Chapter 14

CHEMICAL KINETICS

(Part I)

Dr. Al-Saadi 1
 14.1

Chemical Kinetics
 Chemical Kinetics is the study of how fast reactions
take place.
o Some reactions are fast (combustion, photosynthesis).
o Some reactions are slow (conversion of diamond to
graphite, corrosion).
 Importance of studying chemical reaction rates:
o Speed up desirable reactions.
o Minimize damage and products by undesirable reactions.
o Useful in drug design, pollution control, oil to chemical
conversion and food processing.

Dr. Al-Saadi 2
 14.1

Rate of a Reaction
 For the reaction A  B
- As time progresses, there are more B molecules and less A
molecules.
- Quantities of A and B can be also expressed as
concentrations, i.e. [A] and [B] , as long as it is a fixed-
volume process.

Dr. Al-Saadi 3
 14.1

Rate of a Reaction
 For the reaction A  B
 The rate is expressed as
either:
o Rate of disappearance
of reactants (decrease
in conc. or negative)
or
o Rate of appearance of The rate of growth or decay in a
products (increase in chemical reaction is not linear but
exponential.
conc. or positive)
Dr. Al-Saadi 4
 14.1

Average Reaction Rate

Square brackets [ ] stand
for molar concentration in
 For the reaction A  B mol/L or M.

– Δ[A] Δ[B]
 Average rate = =
Δt Δt

The quantity Δ[A] is negative ([A]f - [A]i = -ve),

because the concentration of A is decreasing.
The quantity Δ[B] is positive ([B]f - [B]i = +ve),
because the concentration of B is increasing.

Dr. Al-Saadi 5
 14.1

Average Reaction Rate

 +
Br2(aq) + HCOOH(aq)  2Br (aq) + 2H (aq) + CO2(g)
Formic acid

Br2 disappears over time

t1 t2 t3
Dr. Al-Saadi 6
 14.1

Average Reaction Rate

 +
Br2(aq) + HCOOH(aq)  2Br (aq) + 2H (aq) + CO2(g)
 How is the concentration for Br2
of Br2 tracked?
The decrease in the
intensity of color (and
therefore in the
concentration) of Br2 can
be monitored using a
spectrophotometer that
measures the absorption
of light by Br2 .

Dr. Al-Saadi 7
 14.1

Average Reaction Rate

 +
Br2(aq) + HCOOH(aq)  2Br (aq) + 2H (aq) + CO2(g)
The change in Br2 concentration over time

What is the average rate

ti [Br2]i over the first 50 seconds
tf [Br2]f time interval?
– Δ[Br2]
Average rate =
Δt

‒ (0.0101 – 0.0120) M
=
50.0 s
= 3.8010-5 M/s
Dr. Al-Saadi 8
 14.1

Average Reaction Rate

 +
Br2(aq) + HCOOH(aq)  2Br (aq) + 2H (aq) + CO2(g)
The change in Br2 concentration over time

What is the average rate

ti [Br2]i over the first 100 seconds
time interval?
tf [Br2]f
– Δ[Br2]
Average rate =
Δt

‒ (0.00846 – 0.0120) M
=
100.0 s
= 3.5410-5 M/s
Dr. Al-Saadi 9
 14.1

Average Reaction Rate

 +
Br2(aq) + HCOOH(aq)  2Br (aq) + 2H (aq) + CO2(g)
The change in Br2 concentration over time

What is the average rate

over the second 100
seconds time interval?
ti [Br2]i
– Δ[Br2]
Average rate =
tf [Br2]f Δt

‒ (0.00596 – 0.00846) M
=
100.0 s
= 2.5010-5 M/s
Dr. Al-Saadi 10
 14.1

Average Reaction Rate

 +
Br2(aq) + HCOOH(aq)  2Br (aq) + 2H (aq) + CO2(g)
The change in Br2 concentration over time

What is the average rate

over the third 100
seconds time interval?
– Δ[Br2]
Average rate =
ti [Br2]i Δt

tf [Br2]f ‒ (0.00420 – 0.00596) M

=
100.0 s
= 1.7610-5 M/s
Dr. Al-Saadi 11
 14.1

Average Reaction Rate

 The average reaction rate depends on the time
interval.
 The average reaction rate changes over time.

