Chapter 1: Reaction Kinetics

Reaction rate

1. Reaction kinetics is the study of the rates of chemical reactions, factors affecting rates, and the
reaction mechanisms by which reactions occur.
2. Reaction rate is the change in the concentration of a reactant or a product with time.
3. Rate 1
Time
4. Unit Rate: Ms-1 / mol L-1 s-1

5. Mathematical formula: Rate = (final concentration) – (initial concentration)

Time
=Δ(concentration)
Δt
6. Graphical interpretation:
Concentration of product increases
over time, showing that product is
formed.

Concentration of reactant decreases

over time, showing that reactant is
consumed.

The differential rate equation

A differential rate equation enables the relationship between the rate of disappearance of
reactants and the formation of products.

1. In general, for a reaction aA + bB ⎯→ cC + dD

1  −d [ A]  1  −d [ B]  1  d [C ]  1  d [ D] 
Rate =  =  = +  = +  
a  dt  b  dt  c  dt  d  dt 
Examples:

N2(g) + 3H2(g) ⎯→ 2NH3(g)

2SO2(g) → 2SO(g) + O2(g)

Exercise:

1 Consider the reaction,

2HI ⎯→ H2 + I2, determine
the rate of disappearance of
HI when the rate of I2
formation is 1.8 x 10-6 M s-1.

(3.6x 10-6 M s-1.)

2 Consider the reaction,

2NO(g)+ O2(g) ⎯→2NO2(g).
Suppose that at a particular
moment during the reaction,
nitrogen monoxide (NO) is
reacting at the rate of 0.066
Ms-1
a) Write the rate
differential equation for
the above reaction.
b) At what rate is NO2
being formed? (0.066
M s-1.)
c) At what rate is oxygen
reacting? (0.033 M s-1.)

3 For reaction
4NH3(g) + 3O2(g)→ 2N2(g)+
6H2O(g),
N2 gas was formed at a rate
of 0.14 M s-1.
a) Write the differential
equation for the above
reaction.
b) Calculate the rate of
depletion of ammonia
and the rate of
formation of steam.

(0.28 M s-1)
(0.42 M s-1)
4 Because it has a non-
polluting product (water
vapour), hydrogen gas is
used as fuel aboard the
space shuttle.

2H2(g) + O2(g) ⎯→ 2H2O(g)

a) Express the rate in

terms of changes in
[H2], [O2] and [H2O]
with time.

b) When [O2] is
decreasing at 0.23 mol
L-1 s-1, at what rate is
[H2O] increasing?
c) Calculate the rate of
usage of hydrogen.
(0.46 mol L-1 s-1)

Rate Law

1. The rate law (or rate equation) for a chemical reaction relates the rate of
reactionto the concentration of reactants raised to some powers.
2. At constant T & P, rate of chemical reaction is proportional to
concentration of reactants.

rate  [reactant] k = rate constant

3. Consider this equation, aA + bB cC m= reaction order with respect to A

rate = k[A]m[B]n n = reaction order with respect to B

m + n = order of reaction
4. Order of reaction:
❖ The sum of the powers to which all reactant concentrations in the rate
law are raised.
❖ Reaction orders are determined experimentally.
❖ Reaction orders are NOT the stoichiometric coefficients in a
balanced chemical equation.
❖ Example order of reaction: zero order, first order, second order

5. Rate constant, k
❖ A constant of proportionality between the reaction rate and the
concentrations of reactants.
❖ The rate constant, k and its value depend on a specific reaction,
temperature & catalyst.
❖ They are generally small numbers, can be positive/ negative.
❖ Units of k depend on the values of m, n, …
Half-Life (t1/2)

i) Half-life, t1/2 is the time required for the concentration of a

reactant to decrease to half of its initial value.
ii) Example mathematically:

(t1/2)1 = 5 min (t1/2)2 = 5 min

[A]o ½ [A]o 1/4 ( [A]o)

1.0 M ½ (1.0 M) 1/4 (1.0 M)

= 0.5 M = 0.25 M
iii) Graphically:

iv) The magnitude of half life is an indicator for the reactivity or stability
of a chemical substance. A substance with the shorter half-life
indicated that it is a reactive or less stable substance.

