Chemical Kinetics

Chemistry 4
FAD1008

References

1. Chemistry for Matriculation. A. A. Rahman, A. M. Jelan, M.

Sulaiman, J. C. Kotz.& P. M. Treichel. Thomson
2.Physical Chemistry for STPM. C. H. Kho, A. Zaharah, W. L.
Masterton & C. N. Hurley. Thomson
 Thermodynamic vs Kinetics
• Thermodynamic – direction of a reaction.
• Kinetics - Speed of the reaction.

Reaction profile
Exothermic

Potential energy
Ea

Endothermic
∆H Products
∆H

Reactants

Reaction progress Reaction progress

 Chemical kinetics
• The study of rate of reaction.
• To predict and control the reaction rate.
• To formulate the reaction mechanism.
Factors That Affect Reaction Rates

• Physical State of the Reactants

➢ In order to react, molecules must come in
contact with each other. If the reaction is
happening between a solid and a liquid it
will react only on the surface.
➢ The more homogeneous the mixture of
reactants, the faster the molecules can
react.
Factors That Affect Reaction Rates

• Concentration of Reactants
➢ As the concentration of reactants increases,
so does the likelihood that reactant
molecules will collide.
Factors That Affect Reaction Rates

• Temperature
➢ At higher temperatures, reactant
molecules have more kinetic energy,
move faster, and collide more often and
with greater energy.
Factors That Affect Reaction Rates

• Presence of a Catalyst
➢ Catalysts speed up reactions by
changing the mechanism of the
reaction.
➢ Catalysts are not consumed during
the course of the reaction.
 Rate of Reaction
• The change of reactant(s) or product(s) conc
over time.
Average reac tan t  product
− = =
reaction rate t t
 Reaction Rates
C4H9Cl(aq) + H2O(l) ⎯⎯→ C4H9OH(aq) + HCl(aq)

Time (s) [C4H9Cl] In this reaction, the

0.0 0.1000
concentration of butyl
50.0 0.0905
100.0 0.0820
chloride, C4H9Cl, was
150.0 0.0741 measured at various
200.0 0.0671 times.
300.0 0.0549
400.0 0.0448
500.0 0.0368
800.0 0.0200
 Reaction Rates
C4H9Cl(aq) + H2O(l) ⎯⎯→ C4H9OH(aq) + HCl(aq)

Time [C4H9Cl] Average Rate Average rate over each interval;

(s) (M) (Ms-1)
0.0 0.1000
1.90 x 10-4 Average [C4H9Cl]
= -
50.0 0.0905
1.70 x 10-4 rate t
100.0 0.0820
1.60 x 10-4
150.0 0.0741 0.0095 M
1.40 x 10-4 = - 50 s
200.0 0.0671
1.22 x 10-4
300.0 0.0549
1.01 x 10-4
= - 1.90 x 10-4 Ms-1
400.0 0.0448
0.80 x 10-4 Average rate
500.0 0.0368
0.56 x 10-4 for interval #1
800.0 0.0200
 Average vs Instantaneous Rates
C4H9Cl(aq) + H2O(l) → C4H9OH(aq) + HCl(aq)

•A plot of concentration
vs. time for this reaction
yields a curve like this.
•The slope of a line
tangent to the curve at
any point is the
instantaneous rate at that
time.

Chemistry, The Central Science, 10th edition Theodore L. Brown; H. Eugene LeMay, Jr.; and Bruce E. Bursten
 Average vs Instantaneous Rates
C4H9Cl(aq) + H2O(l) → C4H9OH(aq) + HCl(aq)

•All reactions slow down

over time.
•Therefore, the best
indicator of the rate of a
reaction is the
instantaneous rate near
the beginning.
•This is called initial rate.

Chemistry, The Central Science, 10th edition Theodore L. Brown; H. Eugene LeMay, Jr.; and Bruce E. Bursten
 Example 1
Calculate the initial rate for above example.

Solution

Chemistry, The Central Science, 10th edition Theodore L. Brown; H. Eugene LeMay, Jr.; and Bruce E. Bursten
Reaction Rates and Stoichiometry
C4H9Cl(aq) + H2O(l) ⎯⎯→ C4H9OH(aq) + HCl(aq)

•In this reaction, the ratio of C4H9Cl to C4H9OH is 1:1.

