CHM 431

PHYSICAL CHEMISTRY

CHAPTER 4
CHEMICAL KINETIC
Kinetics: Rates and Mechanisms of Chemical
Reactions

12-Sep-17
16.1 Factors That Influence Reaction Rates - LAB

16.2 Expressing the Reaction Rate

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16.3 The Rate Law and Its Components - LAB

16.4 Integrated Rate Laws: Concentration Changes over Time

16.5 The Effect of Temperature on Reaction Rate

16.6 Explaining the Effects of Concentration and Temperature

16.7 Reaction Mechanisms: Steps in the Overall Reaction

16.8 Catalysis: Speeding Up a Chemical Reaction

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 INTRODUCTION

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 Chemical kinetics is the study of reaction rate
,the changes in concentrations of reactant ( or
products ) as a function of time.

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 By the way, the study of motion is called kinetics,
from Greek kinesis, meaning movement.

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REACTIONS OCCUR AT WIDE RANGE OF
RATES

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 In seconds interval
- neutralization, precipitation or

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explosive redox process

 In mins/months interval
- cooking , rusting , ripening, rusting

 In years interval
- human aging
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Figure 16.2 The wide range of reaction rates.

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Figure A faster reaction (top) and a slower reaction
16.1 (bottom).
 Factors That Influence Reaction
Rate
 Particles must collide in order to react.
 The higher the concentration of reactants, the greater
the reaction rate.
 A higher concentration of reactant particles allows a greater
number of collisions.
 The physical state of the reactants influences reaction
rate.
 Substances must mix in order for particles to collide.
 The higher the temperature, the greater the reaction
rate.
 At higher temperatures particles have more energy and therefore
collide more often and more effectively.
 Expressing the Reaction Rate

Reaction rate is measured in terms of the changes in

concentrations of reactants or products per unit time.

For the general reaction A → B, we measure the concentration of A

at t1 and at t2:

change in concentration of A conc A2 - conc A1 D[A]

Rate = =- =-
change in time t2 - t 1 Dt

Square brackets indicate a concentration in moles per liter.

The negative sign is used because the concentration of A is

decreasing. This gives the rate a positive value.
Figure 16.1 Reaction rate: the central focus of chemical kinetics

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 REACTION RATES(CONT.)

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With respect to reaction rates, we may
deal with :

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 average rates,

 instantaneous rates,

 or initial rates

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 REACTION RATES(CONT.)

12-Sep-17
depending on the experimental conditions :
average rate: rate measured between long time

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
interval
 instantaneous rate: rate measured between
very short interval
 initial rate: instantaneous rate at the

beginning of an experiment

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Table 16.1 Concentration of O3 at Various Times in
its Reaction with C2H4 at 303 K

Concentration of O3
Time (s) (mol/L)

0.0 3.20x10-5 D [C2H4]

10.0 2.42x10-5 rate = -
Dt
20.0 1.95x10-5 D [O3]
=-
30.0 1.63x10-5 Dt
40.0 1.40x10-5
50.0 1.23x10-5
60.0 1.10x10-5
Figure 16.5 Three types of reaction rates for the
reaction of O3 and C2H4.
 Instantaneous
rate
Consider the reaction of decomposition of hydrogen iodide:
2HI(g) → H2(g) + I2(g).
The slope is negative because we are measuring the disappearance of HI.

A plot of the concentration of HI versus time for the reaction:

 Instantaneous
rate
[Br2] conc vs time, s

0.014

0.012
Rate at 100s = 0.0000296 M/s

0.01
Rate at 200s = 0.0000209 M/s
[Br2], M

0.008
Rate at 300s = 0.0000148 M/s
0.006

0.004

0.002

0
0 100 200 300 400 500
time, s
 AVERAGE RATE
Example: [Br2] Average
Br2(g) + HCOOH(aq) → time (M) rate
0 0.012 (M/s)
0.0000380
2Br-(aq) + 2H+ (aq) + 50 0.0101
CO2(g) 0.0000328
100 0.00846
Average rate (0-50s) 0.0000272
= -Δ[Br2] / Δt 150 0.0071
0.0000228
= (0.0101 -0.0120) / (50 – 0) s 200 0.00596
= 3.80 x 10-5 M/s 250 0.005 0.0000192
300 0.0042 0.0000160
Average rate in next 50s
= (0.00846 – 0.0101)M / (100- 350 0.00353 0.0000134
50) s 400 0.00296 0.0000114
= 3.28 x 10-5 M/s
Figure 16.6A Plots of [reactant] and [product] vs.
time.

