI when the rate of I2 formation is 1.8106 M s1.

4. Nitrogen monoxide reacts with oxygen gas as follows:

4NO(g) + O2(g)  2N2O3(g)
During an experiment at fix temperature, the concentration of NO is decreasing
at the rate of 1.60104 M s1. Calculate the rate of
a) concentration decrease in O2
b) N2O3 formation
5. Consider the reaction between Mg and HCl to form MgCl2 and H2.
Mg(s) + 2HCl(aq)  MgCl2(aq) + H2(g)
a) Write the differential rate equation for the above reaction.
b) When [H2] is increasing at 0.32 Ms-1, what is the rate of decrease of HCl?

MAPPING COGNITIVE
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1.1 Reaction d) Define rate law, order of reaction and half life √
Rate e) Write rate law with respect to the order of reaction √
RATE LAW / RATE EQUATION
 The rate law or rate equation is an equation that relates the rate of reaction
to the rate constant, k and concentration of the reactants raised to some
powers.
Consider:
A + B  products
Rate  [A]x [B]y
 The rate law Rate = k[A]x[B]y
where: [A] and [B] = concentrations in Molar
k = rate constant
x = order with respect to A / order in A
y = order with respect to B / order in B
x+y = overall reaction order
RATE CONSTANT (k)
 Rate constant, k is a constant of proportionality between the reaction rate

and the concentration of reactants.
 The rate constant, k and its value depend on a specific reaction, temperature
and catalyst.
 The larger the value of k, the faster the reaction proceeds.
 Unit of k depend on order of reaction.

ORDER OF REACTION
Order of reaction  The power to which the concentration of reactant is

raised in the rate law.
Overall order of  The sum of the powers to which all reactant

reaction concentrations appearing in the rate law are raised.
 Reaction order is usually defined in terms of reactant concentration.

Consider:
Rate = k[A]x[B]y
 x and y:
 are determined experimentally
 are independent of the stoichiometric coefficients
 can be fractional numbers, +ve or ve integers
 overall reaction order = x + y
KEEP IN MIND!!
 Components of rate laws
(rate, reaction orders, and rate constant)
– are always determined experimentally.
 Order of a reactant is not related to stoichiometric coefficient of
reactant in the balanced chemical equation.
Example:
F2 (g) + 2ClO2 (g)  2FClO2 (g)
rate = k [F2] [ClO2]

Exercise:
1) 2N2O5(g)  4NO2(g) + O2(g)
determined experimentally:
rate = k [N2O5]
 Order of reaction with respect to N2O5: ___

 Overall reaction order: ____________
2) 2NO2(g) + O3(g)  N2O5(g) + O2(g)
rate = k[NO2][O3]
 Order of reaction with respect to NO2: ___

 Order of reaction with respect to O3: _____
 Overall reaction order: _____________
3) CHCl3(g) + Cl2(g)  CCl4(g) + HCl(g)
reaction rate = k[CHCl3][Cl2]1/2
 Order of reaction with respect to CHCl3: ___

 Order of reaction with respect to Cl2: ______
 Overall reaction order: ______________

Order of Reaction
Zero order First order Second order
RATE LAW
rate = k[A]0 rate = k[A] rate = k[A]2
 Rate is not dependent  If [A] is doubled,  If [A] double, rate

on [A] at all. rate also doubled. quadruples/four fold.
 Zero order in A.  First order in A.  Second order in A.
 Zero order overall.  First order overall.  Second order overall.
 Quite common in  Example: radioactive
metal-catalyzed and reaction.
biochemical processes.
UNIT OF k (RATE CONSTANT)
Unit of the rate constant depends on the overall reaction order.

rate = k [A]0[B]0 rate = k [A]1 @ rate = k [A]1[B]1 @

=k rate = k [B]1 rate = k [A]2 @
rate = k [B]2
Unit: Unit: Unit:
GRAPH
rate rate rate
[A] [A] [A]