Integrated Rate Laws

i) The integrated rate law is an equation that describes the concentration of a reactant
as a function of time.
ii) It can be used to determine rate constant, half life and concentration of
reactant at specific time.
iii) The integrated rate equation for zero, first and second order reaction are
shown in the table.

The following equations and graphs are relevant for mono-reactant reaction:
A products

Zero Order Reaction First Order Reaction Second Order

Reaction
Expression rate = k rate = k[A] rate = k[A]2

Effect of Double the [A] has Double the [A], the Double the [A], the
doubling [A] no effect on rate rate increases rate increases by
doubled (2x) the factor 4 or (4
times)
Integrated [A]0 -[A] = kt ln [A]0 - ln [A] = kt 1 - 1 = kt
Rate Equation [A] [A]0

Unit of k M s-1 s-1 M-1s-1

Mol L-1s-1 Mol-1 L s-1
Half-life, t½ t1/2= [A]0 / 2k t1/2=ln2 / k t1/2= 1 / k[A]0
Graph of
rate vs t

Interpretation
of linear
graph (I)

Interpretation
of linear
graph (II)

Comparison Concentration Concentration Concentration

of 1st and 2nd
A0 A0
half-life A0
½ A0
½ A0 ½ A0

¼ Ao ¼ A0
¼ A0
t t

X 1/2X X X X 2x t
Examples:

1 NO(g) + O2(g) ⎯→ 2NO2(g)

Given rate = k[NO]2 [O2], determine

a) The reaction order with respect to

NO.
b) The reaction order with respect to
O2
c) The overall reaction order.
2 S2O82- (aq) + 3 I- (aq) ⎯→ 2 SO42- (aq) +
I3-(aq)

The above reaction is first order with

respect to iodide ion and to thiosulphate
ion.
a) Write the rate equation for the
reaction.
b) Determine the overall reaction oder.
c) What is the unit of rate constant, k?
3. The decomposition of N2O5 at 450C is first
order.

2N2O5(g) 4NO2 (g) +O2(g)

a) Write an expression for the rate
equation

b) Calculate the rate constant if the

concentration of N2O5 is 1.5x10-3 M at a
dissociation rate of 8.6 x10-7 Ms-1
(5.73 10-4s-1)

4 Write the rate law for this reaction

A + B ⎯→ C

a) When [A] is double, rate also

double. But double the [B] has no
effect on rate.

b) When [A] is increased 3 times, rate

increases 3 times and increase of
[B] 3 times, rate is also increase3
times.

c) Reduce [A] by half has no effect on

the rate, but reduce [B] by half will
cause the rate to be half of the initial
rate.
1. Determination order of reaction can be determined by:
❖ Unit of rate constant
❖ Initial rate method
❖ Graphical method (graph half-life or linear graph)

❖ Unit of rate constant

0 order 1st order 2nd order
mol L-1 time-1 or M time-1 time-1 M-1 time-1

NOTE: time can be in year, month, hour, minute or second.

Example
1. The reaction A → B has rate constant 9.52x10-3 Ms-1. How long will it take for A to
decrease from 0.20M to 0.15M? What is the half-life of this reaction?

Solution
Unit of k=Ms-1, it is zero order
reactionIntegrated Rate Equation
[A]0 -[A] = kt
(0.20)-(0.15) = (9.52 x10-3)t
t=5.25 s

t 1/2 = [A]0 / 2k
= (0.20)
2(9.52x10-3)
=10.50s

❖ Initial rate method

1 2NO(g) + Cl2(g) ⎯→ 2NOCl(g)

Exp. Initial Initial Initial rate,

[NO] [Cl2] Ms-1
M M
1 0.0125 0.0255 2.27 x 10-5
2 0.0125 0.0510 4.55 x 10-5
3 0.0250 0.0255 9.08 x 10-5

Determine
a) the rate equation
b) the rate constant, k (5.69)

2 ClO2(aq) + 2OH- (aq) ⎯→ products

Exp Initial Initial Initial rate,

. [ClO2] [OH-] Ms-1
M M
1 0.0421 0.0185 8.21 x 10-3
2 0.0522 0.0185 1.26 x 10-2
3 0.0421 0.0285 1.26 x 10-2

Determine
a) The rate law/rate
 equation
b) The rate constant, k
c) The reaction rate if the
concentration of both
ClO2 and OH- are both
0.05 M.