C2H4 + O3 → C2H4O + O2

[O2] increases just as fast as

[C2H4] decreases.

D[C2H4] D[O3]
Rate = - =-
Dt Dt

D[C2H4O] D[O2]
= =
Dt Dt
Figure 16.6B Plots of [reactant] and [product] vs.
time.

H2 + I2 → 2HI
[HI] increases twice as
fast as [H2] decreases.

D[H2] D[I2] 1 D[HI]

Rate = - =- =
Dt Dt 2 Dt

D[HI] D[H2] D[I2]

Rate = = -2 = -2
Dt Dt Dt

The expression for the rate of a

reaction and its numerical value
depend on which substance serves as
the reference.
In general, for the reaction

aA + bB → cC + dD

where a, b, c, and d are the coefficients for the balanced equation,

the rate is expressed as:

1 D[A] 1 D[B] D[C] D[D]

rate = - =- = 1 = 1
Dt Dt Dt Dt
a b c d
CONSIDER THIS REACTION
BR2(AQ) + HCOOH(AQ) → 2BR-(AQ) +2H+(AQ) + CO2(AQ)
Time(s) [Br2] (M) Reaction Rate k (s-1)

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(M/s) x 10-5 X 10-3
0.0 0.0120 4.20 3.50

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50.0 0.0101 3.52 3.49
100.0 0.00846 2.96 3.50
150.0 0.00710 2.49 3.51
200.0 0.00596 2.09 3.51
250.0 0.00500 1.75 3.50
300.0 0.00420 1.48 3.52
350.0 0.00353 1.23 3.48
400.0 0.00296 1.04 3.51 20
TO CALCULATE AVERAGE RATE

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Average rate = - d[Br2]
dt

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= -[Br2]final – [Br2]initial
t final – t initial
= -(0.0101 – 0.0 120)M
50 -0
= 3.80 x 10-5 Ms-1

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 Table 16.1 Concentration of O3 at Various Time in its
Reaction with C2H4 at 303K

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C2H4(g) + O3(g) C2H4 O(g) + O2(g)

Time (s) Concentration of O3 (mol/L)

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0.0 3.20x10-5
D (conc A)
- 10.0 2.42x10-5
Dt
20.0 1.95x10-5
30.0 1.63x10-5
40.0 1.40x10-5
50.0 1.23x10-5
60.0 1.10x10-5
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Figure 16.5
The concentrations of O3 vs. time during its reaction with C2H4
C2H4(g) + O3(g) C2H4 O(g) + O2(g)

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rate =

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D [C2H4]
- =
Dt

D [O3]
-
Dt

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 Figure 16.6 Plots of [C2H4] and [O2] vs. time.

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Dr NORAINI HAMZAH
Tools of the
Laboratory

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 Sample problem 1:

Ammonium cyanate rearranges in water to give urea. The kinetics

of this reaction were studied.

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NH4NCO(aq)  (NH2)2CO(aq)

Time (min) [NH4NCO] (M)

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1 0 0.458
2 45 0.370
3 107 0.292
4 230 0.212

1. Calculate the average rate of reaction between 45 minutes

and 230 minutes.
2. Use the graph above to calculate the instantaneous rate at 45
minutes.

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MEASURING REACTION RATE
 To measure a reaction rate, we usually monitor either a

12-Sep-17
product or a reactant for its change.

 Some of the characteristics to be monitored are:

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- changes in pressure
- changes in color (use spectrofotometer )
- changes in temperature (for exothermic or
endothermic reaction) and
- presence of catalyst

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 concentration

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Dr NORAINI HAMZAH
Catalyst Factor That affect
Reaction Rate Temperature

Nature of reactant

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COLLISION THEORY
molecules must:

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 collide in order for a reaction to occur

Not all collision between molecules result in

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
chemical reaction.