To determine the order of reaction from experimental data by analysing changes in

concentration of the reactant and its rate:
Order of reaction Concentration of reactant Change in rate
ZERO Varies (any amount) Remains unchanged
FIRST Double Double
SECOND Double Increases 4 times (quadruples)
Example:
1. The reaction A+2B  products was found to have the rate law,
rate = k [A] [B]2. Predict by what factor the rate of reaction will increase when the
concentration of B is doubled and the concentration of A remained unchanged.
2
2. Given, rate= k [NO ] [Cl ], by what factor does the rate increase if each of the
2 2
following changes occurs.
a) [NO2] is tripled
b) [NO2] and [Cl2] are doubled (UPS 2014/2015)

3. Write rate law for this equation,

A+B  C
a) When [A] is doubled, rate also doubles. But doubling the [B] has no effect on
rate.
b) When [A] is increased 3x, rate increases 3x, and increasing of [B] 3x causes
the rate to increase 9x.
c) Reducing [A] by half has no effect on the rate, but reducing [B] by half
causes the rate to be half the value of the initial rate.
4. The rate of a reaction increases eight-fold when the concentration of one of the
reactants is doubled. Determine the order of the reaction with respect to that
reactant.
Rate = k[A]a

HALF-LIFE, t ½
 Definition: The time required for the amount of a reactant to decrease to

half its initial value.
 amount of reactant may be in unit of concentration, mass, moles, atoms,

molecules and so on.
Example:
Radium-224 is a radioisotope of radium. If a sample of 1.0 g radium-224 was
found to weigh 0.25 g after 7 days, what is its half-life?
The mass of radium-224 decrease as follow:
Thus, the time taken for the mass to reduce from 1.0 g to 0.25 g is equivalent to
_________
Order Zero Order First Order Second Order
Formula of t1/2 = [A]0 t1/2 = ln 2 t1/2 = 1

half-life, t½ 2k k k[A]o

Calculation half-life:
1. The decomposition of ethane C2H6 to methyl radicals is a first order reaction
with a rate constant of 5.36 x 10-4 s-1 at 700°C
C2H6 (g)  2CH3 (g)
Calculate the half-life of the reaction in minutes.
2. The decomposition of ammonia on tungsten at 1100°C is zero order reaction

with the rate constant of 2.5 x 10-4 M min-1. The reaction equation:
NH3 (g)  ½ N2 (g) + 3/2 H2 (g)
a) Write the rate equation for this reaction.
b) What is the half-life of the reaction when ammonia is 0.75 M?
c) How fast is a 0.475 M of ammonia being changed to nitrogen and
hydrogen?
3. What is the half-life of a compound if 75% of a given sample of the compound

decomposes in 60 min? Assume it is first order reaction.

4. Plutonium-240, which is produced in nuclear reactors, has a half-life of

6.58 x 103 years. Calculate the rate constant for the decay of plutonium-240.
(HINT! Radioactive is first order reaction)

5. Iodine atoms combine to form molecular iodine in gaseous phase:
2I(g)  I2(g)
This reaction follows second-order kinetics and has a rate constant of
7.0109 M1s1 at 23 oC.
a) If the initial concentration of I(g) was 0.86 M, calculate the concentration after
1.5 minutes.
b) Calculate the half-life of the reaction if the initial concentration of iodine atom
is i. 0.60 M
i. 0.42 M.

MAPPING COGNITIVE
C1 C2 C3 C4
f) Write the integrated rate equation for zero, first and second order
1.1 Reaction √
reactions
Rate
h) Perform calculation using integrated rate equation equations √ √
INTEGRATED RATE LAW
 Integrated rate law is used to derive the rate law for zero order, first order
and second order reactions.
Consider: A  product
Zero Order First Order Second Order
Rate law: Rate law: Rate law:
Integrated rate law: Integrated rate law: Integrated rate law:
[A]0  [A]t = kt 1 1
[𝐴]𝑜 − = 𝑘𝑡
ln = 𝑘𝑡 [𝐴]𝑡 [𝐴]𝑜
[𝐴]𝑡
where:
[A]0 = initial concentration of A
[A]t = concentration of A at t
k = rate constant
t = time of reaction