•Thus, the rate of disappearance of C4H9Cl is the same
as the rate of appearance of C4H9OH.

-[C4H9Cl] [C4H9OH]
Rate = =
t t
 • In general, for a reaction;
aA + bB cC + dD

1 dA  1 dB 1 dC 1 dD

Reaction rate = − =− = = = k[A]x[B]y
a dt b dt c dt d dt

Decreasing concentrations
 Example 2
Write the relative rate of changes in conc of
reactant and products for the following
reaction;
4 PH3 (g) P4 (s) + 6H2 (g)

Given, the rate of H2 formation is 0.50 mol dm-3

s-1, what is the rate of consumption of PH3?
Example 2: Answer
 The Rate Law
• Two types:
– Differential rate law relate the reaction rate with
conc of reactant(s).
– Integrated rate law describe the change of conc
with time.
 Differential rate law
• Consider a reaction;
aA + bB + cC product(s)

Reaction rate α [A]w [B]x [C]y NB: the values of w, x

and y are not related to
Reaction rate = k[A]w [B]x [C]y
stoichiometric
coefficient(s)!!!
k = rate constant
w = reaction order with respect to A
x = reaction order with respect to B
y = reaction order with respect to C
Diff. rate law w + x + y = overall order of the reaction
Determining the Rate Law: Initial Rate Method

• Objective: to determine;
– Order of reaction
– Rate constant.
• A series of experiments are conducted.
• Vary one initial conc of a reactant while fixing
the others.
• Graph of conc vs time is plotted.
• Initial rate is determined from the slope of the
tangent at t = 0.
Determining the Rate Law: Initial Rate Method

Tangent at t = 0

[C]

Time
 Example 3
Initial rate for the reaction;

NH4+ + NO2- N2 + 2H2O

was studied at 540 K. Determine the rate law

for this reaction from the following data:

Experiment [NH4+]0 / M [NO2-]0 / M Initial Rate

1 0.1 0.005 1.35 x 10-7
2 0.1 0.01 2.70 x 10-7
3 0.2 0.01 5.40 x 10-7
Example 3: Solution
Example 3: Solution (cont’)
 Determining the Rate Law

• Practically, Initial Rate Method is difficult and

tedious.
• Therefore, the average rate is used.
• This is done by recording the time taken for a
certain changes to occur.
 Example 4
An experiment was conducted to determine the
rate law for the following reaction:
NH4+(aq) + NO2−(aq) N2(g) + 2 H2O(l)

A series of experiments was conducted with

varying initial concentrations of NH4+ and NO2-.
The time taken for the pressure of N2 gas to
increase by 0.10 atm was measured, and the
following data was obtained.
 Example 4
Expt [NH4+] [NO2-] Time (mins)
1 0.010 0.200 684
2 0.020 0.200 342
3 0.040 0.200 171
4 0.060 0.200 114
5 0.200 0.020 342
6 0.200 0.040 171

Determine the rate law for this reaction.

Example 4: Solution
Example 4: Solution (cont’)
 Integrated Rate Law : zero order
• Consider a zero order reaction:
A product(s)

d  At
Reaction rate = − = k [A]t0
dt

OR − d  At = kdt

−  At = kt + C
substitute
Integrate,

When t = 0, [A]t = [A]0 − A 0 = k (0) + C

C = −A 0
Integrated Rate Law : Zero order
(cont’)
A0 − At = kt Integrated rate law for
zero order reaction
OR [A]
At = −kt + [ A]0 [A]0

Slope = - k
y = mx + c
t
Half – life, t1/2
• Half – life is the time required for the conc of
the reactant(s) to decrease to half of its initial
value.
When t = t 1  ,
At =
 A0
2 2