 Only a small fraction of the total number of

collision is effective and it results in the
formation of products.

 In order to react, the molecules must be oriented

so that correct “ends” of the molecules come in
contact
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Figure 16.4 Collision energy and reaction rate.

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FACTORS THAT INFLUENCE REACTION RATES

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1) Nature of Reactants

 Physical state

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Acid-base reactions, formation of salts, and exchange of ions are
fast reactions.

 Size of particle
Reactions in which large molecules are formed or break apart are
usually slow.

 Bonding
Reactions breaking strong covalent bonds are also slow.

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Effect of crushing a
solid.

When a single solid is

subdivided into much
smaller pieces, the total
surface area on all of the
pieces becomes very
large.
FACTORS INFLUENCE REACTION RATES (CONT.)

2) Temperature

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 Usually, the higher the temperature, the faster the reaction.

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 The number of molecule which have kinetic energy equal
or more with Ea increasing.

 Therefore, it will increase the frequency of effective

collision.

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Figure 16.14
The effect of temperature on the distribution of collision energies
FACTORS INFLUENCE REACTION RATES
(CONT.)

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3) Concentration
 Usually, higher concentration will

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increase the reaction rate.

 At higher concentration, the number of

molecule will increase, so it will increase
the frequency of effective collision.

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FACTORS INFLUENCE REACTION RATES
(CONT.)

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4) Catalysts

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 substances used to speed up the rate of
reactions (Ea lower) without being
consumed in the reaction.

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 WHAT ARE CATALYSTS?

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A catalyst is a substance which speeds up
a reaction, but is chemically unchanged at

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the end of the reaction.

 When the reaction has finished, you would

have exactly the same mass of catalyst as
you had at the beginning.

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 TYPE OF CATALYSIS

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a) Homogeneous
 The catalyst is in the same phase as

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the reactants.

b) Heterogeneous
 The catalyst is in a different phase
than the reactants – often a solid
catalyst and liquid or gaseous
reactants. 37
 CATALYSTS

•Each catalyst has its own specific way of functioning.

•In general a catalyst lowers the energy of activation.
•Lowering the Ea increases the rate constant, k, and
thereby increases the rate of the reaction
•A catalyst increases the rate of the forward AND the
reverse reactions.
•A catalyzed reaction yields the products more quickly,
but does not yield more product than the uncatalyzed
reaction.
•A catalyst lowers Ea by providing a different mechanism,
for the reaction through a new, lower energy pathway.
 Catalysts provide an alternative pathway from reactants

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to products.

catalyst does not increase the amount of product.

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

 Catalyst does not change the value of DH

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Figure 16.22

Reaction energy diagram of a catalyzed and an uncatalyzed process.

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ACTIVATION ENERGY, EA

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 The minimum energy required by the reactant to
form an activated complex in the transition state.

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ACTIVATION ENERGY(CONT.)

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The height of the
activation barrier
influences the rate:

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 If Ea is large, the rate is
slow.

 If Ea is small, rate is
faster.

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Figure 16.15 Energy-level diagram for a reaction

ACTIVATED STATE

Ea (forward)

Ea (reverse)
Collision

Collision
Energy

Energy
REACTANTS

PRODUCTS

The forward reaction is exothermic because

the reactants have more energy than the
products.
ACTIVATED COMPLEX
( TRANSITION STATE THEORY)

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 The activated complex is a species intermediate
between reactants and products with the maximum

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potential energy.

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Figure 16.17

The importance of molecular orientation to an effective collision.

12-Sep-17
NO + NO3 2 NO2

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A is the frequency factor
Z is the collision frequency
A = pZ where
p is the orientation probability factor 46
Figure 16.18
Nature of the transition state in the reaction between CH3Br and OH-.

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CH3Br + OH- CH3OH + Br -

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transition state or activated complex
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Figure 16.19 Reaction energy diagram for the reaction of CH3Br and OH-.

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Figure 16.20
Reaction energy diagrams and possible transition states.