Plot of [Br2] vs time is

a curve and not linear

Dr. Al-Saadi 12
 14.1

Instantaneous Rate
 When we make Δt
shorter and shorter,
instantaneous rates
could be obtained.
 instantaneous rate
is the rate at a
specific instance of
time (slope of a
tangent to the
curve).

Dr. Al-Saadi 13
 14.1

Instantaneous Rate
 Instantaneous rate is
a more useful
quantity (and more
frequently used by
chemists) than the
average rate.
 For example,
at 100 s:
[Br2] = 0.00846 M
Rate = 2.96×10-5 M/s
Dr. Al-Saadi 14
 14.1

Instantaneous Rate
 Instantaneous rate is
a more useful
quantity (and more
frequently used by
chemists) than the
average rate.
 For example,
at 200 s:
[Br2] = 0.00596 M
Rate = 2.09×10-5 M/s
Dr. Al-Saadi 15
 14.1

Instantaneous Rate

Dr. Al-Saadi 16
 14.1

Instantaneous Rate

 What can you conclude?

When the [Br2] is halved; the rate is halved.

 Is this conclusion consistent with any other selected

data?

Dr. Al-Saadi 17
 14.1

Instantaneous Rate

Dr. Al-Saadi 18
 14.1

Instantaneous Rate

 Is this conclusion consistent with any other selected

data?
YES. Rate is directly proportional to [Br2], and the
relationship is linear. rate α [Br2]
rate = k [Br2] Rate Law

Dr. Al-Saadi
Rate Constant 19
 14.1

Rate vs. Concentration

rate = k [Br2]

Slope = k (s-1)

Dr. Al-Saadi 20
 14.1

Rate Constant
Slope = k
rate = k [Br2]
k is a proportionality
constant and is
constant as long as the
temperature remains
unchanged.
 Calculate the value of the rate constant (k) for this
reaction.
You can use the data for any given time to get the
answer.
Dr. Al-Saadi 21
 14.1

Rate Constant
rate = k [Br2]
 Calculate the value of the rate
constant (k) for this reaction.

3.52 10 5 M / s
at t = 50.0 s k  3.49 10 3 s 1
0.0101 M

1.48 10 5 M / s
at t = 300.0 s k  3.52  10 3 s 1
0.00420 M

The calculated k is almost identical and has a unit of s-1.

Dr. Al-Saadi 22
 14.1

Rate Constant for Gaseous Products

 Rate constant can be calculated
for reactions involving gaseous
reactants and/or products by
monitoring their pressures.

2H2O2(aq)  2H2O(l) + O2(g)

The rate of appearance of the
O2 gas can be determined by
monitoring its pressure.

Dr. Al-Saadi 23
 14.1

Rate Constant for Gaseous Products

 Rate constant can be calculated
for reactions involving gaseous
reactants and/or products by
monitoring their pressures.

2H2O2(aq)  2H2O(l) + O2(g)

The rate of appearance of the
O2 gas can be determined by
monitoring its pressure.

Dr. Al-Saadi 24
 14.1

Rate Constant for Gaseous Products

2H2O2(aq)  2H2O(l) + O2(g)
PO2V = nO2RT
PO2 = (nO2 / V ) RT
= [O2] RT
[O2] = (1/RT) PO2
Δ[O2] 1 ΔPO2
=
Average rate = Δt RT Δt

Dr. Al-Saadi 25
 14.1

Rate Constant for Gaseous Products

2H2O2(aq)  2H2O(l) + O2(g)
The rate of appearance
of O2 gas can be related
to the change in PO2 .
Δ[O2] 1 ΔPO2
rate = =
Δt RT Δt
Instantaneous rate can
be determined at any
point on the PO2 curve.
Dr. Al-Saadi 26
 14.1

Stoichiometry and Reaction Rate

 Recall that for the reaction A  B

– Δ[A] Δ[B]
Average rate = =
Δt Δt

 What do you think the rate would be for the reaction:

A  2B ?
Note that B appears at twice the rate that A
disappears.

rate = – Δ[A] and 2 × rate = Δ[B]

Δt Δt
Dr. Al-Saadi 27
 14.1

Stoichiometry and Reaction Rate

 For the reaction:
A  2B
– Δ[A] 1 Δ[B]
rate = =
Δt 2 Δt

• When stoichiometric ratios are not 1:1

aA + bB  cC + dD

rate =  1 D [A]   1 D [B]  1 D [C]  1 D [D]

a Dt b Dt c Dt d Dt
Dr. Al-Saadi 28
 14.1

Stoichiometry and Reaction Rate

 Exercise:
Write the rate expression for the following reaction:
2NO(g) + O2(g)  2NO2(g)

Dr. Al-Saadi 29
 14.1

Stoichiometry and Reaction Rate

 Exercise:
4PH3(g)  P4(g) + 6H2(g)
If molecular hydrogen is formed at a rate of 0.168
M/s, at what rate is P4 being produced?
The rate expression for the reaction is:
1 D [PH3] 1 D [P4] 1 D [H2]
rate = 4 Dt  1 Dt  6 Dt


1 D [H2] 1
 (0.168 M /s)  0.028 M /s
6 Dt 6
1 D [P4]
 0.028 M /s
Dr. Al-Saadi
1 Dt 30
 14.1

Stoichiometry and Reaction Rate

 Exercise:
4PH3(g)  P4(g) + 6H2(g)
At what rate is PH3 being consumed if the rate of
formation of H2 is 0.168?
The rate expression for the reaction is:
1 D [PH3] 1 D [P4] 1 D [H2]
  
rate = 4 Dt 1 Dt 6 Dt

Dr. Al-Saadi 31
 14.2

The Rate Law

Br2(aq) + HCOOH(aq)  2Br(aq) + 2H+(aq) + CO2(g)
rate = k [Br2]
 The equation that relates the rate of the reaction to
the concentration of the reactants is the rate law.
 In general, for a chemical reaction:
aA + bB  cC + dD
rate = k [A]x [B]y
o k : proportionality constant known as the rate constant.
o x and y : the order of the reaction with respect to each
reactant. The values of x and y are determined
experimentally.
Dr. Al-Saadi 32
 14.2

The Rate Law

Br2(aq) + HCOOH(aq)  2Br(aq) + 2H+(aq) + CO2(g)
 Applying the general rate law equation to the reaction
gives:
rate = k [Br2]x [HCOOH]y
o From experiment:
x = 1 and y = 0.
• The reaction is first order with respect to Br2 .
• The reaction is zeroth order with respect to HCOOH.
• The overall order of the reaction (reaction order) is equal
to 1.

Dr. Al-Saadi 33
 14.2

Reaction Order
 The order of the reaction:
o can only be determined from experimental data.
o is not related to the stoichiometric coefficients.
o is always defined in terms of reactant (and not
product) concentrations.
o can be:
• Zeroth order - no relationship, and the reaction rate is
independent of the reactant concentration.
• First order - rate directly proportional to concentration.
• Second order - exponential relationship.
• The sum of exponents (orders) indicates the overall
reaction order.
Dr. Al-Saadi 34
 14.2

Reaction Order
 Example:
The following reaction:
CH3CH2Br + OH  CH3CH2OH + Br
has the rate law:
rate = k [CH3CH2Br] [OH]

The reaction rate is ………… order with respect to CH3CH2Br.

The reaction rate is ………… order in OH.
The overall reaction order is ………..

Dr. Al-Saadi 35
 14.2

How is a Reaction Order Determined?

F2 (g) + 2ClO2 (g)  2FClO2 (g)
 Initial rate is the instantaneous rate at the beginning
of the reaction (time = 0 s).
The initial rate of the reaction changes by varying the
initial concentrations of the reactants.