A0 − A0
= kt 1
[A]0
2 2
[A]0

t1 =
A0 2
2 2k t1/2
t
 Integrated Rate Law : First order
• Consider a zero order reaction:
A product(s)

d  At
Reaction rate = − = k [A]t1
dt
d At
OR −
At = k dt

Integrate, − lnAt = kt + C

When t = 0, [A]t = [A]0 C = − ln A 0

Integrated Rate Law : First order
(cont’)
lnA0 − ln At = kt
Integrated rate law for
OR first order reaction
ln At = −kt + ln[ A]0
Half – life, t1/2

When t = t1 At =  A0

2 2

ln A 0 − ln
A 0
= kt 1
2 2

ln 2
t1 =
2 k
 Example 5
At 55 ºC, the gas phase decomposition of N2O5
is first order with specific rate constant 1.42 x
10-3 s-1.
a) Calculate the half life for the decomposition
b) If the initial partial pressure of N2O5 is 2.84
atm, how long will it take for the partial
pressure to drop to 0.355 atm.
 Example 5: Solution
lnA0 − ln At = kt

When t = t1 At =  A0

2 2

ln A 0 − ln
A 0
= kt 1
2 2

ln 2 ln 2
t1 = = −3 −1 = 488 s
2 k 1.42x10 s
 Example 5: Solution (cont’)
[N2O5]0 = k1(2.84) M
k1 = constant.
[N2O5] = k1(0.355) M

ln A 0 − ln A  = kt

 k1 (2.84) 

ln  
 ( )
= 1.42 x 10 s t
-3 -1

 k1 (0.355) 

t = 1460 s
C) Integrated Rate Law : 2nd order
• Consider a second order reaction:
A product(s)

d  At
Reaction rate = −
2
= k [A]t
dt
d At
OR −
At2 = k dt

1
Integrate, = kt + C
At
 1
When t = 0, [A]t = [A]0 C=
A0
After substitution,
1 1 1 1
− = kt = kt +
At A0 OR
At [ A]0

Thus, the plot of 1 / [A] vs time gives a

straight line with slope k
Half – life, t1/2

When t = t1 At =  A0

2 2
2 1
− = kt 1
A0 A0 2

1
t1 =
2 kA0
 D) Integrated Rate Law : Pseudo-zero order

• In practice, when a reaction involves more

than one reactants, it is easier to study the
order with respect to one reactant while the
other order(s) are made zero (pseudo-zero
order).
• This is achieved by using a relatively high conc
of the other reactant(s) while varying the
concentration of the reactant understudy.
 D) Integrated Rate Law : Pseudo-zero order

• For example, for the following reaction,

Na2S2O3 + 2 H+ → H2O + SO2 + S + 2 Na+

• Suppose the rate law is: Rate = k1[Na2S2O3]x[H+]y

• By using a high conc of HNO3, the change in conc
of H+ is negligible, and hence, can be considered
constant.
• Thus, the rate law can be simplified as:
Rate = k[Na2S2O3]x
 Something to memorize
Zero Order First Order Second Order
Rate Law

Integrated Rate
Law

Units of Rate
Constant {k}

Linear Plot [A] vs. t ln([A]) vs. t 1/[A] vs. t

Half-life
 Example 6
In an experiment on decomposition of
phosgene at 45 °C, the following data were
obtained.
[Cl2CO] (M) Time (mins)
2.08 3.07
1.67 8.77
1.36 14.45
0.72 31.28
What is the integrated rate law for the
reaction? Calculate the initial conc and
determine the initial rate.
 Example 6: Solution
Time (mins) 3.07 8.77 14.45 31.28
[Cl2CO] (M) 2.08 1.67 1.36 0.720
ln [Cl2CO] 0.732 0.513 0.307 - 0.329
1 / [Cl2CO] 0.481 0.599 0.735 1.39

Since the plot of ln[Cl2CO] vs t is a straight line,

the reaction is first order.
 1.00
ln [Cl2CO] vs time
0.80 [0.85]

0.60
m = - 0.038 min-1
ln [Cl2CO]

0.40

0.20

0.00
0 10 20 30 40
-0.20

-0.40
t (min)
 Example 6: Solution (cont’)

At t = 0, ln [Cl2CO] = 0.85
[Cl2CO] = 2.34 M.