CALCULATION USING INTEGRATED RATE EQUATION
1. The following equation shows the decomposition of SO2Cl2 with a rate constant,
k = 5.09 x 10-4 s-1 at 320 K:
SO2Cl2(g)  SO2(g) + Cl2(g)
At 320 K, 1.0 mol of SO2Cl2 is left to decompose in a 2.0 L container. Determine the
concentration of SO2Cl2 after 30 minutes.
2. The rate constant for the decomposition of nitrosyl bromide, NOBr is

48 M-1min-1 at the certain temperature.
NOBr(g)  NO(g) + ½ Br2(g)
a) Determine the order of reaction.
b) Find the time taken to decompose 90% of a 0.02 M solution of NOBr
3. Decomposition of H2O2 is first order, given that k = 3.66 x 10-3 s-1 and
[H2O2] = 0.882 M, determine
a) The time at which [H2O2]t = 0.600 M
b) The [H2O2]t after 225 s

4. The decomposition of sulphuryl chloride, SO2Cl2 occurs at as

2SO2Cl2(g)  SO2(g) + Cl2(g)
The reaction is a first order reaction. The rate constant, k at temperature 593K
is 2.20 x 10-5 s-1. Calculate the percentage decomposition of SO2Cl2 after 1 hour.
5. The decomposition of nitrosyl chloride …

NOCl(g)  NO(g) + ½ Cl2 (g)
is a second order reaction. If it takes 0.20 min to decompose 15% of a 0.300 M
solution of nitrosyl chloride, what is the value of k for the reaction?
6. Consider the following reaction

2HI (g)  H2 (g) + I2 (g)
The rate constant for the decomposition at 443°C is 30.0 dm3 mol-1 min-1.
a) How long does it take for the initial concentration of HI of 0.1 M to reduce to 0.01
M at this temperature?
b) How fast does the reaction occur if the initial concentration of HI is 0.75 M?

MAPPING COGNITIVE
C1 C2 C3 C4
g) Determine the order of reaction involving single reactant using:
1.1 Reaction i. Initial rate method
Rate
ii. Half-life based on graph of concentration against time √ √
iii. Linear graph method based on the integrated rate equation
and rate law
Determine the order of reaction
Initial rate method
Half-life method
Linear graph method
The unit of rate constant, k (from question)
The unit of rate constant, k

 The order of reaction can also be determined by looking at the unit of k
Unit of k Order of Reaction
M time-1
time-1
M-1 time-1
(notes: time can be in seconds, minutes, hour, etc)

Initial rate method

 The initial rate method is used when the data is reaction rate at several initial
concentration of reactant.
Example 1:
The initial reaction rates for the reaction
A + B  product
are given in the table below.
-3 -3
[A]0 / mol dm [B]0 / mol dm Initial rate /
-3 -1
mol dm s
2.0 2.0 0.6
4.0 2.0 2.4
2.0 4.0 1.2
2.0 6.0 1.8
Determine the
a) rate law
b) the overall reaction order
c) rate constant

Half-life method
 The reaction order also can be determined by the half-life by plotting graph of concentration against time.
Order of reaction Note Graph of concentration against time
Zero Order  The half-life of a zero order is directly

proportional to [A]0
[𝑨]𝟎
t1/2 = 𝟐𝒌
 Initial concentration, [A]0 = t½ = x

 Initial concentration, ½ [A]0 = t½ = ½ x
First Order  Half-life is constant

 Half-life is independent of [A]0
𝒍𝒏 𝟐
t1/2 = 𝒌

 Initial concentration, ½ [A]0 = t½ = x
Second Order  The half-life inversely proportional to [A]0

𝟏
t1/2 = 𝒌[𝑨]
𝟎

 Initial concentration, ½ [A]0 = t½ = 2x

Example:
Data obtained from an experiment of dissociation of N2O5 at T = 45 C are as
follows:
Time (min) 0 10 20 30 40 50 60
[N2O5]104(M) 176 124 93 71 53 39 29
Determine:
a) order of reaction
b) rate constant
Solution:
Plot of [N2O5] versus time
180
160
140
120
[N2O5] (M)
100
80
60
40
20
0
0 10 20 30 40 50 60 70
time (min)