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Sample Problem 16.7 Drawing Reaction Energy Diagrams and
Transition States
PROBLEM: A key reaction in the upper atmosphere is

12-Sep-17
O3(g) + O(g) 2O2(g)
The Ea(fwd) is 19 kJ, and the DHrxn for the reaction is -392 kJ. Draw a
reaction energy diagram for this reaction, postulate a transition state, and

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calculate Ea(rev).
PLAN: Consider the relationships among the reactants, products and
transition state. The reactants are at a higher energy level than the
products and the transition state is slightly higher than the
reactants.

SOLUTION: Ea= 19kJ

Potential Energy

O3+O transition state Ea(rev)= (392 + 19)kJ =

DHrxn = -392kJ 411kJ
breaking
O bond
2O2 O O 50
forming O
bond
Reaction progress
 REACTION RATES AND STOICHIOMETRY
In acidic solutions, hydrogen peroxide and iodide

12-Sep-17
ion react according to the equation:
H2O2 + 2H+ + 3I-  2H2O + I3-.

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In this reaction, the reaction Rate can be expressed
as : decreasing Rate of H2O2 : -d[H2O2]/dt
decreasing Rate of H+ : -d[H+]/dt
decreasing Rate of I- : -d[I-]/dt
increasing Rate of H2O : +d[H2O] /dt
increasing Rate of I3- : +d[I3-]/dt

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In general, for the reaction

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aA + bB cC + dD

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1 D[A] 1 D[B] 1 D[C] 1 D[D]
rate = - = - = + = +
a Dt b Dt c Dt d Dt

The numerical value of the rate depends upon the substance that
serves as the reference. The rest is relative to the balanced
chemical equation.

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 REACTION RATES AND STOICHIOMETRY

However, from the stoichiometry, you

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can easily see the following relationship:

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d[H2O2] 1 d[H+] 1 d[I-] 1 d[H2O] d[I3-]
- ------- = - ------ = - ------- = + ------ = + ------
- dt 2 dt 3 dt 2dt dt

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Sample Problem 16.1 Expressing Rate in Terms of Changes in
Concentration with Time

PROBLEM: Because it has a nonpolluting product (water vapor), hydrogen

12-Sep-17
gas is used for fuel aboard the space shuttle and may be used
by Earth-bound engines in the near future.
2H2(g) + O2(g) 2H2O(g)

Dr NORAINI HAMZAH
(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*s, at what rate is [H2O]
increasing?
PLAN: Choose [O2] as a point of reference since its coefficient is 1. For every
molecule of O2 which disappears, 2 molecules of H2 disappear and 2
molecules of H2O appear, so [O2] is disappearing at half the rate of
change of H2 and H2O.
SOLUTION: D[H2] D[O2] D[H2O]
1 1
(a) rate = - =- =+
2 Dt Dt 2 Dt
D[O2] D[H2O] D[H2O]
(b) - = - 0.23mol/L*s =+ 1 ; = 0.46mol/L*s54
Dt 2 Dt Dt
 EXAMPLES
Consider the reaction for the combustion

12-Sep-17
of methane, CH4 ,
CH4(g) + 2O2(g)  2N2(g)+ 6H2O(g)

Dr NORAINI HAMZAH
If the methane is burning at a rate of
0.16 molL-1s-1 , at what rates are N2
and H2O being formed?

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SOLUTION

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CH4(g) + 2O2(g)  2N2(g)+ 6H2O(g)
Given d[CH4] = 0.16 molL-1s-1

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dt

so; d[CH4] = d[N2] = d[H2O]

dt 2 dt 6 dt

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SOLUTION

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To calculate rate of N2;

Dr NORAINI HAMZAH
d[N2] = 2 x d[CH4]
dt dt

= 2 x 0.16 molL-1s-1
= 0.32 molL-1s-1

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SOLUTION

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To calculate rate of H2O;

Dr NORAINI HAMZAH
d[H2O] = 6x d[CH4]
dt dt

= 6 x 0.16 molL-1s-1
= 0.96 molL-1s-1

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 RATE LAW
The rate law is an expression for the reaction rate

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in terms of concentrations of chemical species
involved in the reaction.
For example,

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Rate = k [A]m [B]n

where :
k is a rate constant,
m is reaction order with respect to A,
n is reaction order with respect to B,
m+n is the overall reaction order.
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 The Rate Law
For any general reaction occurring at a fixed temperature

aA + bB → cC + dD

Rate = k[A]m[B]n

The term k is the rate constant, which is specific for a given

reaction at a given temperature.