Initial rate = k [Cl2CO]

= -(- 0.038) (2.34)
= 0.089 M min-1
 Example 7
Sucrose decomposes to fructose and glucose in
acid solution with the rate equation;

Rate = k [sucrose]1 , k = 3.47 x 10-3 min-1

How long will it take for 87.5 % sucrose to

decompose from the initial quantity? Calculate
the half – life for this reaction.
Example 7: Solution
Example 7: Solution (cont’)
 Collision Theory
• In order for a reaction to occur,
1) particles must collide
2) particles must possess sufficient kinetic
energy to break the existing bonds.
3) Particles must collide with the right
orientation which leads to rearrangement of
atoms.
E.g. N2O (g) + NO (g) N2 (g) + NO2 (g)

(a) Favourable collision

(b) Unfavourable collisions

• Collisions which end up with reactions are
called effective collisions.
• Any factor that change the number of
effective collisions will change the rate of
reaction.
• Change in concentration will change the
number of particles per unit volume and thus
change the number of collision per unit time.
• Change in temperature will change the kinetic
energy of the particles and hence, the number
of particles which possess sufficient energy to
react will also change.
• The minimum energy required for the reaction
to occur is called activation energy which is a
kind energy barrier for the reaction.
• For example;
N2O (g) + NO (g) N2 (g) + NO2 (g)
Reaction profile
Effect of temperature
 Arrhenius Equation
 − E a  , where
k = A exp  k = rate constant
 RT  A = frequency factor
Ea = activation energy
T = absolute temperature
R = gas constant
• Can also be written as;

Ea 1
ln k = −   + ln A
R T

• Thus, the Ea can be

determined by
plotting ln k vs 1/T
with the slope of –
Ea/R.
 Example 8
The activation energy of a first order reaction
is 50.2 kJ/mol at 25oC. At what temperature
will the rate constant double?
Example 8: Solution
Example 8: Solution (cont’)
 Transition state theory
• Reactant(s) go through a transition state
before become product(s).
A + B AB# C + D

• AB# is called transition state or activated

complex, the highest energy in a reaction
step.
• It is highly reactive and unobservable.
• Could be more than one transition states.
 Energy profile for an exothermic single step
reaction

AB#

Ea (forward)
Energy

Ea (backward)

A + B
ΔH
C + D
Reaction progress
 Example 9
Decomposition of an organic compound, A to
give B and C, is endothermic. The reaction
involves the formation of carbocation as an
intermediate. Sketch the energy profile for the
reaction showing the activation energies
(forward only), transition states, intermediate
and reaction enthalpy.
Example 9: Answer
 Catalysis
• A catalyst increases the reaction rate without
being consumed at the end of the reaction.
• Provides an alternative reaction pathway with
lower activation energy.
• Increases effective collisions.
• A catalyst does participate in the reaction but
does not undergo overall change.
 Homogeneous Catalysis
• In the same phase with the reactant(s).
• Either in liquid or gas phase.
• Eg. S2O82- + 2I- 2SO42- + I2 (Slow)
• With Fe2+ catalyst;
S2O82- + 2Fe2+ 2SO42- + 2Fe3+
2Fe3+ + 2I- I2 + 2Fe2+

S2O82- + 2I- 2SO42- + I2

 Heterogeneous catalysis
• The catalyst and the reactant(s) are in
different phases.
• E.g. the the conversion of NO and CO gases
into N2 and CO2 in the catalytic converter.
• Heavy metals such as Rh provide plenty of low
energy empty orbitals for adsorption.
• Increases the local concentration and provides
better orientation
 CO NO CO

O C O N N O C O

Rhodium surface

2 CO + 2 NO 2 CO2 + N2
 O C O N N O C O

Rhodium surface

2 CO + 2 NO 2 CO2 + N2
CO2 N2 CO2

O C O N N O C O

Rhodium surface

2 CO + 2 NO 2 CO2 + N2
 Reaction Mechanism
• Single step reactions are very rare.
• Most reactions involve more than one steps.
• A series of steps involve is called reaction
mechanism.
• Each step in the series is called elementary
reaction which shows the actual molecules
involves in a collision.
• Elementary reaction might be unimolecular,
bimolecular or termolecular reactions.
 Intermediate
Elementary reactions Rate determining step