Dr. Al-Saadi 36
 14.2

How is a Reaction Order Determined?

rate = k [F2]x [ClO2]y

 The reaction order with respect to F2 can be
determined by holding [ClO2] constant.
[F2] [rate] 3 M /s
3  2.4 �10
3  0.20 M  2 2
[rate] 3
1.2 �10 M /s
[F2] 0.10 M
1 1

Dr. Al-Saadi 37
 14.2

How is a Reaction Order Determined?

rate = k [F2]1x [ClO2]y

 The rate doubles as [F2] doubles. Thus, the rate is

linearly proportional to [F2].
The reaction is 1st order with respect to F2 .
x=1
Dr. Al-Saadi 38
 14.2

How is a Reaction Order Determined?

rate = k [F2]1 [ClO2]y

 The reaction order with respect to ClO2 can be
determined by holding [F2] constant.
[ClO2] [rate] 3 M /s
2  0.040 M  4 2  4.8 �10
4
[ClO2] 0.010 M [rate]  3
1.2 �10 M /s
1 1
Dr. Al-Saadi 39
 14.2

How is a Reaction Order Determined?

rate = k [F2]1 [ClO2]1y

 The rate quadruples as [F2] quadruples. Thus, the

rate is also linearly proportional to [ClO2].
The reaction is 1st order with respect to ClO2 .
y=1
Dr. Al-Saadi 40
 14.2

How is a Reaction Order Determined?

F2 (g) + 2ClO2 (g)  2FClO2 (g)

 The rate law of the reaction is:

rate = k [F2][ClO2] Notice that a reaction
order is not related to the
 The reaction is : reaction stoichiometric
coefficients.
o first order in F2
o first order in ClO2
o second order overall.

Dr. Al-Saadi 41
 14.2

How is a Reaction Order Determined?

F2 (g) + 2ClO2 (g)  2FClO2 (g)

 The rate law of the reaction is:

rate = k [F2][ClO2]
 Rate constant can be calculated (Consider Expt. 1)

rate 1.2  10 3 M / s
k   1.2 M 1s 1
[F2 ][ClO2 ] (0.10 M)(0.010 M)

Dr. Al-Saadi 42
 14.2

How is a Reaction Order Determined?

F2 (g) + 2ClO2 (g)  2FClO2 (g)

 The rate law of the reaction is:

rate = k [F2][ClO2]
 Rate constant can be also calculated from another
set of date (Now consider Expt. 2)

rate 4.8  10 3 M / s
k   1.2 M 1s 1
[F2 ][ClO2 ] (0.10 M)(0.040 M)
Dr. Al-Saadi 43
 14.2

Reaction Order
 Exercise:
2NO(g) + 2H2(g)  N2(g) + 2H2O (g)
The following experiments were run at 1280C.
Expt. [NO] (M) [H2] (M) Initial Rate (M/s)
1 5.0 × 10-3 2.0 × 10-3 1.3 × 10-5
2 1.0 × 10-2 2.0 × 10-3 5.1 × 10-5
3 1.0 × 10-2 4.0 × 10-3 1.0 × 10-4

(a) Write down the correct rate law.

(b) Determine the rate constant.
(c) What is the rate of the reaction when [NO] is
4.8 × 10-3 M and [H2] is 6.2 × 10-3 M?
Dr. Al-Saadi 44
 14.2

Units of Rate Constant

 The units of the rate constant (k) depend on the

overall reaction order.

Dr. Al-Saadi 45
 14.3

Integrated Rate Law 1 order reactions

st

• Consider the following first-order reaction:

A  products
The reaction rate can be expressed either as:
rate = k[A] (Rate law)
or:
Δ[A]
rate = ‒ (Average rate)
Δt

Then,
‒ Δ[A] = k[A]
Δt
Dr. Al-Saadi 46
 14.3

Integrated Rate Law 1 order reactions st

• Consider the following first-order reaction:

A  products

integrating both sides from t = 0 to t gives:

ln ( [A]t ) = ‒ kt Integrated
rate law
[A]0
which can be rearranged as:
ln[A]t = ‒ kt + ln[A]0 linear equation

y = m x + b

Dr. Al-Saadi 47
 14.3

Integrated Rate Law 1 order reactions st

 For a 1st order reaction, a plot of ln[A] vs. time yields

a straight line with slope =  k (the rate constant).