Linear graph method

.01000
 It is known that for the following reaction order, linear graph is obtained by
plotting:
Zero order: [A]0  [A]t = kt; plot [A] vs t
First order: ln [A]0  ln [A]t = kt; plot ln [A] vs t
Second order: 1  1 = kt; plot 1 vs t
[ A ] t [ A ]0 [ A]
Example 1:
The table below shows the data obtained from the dissociation reaction of A.
Time (min) 0 5 10 15 20 25 30
[A] (M) 5.00 3.25 2.50 2.05 1.70 1.45 1.31
a) Plot a linear graph to determine the order of reaction.
b) Determine the rate constant of the reaction.
Solution:
Time(min) 0 5 10 15 20 25 30
[A] (M) 5.00 3.25 2.50 2.05 1.70 1.45 1.31
ln[A] 1.609 1.179 0.916 0.718 0.531 0.372 0.270
1 (M1)
0.200 0.308 0.400 0.488 0.588 0.690 0.763
[ A]

Plot of [A] versus time
6.00
5.00
4.00
[A
3.00
2.00
1.00
0.00
0 5 10 15 20 25 30 35
time (min)
Plot of ln[A] versus time
1.800
1.600
1.400
1.200
ln[
1.000
0.800
0.600
0.400
0.200
0.000
0 5 10 15 20 25 30 35
time (min)

Plot of 1 versus time

[ A]
0.900
0.800
0.700
0.600
0.500
1/[A]
0.400
0.300
0.200
0.100
0.000
0 5 10 15 20 25 30 35
time (min)
1 vs t is a linear graph
[ A]
 the reaction is __________________
Rate constant, k = slope of the graph
= 0.72 - 0.24
27  2
= 0.0189 M1 min1

Example 2:
Data obtained from an experiment of dissociation of N2O5 at T = 45 C are as
follows:
Time (min) 0 10 20 30 40 50 60
[N2O5]104(M) 176 124 93 71 53 39 29
Plot a linear graph to determine:
a) order of reaction
b) rate constant
Solution:
Time (min) 0 10 20 30 40 50 60
[N2O5]104
176 124 93 71 53 39 29
(M)
ln[N2O5] 4.04 4.39 4.68 4.95 5.24 5.55 5.84
1 (M1)
58.8 80.6 107.5 140.8 188.7 256.4 344.8
[N2O5 ]
Plot of [N2O5] versus time
180
160
140
120
[N2O5] (M)
100
80
60
40
20
0
0 10 20 30 40 50 60 70
time (min)

Plot of ln[N2O5] versus time
-4
0 20 40 60 80
-4.5
ln[N2O5]
-5
-5.5
-6
time (min)
a)  the reaction follows ____________

b) rate constant, k = m = (0.030) = 0.030 min1
 Advantage of half-life method

 easy to plot, data is taken straight from experiment
 only need to plot 1 graph
 Disadvantage of half-life method

 determination of k is less accurate
 Applicable only to zero, 1st and 2nd order
 Advantage of linear graph method

 k can be determine straight from graph
 k is more accurate than half-life method
 Disadvantage of linear graph method

 [A] has to be converted to ln[A] and 1/[A]
 Several graphs have to be plotted
 Applicable only to zero, 1st and 2nd order reaction

MAPPING COGNITIVE
C1 C2 C3 C4
a) Explain collision theory √
1.2 Collision b) Define activation energy √
Theory c) Explain transition state theory √
d) Draw energy profile diagram of a reaction √
COLLISION THEORY
 Definition: Collision Theory is the theory to explain the rate of chemical

reactions. It is based on;
rate  number of effective collisions
time
 Collision theory states that for a reaction to occur:

1. Molecules must collide to react.
2. Molecule must possess a certain minimum energy (activation energy) to
initiate the chemical reaction.
3. Molecules must collide in the correct orientation in order reaction to occur.
 Consider the following reaction:

A + B  products
According to the collision theory, the molecules of A must be

collide with molecules B before products can be formed
 Not all collisions will result in the formation of product.
 Only effective collision between molecules will results in the formation of

products.
 2 factors causing effective collision:

a) The colliding molecules possess a minimum energy (activation energy)
which is equal to or greater than activation energy (Ea) to initiate a
chemical reaction.
b) The reactant molecules must collide at the correct orientation.
ACTIVATION ENERGY (Ea)
 Activation energy (Ea), is the minimum energy required for effective

collisions in order to initiate a chemical reaction
ENERGY PROFILE DIAGRAM

Exothermic Reaction Endothermic Reaction
Energy of reactant is higher than Energy of reactant is lower than

that of product. that of product.
∆H is negative ∆H is positive

Example:
1. For the reaction A + B  C + D , the enthalpy change of the forward reaction is
+21 kJ mol-1. The activation energy of the forward reaction is 84 kJ mol-1.
a) Sketch the reaction profile of this reaction.
b) What is activation energy of the reverse reaction?
2. For reaction below, the Ea of the forward reaction is 150 kJ mol-1.

N2O (g) + NO (g)  N2 (g) + NO2 (g) ΔH = 110 kJ mol-1.
Draw and labelled energy profile diagram for the reaction and calculate the Ea of the
reverse reaction.

TRANSITION STATE THEORY
 Transition state theory is used to explain in detail what happen when reactant
molecules collide with each other.
 Transition state is the configuration of atoms of the colliding species
at the time of the collision.
 The collision between reactant molecules may or may not result in successful
reaction.
 During collision reactants molecules formed temporary species in the
transition state called activated complex with maximum potential energy.
 Activated complex  species formed at transition state.

Characteristics of Activated Complex
 Is the very unstable species, formed temporarily in an effective collision of
reactants when the system is at the highest energy.
 Its potential energy is greater than reactants or products.
 The activated complex and the reactants are in chemical equilibrium.
 It decomposes to form products or reactants.
Example:
CO(g) + NO (g) CO (g) + NO(g)
2 2

MAPPING COGNITIVE
C1 C2 C3 C4
1.3 Factors a) Explain the effect of the following factors on the reaction rate:
√
Affecting Concentration or pressure, temperature, catalyst and particle size
Reaction b) Illustrate the effect of temperature on the reaction using Maxwell
Boltzmann Distribution curve
√ √
Rate
Factors affecting reaction rate

.01000
Concentration of reactant Particle size Catalyst
.01000 .01000 .01000
Pressure Temperature
.01000 .01000
Concentration of reactant
.01000  When the concentration of reactant
increases, the number of particles per
unit volume increase.
 The frequency of collisions of molecules
increase.
 The number of effective collisions also
increase.
 Thus, the reaction rate increase.
Pressure
.01000
 When pressure increases, the number of
molecules per unit volume increase.
 The gas molecules closer to one another.
 The frequency of collisions of molecules
will increase.
 The number of effective collisions also
increase.
 Thus, reaction rate increase.
Particle size
.01000
 When the particle size decrease, the surface area exposed for a reaction increase.
 The frequency of collisions of molecules will increase.
 The number of effective collisions also increase.
Temperature
.01000
 When temperature increase, the average kinetic energy of molecules
increases.
 The numbers of molecules with the energy equal to or greater than
activation energy, Ea will increase.
 The number of effective collisions also increase.
MAXWELL-BOLTZMANN DISTRIBUTION CURVE
 Analyzed the behavior of gas molecules at different temperatures.
 The above diagram shows Maxwell Boltzmann distribution for a gas at

temperature T1 and T2.
 The shaded areas represent the number of molecules possessing kinetic
energy equal to or greater than activation energy, Ea.
As temperature increase,
 the average kinetic energy of molecules increase.
 More molecules have kinetic energy equal to or greater than activation
energy, Ea.
 The number of effective collisions also increases.
 Thus, reaction rate increase

MAPPING COGNITIVE
C1 C2 C3 C4
1.3 Factors
Affecting c) Compare the curve of the energy profile diagram for a reaction with
√
Reaction and without catalyst
Rate
Catalyst
.01000
 Catalyst is a substance that provides an alternative pathway by lowering
activation energy to increase the rate of reaction without itself being
consumed.
Example:
EXOTHERMIC REACTION ENDOTHERMIC REACTION
Ea = activation energy without catalyst

Ea = activation energy without catalyst
Ea’ = activation energy with catalyst
Ea’ = activation energy with catalyst
Effect of a catalyst on activation energy

 A catalyst increase the rate of reaction by increasing the frequency of

effective collision. That is with lowering Ea and with correct orientation.
 Catalyst will not affect the enthalpy of reactant or product.
 When catalyst is added to the reaction,
 Ea is lowered.
 Therefore, the number of particles that have higher energy than Ea
increase.
 Frequency of effective collision increase, rate of reaction increase.