NO2 + NO2 NO3 + NO (Slow)

Mechanism
NO3 + CO CO2 + NO2 (Fast)

NO2 + CO CO2 + NO Overall reaction

From experiment, the rate law is; rate = k [NO2]2

• For an elementary reaction, the order with
respect to a reactant is the stoichiometric
coefficient for the reactant in a balanced
chemical equation.
• The slowest step in the mechanism is the rate
determining step.
• Elementary processes can be reversible
reactions; sometimes rates of forward and
reverse reactions are equal (we say that the
two reactions are et equilibrium).
• A plausible reaction mechanism must be
consistent with:
a) stoichiometry of overall reaction, and
b) experimentally determined rate law.
 Example 10
For the reaction;
2H2 + 2NO N2 + 2H2O
the observed rate law is :
Rate = k [NO]2[H2]

Three mechanism has been proposed;

Mechanism 1
k1
2H2 + 2NO N2 + 2H2O
 Example 10
Mechanism 2
k2
H2 + NO H2O + N (Slow)
Keq1
N + NO N2 + O (Fast)

O + H2 H2O (Fast)

Mechanism 3
Keq1
2NO N2O2
k3
H2 + 2NO N2O + H2O (Slow)
Keq2
N2O + H2 N2 + H2O (Fast)

Determine whether each mechanism is a plausible.

 Example 10: Solution
Mechanism 1
k1
2H2 + 2NO N2 + 2H2O

2 2
Rate = k1[NO] [H 2 ] not plausible!
Example 10: Solution (cont’)
Mechanism 2
k2
H2 + NO H2O + N (Slow)
Keq1
N + NO N2 + O (Fast)

O + H2 H2O (Fast)

2H2 + 2NO N2 + 2H2O

Rate = k 2 [NO] [H 2 ] not plausible!

 Example 10: Solution (cont’)
Mechanism 3
Keq1
2NO N2O2 (Fast)
k3
H2 + N2O2 N2O + H2O (Slow)
Keq2
N2O + H2 N2 + H2O (Fast)

2H2 + 2NO N2 + 2H2O

Rate = k3 [N 2 O 2 ] [H 2 ]
 Example 10: Solution (cont’)
[N 2 O 2 ]
K eq1 = [ N 2 O 2 ] = K eq1 [NO] 2
[NO]2

Substitute into the above rate equation,

we have
2
Rate = k3K eq1 [NO] [H 2 ]

, k = k3K eq1
2
= k[NO] [H 2 ]
Since the rate law is consistent with the
experiment, the above mechanism is plausible.
 Example 11
From an experiment, the rate law for the
following reaction;
Cl2 + CO COCl2

is: d[COCl
dt
]2
= k [CO] [Cl ] 2

Prove that the following mechanism is plausible

for the above reaction.
Keq1
Cl2 2Cl (fast)
Keq2
Cl + CO COCl (fast)
k4
Cl + COCl COCl2 (slow)
 Example 11: Solution

Keq1
Cl2 2Cl (fast)
Keq2
Cl + CO COCl (fast)
k4
Cl + COCl COCl2 (slow)

Cl2 + CO COCl2
 Example 11: Solution (cont’)
Rate = k 4 [Cl] [COCl]

[Cl]2
K eq1 =
[Cl2 ]
[Cl] = (K eq1 )
[Cl 2 ]

[COCl]
K eq 2 = [COCl] = K eq 2 [CO] [Cl]
[Cl] [CO]
( )
= K eq 2 [CO] K eq1 [Cl 2 ]
1
2

Substitute into the above rate equation,

we have
 Example 11: Solution (cont’)
1
2 
Rate = k 4 (K eq1 [Cl 2 ]) K eq 2 [CO] (K eq1 [Cl 2 ])
1
2 
= k 4 K eq1 K eq 2 [Cl 2 ] [CO]

Rate = k[Cl 2 ] [CO] , k = k 4 K eq1 K eq 2

Since the rate law is the same as the one

determined by experiment, the above mechanism
is plausible.