The exponents m and n are reaction orders and are

determined by experiment.
The values of m and n are not necessarily related in any
way to the coefficients a and b.
 Individual and Overall Reaction
Orders
For the reaction 2NO(g) + 2H2(g) → N2(g) + 2H2O(g):

The rate law is rate = k[NO]2[H2]

The reaction is second order with respect to NO, first order

with respect to H2 and third order overall.

Note that the reaction is first order with respect to H2 even

though the coefficient for H2 in the balanced equation is 2.

Reaction orders must be determined from experimental data

and cannot be deduced from the balanced equation.
 Reaction Orders
A reaction has an individual order “with respect to” or “in” each
reactant.

For the simple reaction A → products:

If the rate doubles when [A] doubles, the rate depends on [A]1 and
the reaction is first order with respect to A.

If the rate quadruples when [A] doubles, the rate depends on [A]2
and the reaction is second order with respect to [A].

If the rate does not change when [A] doubles, the rate does not
depend on [A], and the reaction is zero order with respect to A.
Sample Problem 16.2 Determining Reaction Order from Rate Laws

PROBLEM: For each of the following reactions, determine the reaction order

12-Sep-17
with respect to each reactant and the overall order from the
given rate law.
(a) 2NO(g) + O2(g) 2NO2(g); rate = k[NO]2[O2]

Dr NORAINI HAMZAH
(b) CH3CHO(g) CH4(g) + CO(g); rate = k[CH3CHO]3/2
(c) H2O2(aq) + 3I-(aq) + 2H+(aq) I3-(aq) + 2H2O(l); rate = k[H2O2][I-]

PLAN: Look at the rate law and not the coefficients of the chemical reaction.

SOLUTION:

(a) The reaction is 2nd order in NO, 1st order in O2, and 3rd order overall.

(b) The reaction is 3/2 order in CH3CHO and 3/2 order overall.
(c) The reaction is 1st order in H2O2, 1st order in I- and zero order in H+,
while being 2nd order overall.
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Figure 16.7 Plots of reactant concentration, [A], vs.
time for first-, second-, and zero-order
reactions.
Figure 16.8 Plots of rate vs. reactant concentration,
[A], for first-, second-, and zero-order
reactions.
RATE CONSTANT
 The rate constant is independent of the

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concentrations of the chemical species involved in the
reaction.

Dr NORAINI HAMZAH
 However, it depends on other factors such as
temperature or ionic strength, e.g., k(T).

 The units of the rate constant depend on the

overall reaction order.

 In general, the form of the rate law is NOT

determined by the reaction stoichiometry, but is
determined by the reaction mechanism.

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UNITS OF THE RATE CONSTANT

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Example: second order

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Rate = k [A][B] or

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UNITS OF THE RATE CONSTANT
(CONT.)

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Assuming time in second(s).

Order Unit of rate constant

Dr NORAINI HAMZAH
Zero moldm-3s-1( Ms-1)
First s-1
Second dm3mol-1s-1 (M-1s-1)
Third dm6mol-2s-1 (M-2s-1)

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RATE CONSTANTS AND THE ORDERS
2NO + O2  2NO2

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Usually, the rate of a reaction is a function
of the concentrations of reactants .

Dr NORAINI HAMZAH
example :
Rate = k [O2] [NO]2

The orders of 1 and 2 for [O2] and [NO]

respectively has been determined by
experiment, NOT from the chemical
equation.
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RATES AS FUNCTIONS OF
REACTANT CONCENTRATIONS

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In a general reaction,
a A + b B +  products

Dr NORAINI HAMZAH
Rate = k[A]x[B]y

If concentrations of B is kept
constant, you can measure the reaction
rate of A at various concentrations.