(sec) (sec)

ln[A]t = ‒ kt + ln[A]0
Dr. Al-Saadi 48
 14.3

Integrated Rate Law 1 order reactions

st

 Exercise:
2A  B
The above reaction is 1st order in A, and its rate
constant is 7.5 x 10-3 s-1 at 110C. How many minutes
will it take for [A] to decrease from 1.25 M to 0.71
M?
[A]t
ln ( ) = ‒ kt
[A]0

Dr. Al-Saadi 49
 14.3

Half Life 1 order reactions

st

 Half-life (t1/2) is the time that it takes for the reactant

concentration to drop to half of its original value.
 For 1st order reactions:
[A]t
ln ( [A] ) = ‒ kt
0

when t = t1/2 , [A]t = ½[A]0 . Then,

ln2 = 0.693
1 [A]0
t1/2 = ln ( )
k ½[A]0
ln2 0.693
For 1 order reaction, t1/2 =
st
k =
k
Dr. Al-Saadi 50
 14.3

Half Life 1 order reactions

st

 For 1st order reactions,

the t1/2 is independent of
the initial concentration
of the reactant.
For a 1st order reaction, it
takes the same time for a
reactant conc. to
decrease from 1.0 M to
0.5 M as it does for the
conc. to decrease from
0.5 M to 0.25 M.
Dr. Al-Saadi 51
 14.3

Half Life and Rate Constant

0.693
For 1 order reaction, t1/2 =
st
k

o The half life is inversely

proportional to the rate constant of
the reaction. A short half-life
corresponds to a larger rate
constant (faster reactions).
o Measurement of the half-life is one
way to determine the rate constant.

Dr. Al-Saadi 52
 14.3

2 Order Reactions
nd

 The integrated rate law and half-life for 2nd order

reactions can be also derived.

1 1
o Integrated rate law = kt +
[A]t [A]0

1
o Half-life t1/2 =
k[A]0
The half-life of a second-order
reaction is NOT constant, and it
depends on the initial conc. of
the reactant.

Dr. Al-Saadi 53
 14.3

2 Order Reactions
nd

1 1
= kt +
[A]t [A]0

Dr. Al-Saadi 54
 14.3

Integrated Rate Law & Half Life

Dr. Al-Saadi 55
 14.4

Collision Theory
 Particles must collide so that they can react.
 Collision Theory: The greater the frequency of
collisions, the higher the reaction rate.
number of collisions
rate 
1 second
Does every collision result with a chemical reaction?
Is every collision an effective collision?

Dr. Al-Saadi 56
 14.4

Collision Theory
 In order to have an effective collision which causes
a reaction to proceed, some factors must be met:
o Proper orientation of the reactant molecules.
o Sufficient kinetic energy (faster motion) of the
reactant molecules.
Kinetic Vibrational
energy Collisions energy
Molecules vibrate
Greater Effective more strongly and
kinetic energy collisions some chemical bonds
break
Dr. Al-Saadi 57
 14.4

Collision Theory
Cl + NOCl  Cl2 + NO

Proper orientation & sufficient kinetic energy Effective collision

The reaction is more likely to take place

Improper orientation and/or insufficient kinetic energy Ineffective collision

The molecules bounce off of each other and the
Dr. Al-Saadi reaction doesn’t take place 58
 14.4

Activation Energy
 Activation energy (Ea) is the minimum amount of
energy required to initiate a chemical reaction.

An activated
complex or
transition state is a
temporary species
that forms upon
Cl + NOCl effective collisions.
Cl2 + NO

Potential energy profile for the reaction:

Dr. Al-Saadi Cl + NOCl  Cl2 + NO 59
 14.4

Activation Energy
 Activation energy (Ea) is the minimum amount of
energy required to initiate a chemical reaction.
Ea is an energy barrier
that prevents less
energetic molecules
from proceeding to the
product side.
Cl + NOCl
The higher Ea is, the
Cl2 + NO
smaller the rate
constant is.
Potential energy profile for the reaction:
Dr. Al-Saadi Cl + NOCl  Cl2 + NO 60
 14.4

Do Reactions Depend on Temperature?

 Cocking food at 200C and at 20C.