MAPPING COGNITIVE
C1 C2 C3 C4
1.3 Factors d) State Arrhenius equation
√
Affecting
Reaction e) Explain the relationship between temperature and activation
√
Rate energy to the rate constant based on Arrhenius equation
ARRHENIUS EQUATION
 The relationship between the rate constant of a reaction and temperature is

expressed by Arrhenius equation.
 where k = rate constant

A = collision frequency factor
e = natural log exponent
Ea = activation energy
R = gas constant (8.314 J mol-1 K-1)
T = absolute temperature (K)
Factor affect the rate constant

Temperature Activation Energy (Catalyst)
 When temperature increase,  When activation energy decrease,
 Term e – Ea/RT become ________  Term e – Ea/RT become ________
 Value of rate constant, k _______  Value of rate constant, k _______
 Rate of reaction _________  Rate of reaction _________

MAPPING COGNITIVE
C1 C2 C3 C4
1.3 Factors
Affecting f) Determine k, Ea, T and A using Arrhenius equation by calculation
Reaction and graph
√ √
Rate
Arrhenius Equation – Derivation
 The relationship between k and T is clearer when further derive the Arrhenius
equation:
k = Ae – Ea/RT
ln k = ln (Ae – Ea/RT)
ln k = ln A + ln (e – Ea/RT)
ln k = (– Ea/RT) ln e + ln A (but ln e = 1)
Thus,
Ea
ln k =  + ln A
RT
Arrhenius equation using graphical method
𝟏
 plot of ln k versus gives a linear graph :
𝐓
𝐸𝑎
 – = slope of the graph (negative slope)
𝑅
 y-intercept = ln A
** R must be 8.314 J mol-1 K-1 NOT 0.08206 atm L mol-1 K-1 because the
unit of Ea is in J or kJ !

Example:
The rate constants of the decomposition of hydrogen iodide,
2HI(g)  H2(g) + I2(g)
were determined at five different temperatures. The data are shown below.
k (M1 s1) T (C)
3.52107 283
3.02105 356
2.19104 393
1.16103 427
3.95102 508
Determine the activation energy (in kJ mol1) for the reaction.
Solution:
1
k (1/M s) T (K) ln k (K1)
𝑇
3.52107 556 14.860 1.80103
3.02105 629 10.408 1.59103
2.19104 666 8.426 1.50103
1.16103 427 6.759 1.43103
3.95102 781 3.231 1.28103
𝟏
plot ln k versus
𝑻
0
m = 2.24104 K
-20.001 0.0012 0.0014 0.0016 0.0018 0.002
-4 𝐸𝑎
m=–
-6 𝑅
Ea = mR
lnk
-8
-10
= 2.24104 K 
-12
8.314 J K1 mol1
-14
-16 = 1.86105 J mol1
1/T = 186 kJ mol1

Arrhenius equation using calculation
 rate constants of a reaction are determined at two different temperatures
Ea
at T1: lnk1 = lnA 
RT1
Ea
at T2: lnk2 = lnA 
RT2
Ea Ea
 lnA = lnk1 + = lnk2 +
RT1 RT2
Ea Ea
lnk1  lnk2 = 
RT2 RT1
k 1 Ea  1 1 
ln =   
k2 R  T2 T1 
Example: Determine k, Ea, T and A using Arrhenius equation by calculations.
1. The decomposition of hydrogen iodide,
2HI (g) → H2 (g) + I2 (g)
has a rate constants of 9.51 x 10-9 L mol-1 s-1 at 500K and 1.10 x 10-5 L mol-1s-1 at
600K. Find Ea.
(Ans: Ea = 175.9 kJ mol-1)