70
 Determining Reaction
Orders

For the general reaction A + 2B → C + D,

the rate law will have the form
Rate = k[A]m[B]n

To determine the values of m and n, we run a series of

experiments in which one reactant concentration changes while
the other is kept constant, and we measure the effect on the initial
rate in each case.
Table 16.2 Initial Rates for the Reaction between A
and B
Initial Rate Initial [A] Initial [B]
Experiment (mol/L·s) (mol/L) (mol/L)
1 1.75x10-3 2.50x10-2 3.00x10-2
2 3.50x10-3 5.00x10-2 3.00x10-2
3 3.50x10-3 2.50x10-2 6.00x10-2
4 7.00x10-3 5.00x10-2 6.00x10-2

[B] is kept constant for experiments 1 and 2, while [A] is

doubled. Then [A] is kept constant while [B] is doubled.
 Finding m, the order with respect to A:

We compare experiments 1 and 2, where [B] is kept constant but [A]

doubles:

Rate 2 k[A] m [B] n [A]2

m
[A]2 m
2 2 = =
=
Rate 1 k[A] m
1
[B] n
1
m
[A]1
[A]1
m
3.50x10-3 mol/L·s 5.00x10-2 mol/L
=
1.75x10-3mol/L·s 2.50x10-2 mol/L

Dividing, we get 2.00 = (2.00)m so m = 1

 Finding n, the order with respect to B:

We compare experiments 3 and 1, where [A] is kept constant but [B]

doubles:

Rate 3 k[A] m [B] n n

[B]3 [B]3 n
3 3 = =
=
Rate 1 k[A] m
1
[B] n
1
n
[B]1
[B]1
m
3.50x10-3 mol/L·s 6.00x10-2 mol/L
=
1.75x10-3mol/L·s 3.00x10-2 mol/L

Dividing, we get 2.00 = (2.00)n so n = 1

Table 16.3 Initial Rates for the Reaction between
O2 and NO
O2(g) + 2NO(g) → 2NO2(g) Rate = k[O2]m[NO]n

Initial Reactant
Concentrations (mol/L)
Initial Rate
Experiment (mol/L·s) [O2] [NO]
1 3.21x10-3 1.10x10-2 1.30x10-2
2 6.40x10-3 2.20x10-2 1.30x10-2
3 12.48x10-3 1.10x10-2 2.60x10-2
4 9.60x10-3 3.30x10-2 1.30x10-2
5 28.8x10-3 1.10x10-2 3.90x10-2
 Finding m, the order with respect to O2:

We compare experiments 1 and 2, where [NO] is kept

constant but [O2] doubles:

Rate 2 k[O2] m [NO]n

[O2] m
2 = [O2]2
2 2 m
= m n = m
Rate 1 k[O2] 1 [NO]1 [O2]1 [O2]1
m
6.40x10-3 mol/L·s 2.20x10-2 mol/L
=
3.21x10-3mol/L·s 1.10x10-2 mol/L

Dividing, we get 1.99 = (2.00)m or 2 = 2m, so m = 1

The reaction is first order with respect to O2.

Sometimes the exponent is not easy to find by inspection. In those
cases, we solve for m with an equation of the form a = bm:

log a log 1.99

m= = = 0.993
log b log 2.00

This confirms that the reaction is first order with respect to O2.

Reaction orders may be positive integers, zero, negative

integers, or fractions.
Finding n, the order with respect to NO:

We compare experiments 1 and 3, where [O2] is kept constant

but [NO] doubles:

n
Rate 3 [NO]3 n
12.8x10-3 mol/L·s 2.60x10-2 mol/L
= =
Rate 1 [NO]1 3.21x10-3mol/L·s 1.30x10-2 mol/L
Dividing, we get 3.99 = (2.00)n or 4 = 2n, so n = 2.

log a log 3.99

Alternatively: n= = = 2.00
log b log 2.00

The reaction is second order with respect to NO.

The rate law is given by: rate = k[O2][NO]2

 SAMPLE PROBLEM

12-Sep-17
A reaction between substances A and B is represented stoichiometrically by
A+B →C
Observation on the rate of this reaction are obtained in three separate
experiments as follows:

Dr NORAINI HAMZAH
What is the order with respect to each reactant, and what is the value of the
rate constant?