Which one would be faster?
 Hard-boiling eggs in boiling water or
just in warm water. Which process
would be faster?
 Keeping fruits on the shelf, keeping food
inside the refrigerator, or keeping food
in the freezer. Where would the fruit
spoil more slowly?

Dr. Al-Saadi 61
 14.4

Temperature Effect on Reaction Rate

According to kinetic
molecular theory (CHEM
101),
KEave  absolute T
When the temperature is
Cl + NOCl raised, more molecules
will have sufficient KE to
Cl2 + NO
exceed the activation
energy barrier. As a
Potential energy profile for the reaction: result, the reaction
Cl + NOCl  Cl2 + NO
speeds up and its rate
constant (k) increases.
Dr. Al-Saadi 62
 14.4

The Arrhenius Equation

• The dependence of the rate constant of a reaction on

temperature can be expressed by the Arrhenius
equation: Rate constant decreases with
the increase of activation
 Ea
energy, with the decrease of
k  Ae RT
collision frequency, and with
the decrease in temperature
Ea : activation energy.
R : universal gas constant (8.314 J/K∙mol).
T : Kelvin temperature.
A : frequency factor (collision frequency).

Dr. Al-Saadi 63
 14.4

Arrhenius Equation for Two Reaction Points

 Taking (ln) of both sides, followed with a simple

mathematical treatment of Arrhenius equation
gives:
k1 Ea  1 1 
ln    
k2 R  T2 T1 

o If we know the rate constants at two temperatures,

then the activation energy can be calculated.
o If we know the activation energy and the rate constant
at a given temperature, the value of the rate constant
at any other temperature can be calculated.
Dr. Al-Saadi 64
 14.4

Using Arrhenius Equation

 Exercise:
Find the activation energy for the following reaction:
CO(g) + NO2(g)  CO2(g) + NO(g)
The rate constants were found to be 0.028 M–1s–1 at 327oC and 23
M–1s–1 at 527oC.

k1 = 0.028 M–1s-1
@ T1 = 327 + 273 = 600 K

k2 = 23 M–1s–1 @ T2 =
527 + 273 = 800 K

What is the total

order of this reaction?
= 133800 J/mol = 130 kJ/mol
Dr. Al-Saadi 65
 14.4

Linear Form of Arrhenius Equation

 Ea
k  Ae RT

 Arrhenius equation can be expressed in other useful

forms.
Taking the natural Rearrangement gives a linear equation
logarithm of both sides: as:
 Ea
 Ea  1 
ln k  ln Ae RT ln k       ln A
 R  T 
Then:
Ea
ln k  ln A 
RT y slope x intercept

Dr. Al-Saadi 66
 14.4

Plot of Arrhenius Equation

 Ea  1 
ln k       ln A
 R  T 
 The straight line resulting
from plotting the Arrhenius
equation has a slope that is
1/T
equal to ‒ Ea/R.
Thus, the value of the Note that the slope is
–ve. As a result, the value
activation energy (Ea) can be of Ea will be +ve.
determined from knowing
the rate constant (k) at a
Dr. Al-Saadi
specific temperature. 67
 14.4

Using Arrhenius Equation

 Exercise: k (M–1s–1) T (oC)
Consider the reaction: 3.52×10–7 283
2 HI(g)  H2(g) + I2(g) 3.02×10–5 356
The data shown in the table 2.19×10–4 393
were measured at different 1.16×10–3 427
temperatures.
3.95×10–2 508
Find the activation energy.
To answer the question, we need to find:
• ln k
• 1/T ; where T in K
• and then plot ln k vs. 1/T.
The slope of the line will lead us to the activation energy.
Dr. Al-Saadi 68
 14.4

k ln k T (oC) T (K) 1/T (K-1)

3.52×10–7 –14.860 283 556 1.80×10–3
3.02×10–5 –10.408 356 629 1.59×10–3
2.19×10–4 –8.426 393 666 1.50×10–3
1.16×10–3 –6.759 427 700 1.43×10–3
3.95×10–2 –3.231 508 781 1.28×10–3

We select any two points from the straight line.

Dr. Al-Saadi 69