2. The rate constant for the reaction C4H8 (g) → 2C2H4 (g) is 3.2 x 10-2 s-1 at 527°C.
Calculate the rate constant at 577°C if the activation energy for the reaction is 260 kJ
mol-1.
(Ans: k2 = 0.3187s-1)
3. For the reaction NO2Cl + NO  NO2 + NOCl, the frequency factor is

8.3 x 108 dm3 mol-1 s-1 and Ea is 28.9 kJ mol-1. At 25°C the reaction is first order with
respect to NO2Cl and first order with respect to NO. Determine the rate constant for
the reaction.
(Ans: k = 7.174 x 103 M-1s-1)

4. The reaction is first order with an activation energy of 111 kJ mol-1. If the rate
constant, k is 2.00 x 10-5 s-1 at 50°C, determine the frequency factor, A. At what
temperature the value of k will be equal to 1.5 x 10-3 s-1?
(Ans: T2 = 360.9 K)
5. The activation energy for a reaction is 50.2 kJ mol-1 and the rate constant of the
reaction is 3.46 x 10-2 s-1 at 298 K. Calculate the temperature if the rate constant is
6.30 x 10-4 s-1.
(Ans: T2 = 248.81 K)

1 Reaction Kinetics

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1 Reaction Kinetics

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TOPIC 1: REACTION KINETICS

CHAPTER 1.0: REACTION KINETICS

CHAPTER 1  REACTION KINETICS page 1

 Chemical kinetics is the area of chemistry concerned with the speeds or

 Definition: Reaction rate is the change in the concentration of a reactant or

 A reaction rate (r) is a positive quantity

rate = (final concentration) – (initial concentration)

= Δ (concentration) mol L-1

CHAPTER 1  REACTION KINETICS page 2

Consider the following reaction:

 reaction rate = concentration change

 Reaction rate is inversely proportional to time.

CHAPTER 1  REACTION KINETICS page 3

The differential rate equation

Definition: The relationship between the rate of disappearance (or depletion) of

For the reaction A  B

rate =  d[A] = + d[B]

For the reaction 2C  D

rate =  1 d[C] = + d[D]

Generally, for the reaction:

a, b, c and d are the stoichiometry coefficient

the rate expression is:

b) 2SO2(g)  2SO(g) + O2(g)

CHAPTER 1  REACTION KINETICS page 4

a) Write the differential rate equation for the above reaction.

CHAPTER 1  REACTION KINETICS page 5

4. Nitrogen monoxide reacts with oxygen gas as follows:

CHAPTER 1  REACTION KINETICS page 6

RATE LAW / RATE EQUATION

RATE CONSTANT (k)

 Rate constant, k is a constant of proportionality between the reaction rate

CHAPTER 1  REACTION KINETICS page 7

Order of reaction  The power to which the concentration of reactant is

Overall order of  The sum of the powers to which all reactant

 Reaction order is usually defined in terms of reactant concentration.

F2 (g) + 2ClO2 (g)  2FClO2 (g)

rate = k [F2] [ClO2]

CHAPTER 1  REACTION KINETICS page 8

 Order of reaction with respect to N2O5: ___

2) 2NO2(g) + O3(g)  N2O5(g) + O2(g)

 Order of reaction with respect to NO2: ___

3) CHCl3(g) + Cl2(g)  CCl4(g) + HCl(g)

 Order of reaction with respect to CHCl3: ___

CHAPTER 1  REACTION KINETICS page 9

Zero order First order Second order

rate = k[A]0 rate = k[A] rate = k[A]2

 Rate is not dependent  If [A] is doubled,  If [A] double, rate

UNIT OF k (RATE CONSTANT)

Unit of the rate constant depends on the overall reaction order.

rate = k [A]0[B]0 rate = k [A]1 @ rate = k [A]1[B]1 @

rate rate rate

[A] [A] [A]

CHAPTER 1  REACTION KINETICS page 10

To determine the order of reaction from experimental data by analysing changes in

Order of reaction Concentration of reactant Change in rate

ZERO Varies (any amount) Remains unchanged

FIRST Double Double

SECOND Double Increases 4 times (quadruples)

CHAPTER 1  REACTION KINETICS page 11

3. Write rate law for this equation,

CHAPTER 1  REACTION KINETICS page 12

 Definition: The time required for the amount of a reactant to decrease to