(250), (3.12x10-2)

3 Based on the experimental data for

reaction C + D ⎯→ E

Exp Initial [ ], M Tim Change

t [C] [D] e in [C],
inter M
val
min
1 0.10 1.0 30 2.5x10-3
2 0.10 2.0 30 1.0x10-2
3 0.05 1.0 120 5.0x10-3

a) Calculate the rate of reaction for

each set of experiment.
b) Hence write the rate law for this
reaction.
(8.33x10-5 , 3.33x10-4 , 4.2x10-5)

4 Based on the experimental data in the

table below,
Initial Initial rate
Conc (M) of
Exp formation
[ NO ] [ H2 ] of H2O (M
s-1)
A 0.10 0.10 0.00123
B 0.30 0.20 0.00246
C 0.20 0.10 0.00492

a) Write the rate law for the reaction.

b) Determine the order of reaction with
respect to:
i) NO ii) H2
c) Determine the overall order of
reaction.
(Overall order=3)
GRAPHICAL METHOD:HALF-LIFE BASED ON GRAPH OF CONCENTRATION AGAINTS
TIME METHOD
ZERO ORDER FIRST ORDER SECOND ORDER
• A straight line • Half life is • From the graph, the
obtained constant second half life
• From the graph, the • From the graph, (time=2x) is twice
second half life is the first half life than the first half
half(time=x) from and second half life (time=x)
the firsthalf life life is constant Concentration
(time= ½ x) (time=x)
Concentration Concentration

1.0 1.0 1.0

0.5 0.5 0.5

0.25 0.25 0.25

Time Time Time

x x x x 2x
½x
Example:
1. The following results were obtained from an experimental
investigation ondissociation of dinitrogen pentoxide at 45oC
N2O5(g) ⎯→ 2 NO2(g) + ½ O2(g)

Time, t/min 0 10 20 30 40 50 60
[N2O5]x10-4 /M 176 124 93 71 53 39 29

Plot graph of [N2O5] vs time, determine

i) The order of the reaction
ii) The rate constant, k (k=0.0288 s-1)

Please plot the graph in a graph paper (conc. against time)

Based on the above graph

❖ Time taken for concentration of N2O5 to change from 176 x
10-4 M to 88 x 10-4 M is 20 min
❖ Time taken for concentration of N2O5 to change from 88 x
10-4 M to 44 x 10-4 M is also 20 min
❖ The half life for the reaction is a constant and does not
depend on the initial concentration of N2O5
❖ Thus, the above reaction is first order
t 1/2 =
ln2/ k
k= ln 2
20 min

= 0.03 min-1
 GRAPHICAL METHOD: LINEAR GRAPH METHOD
(BASED ON THE INTERGRATED RATE EQUATION AND RATE LAW)
ZERO FIRST SECOND ORDER
ORDER ORDER
[A]o – [A] = kt In [A]o – In [A] = kt 𝟏 𝟏
− = 𝒌𝒕
[A] = -kt +[A]o [𝑨] [𝑨]𝒐
In [A] = -kt + In [A]o
y = mx + c
y = mx + c 𝟏 𝟏
In [A]
[𝑨] =𝒌𝒕+
[A] [𝑨] 𝒐
y = mx + c
[A]o In[A]0 1/[A]

Time Time 1/[A]o Time

EXERCISE
1. The data in the table below represent an unknown rate law. By using
linear graphmethod, answer the question given.
t/min 0 1 2 3 4
[A]/M 1.0 0.79 0.62 0.35 0.18

a) Determine the rate law

b) Calculate the rate constant for the reaction
c) Determine the half-life of the reaction

Please plot the graph in a graph paper