[A]0, M [B]0, M Duration of Final

experiment, concentration,
Δt, h [A]f, M
0.100 1.0 0.50 0.0975
0.100 2.0 0.50 0.0900
79
0.0500 1.0 2.00 0.0450
Sample Problem Determining Reaction Orders from
16.3 Rate Data

PROBLEM:
Many gaseous reactions occur in a car engine and exhaust
system. One of these is
NO2(g) + CO(g) → NO(g) + CO2(g)
rate = k[NO2]m[CO]n
Use the following data to determine the individual and overall
reaction orders:
Initial Rate Initial [NO2] Initial [CO]
Experiment (mol/L·s) (mol/L) (mol/L)
1 0.0050 0.10 0.10
2 0.080 0.40 0.10
3 0.0050 0.10 0.20
Sample Problem 16.3

PLAN: We need to solve the general rate law for m and for n
and then add those orders to get the overall order. We
proceed by taking the ratio of the rate laws for two
experiments in which only the reactant in question
changes concentration.
SOLUTION:
To calculate m, the order with respect to NO2, we compare
experiments 1 and 2:
m
0.080 0.40
=
rate 2 k [NO2]m2[CO]n2 [NO2] 2
m 0.0050 0.10
= =
rate 1 k [NO2]m1 [NO2] 1 16 = (4.0)m so m = 2
[CO]n1

The reaction is second order in NO2.

Sample Problem 16.3

To calculate n, the order with respect to CO, we compare

experiments 1 and 3:

n
n 0.0050 0.20
rate 3 k [NO2]m3[CO]n3 [CO] 3 =
= = 0.0050 0.10
rate 1 k [NO2] 1
m
[CO] 1
[CO] 1
n
1.0 = (2.0)n so n
=0

The reaction is zero order in CO.

rate = k[NO2]2[CO]0 or rate = k[NO2]2

EVALUATION OF ORDER BY
EXPERIMENTS –INITIAL RATE METHOD
Example :
Derive the rate law for the reaction
A + B + C  products
from the following data :

Expriment 1 2 3 4
[A]0 0.100 0.200 0.200 0.100
[B]0 0.100 0.100 0.300 0.100
[C]0 0.100 0.100 0.100 0.400
rate 0.100 0.800 7.200 0.400
12-Sep-17 Dr NORAINI HAMZAH 83
EVALUATION OF ORDER BY
EXPERIMENTS (CONT.)

12-Sep-17
Assume: rate = k [A]x [B]y [C]z
From experiment 1 and 2, we have:

Dr NORAINI HAMZAH
0.800 k [0.2]x [0.1]y [ 0.1]z
----- = ------------------------
0.100 k [0.1]x [0.1]y [0.1]z

Thus, 8 = 2x; and x = ln8 / ln2 = 3

By similar procedures, we get y = 2 and z = 1.

Thus, the rate law is: rate = k [A]3 [B]2 [C]

overall order = 3+2+1 = 6 84
 The following data refers to the following
reaction:

CH3COCH3 + I2 + H+  CH3COCH2I + HI

Expt. [CH3COCH3], [H+], [I2], Initial

M M M rate, Ms
-1

1 3.0 0.2 0.02 6.0 x 10-6

2 3.0 0.4 0.02 12.0 x 10-6
3 4.0 0.4 0.02 16.0 x 10-6
4 4.0 0.2 0.04 8.0 x 10-6
12-Sep-17 Dr NORAINI HAMZAH 85
Based on the above information,

12-Sep-17
 Calculate the order with respect to
CH3COCH3 , I2 and H+.

Dr NORAINI HAMZAH
 Write the rate law for the reaction.
 What is the overall order of the reaction?
 Determine the rate constant,k with the
correct unit.
 Calculate the rate of reaction if the
concentration of propanone, iodine and
hydrogen ion are each 0.5 mol dm-3.

86
SOLUTION I)
Let the rate law equation be :
rate = k [CH3COCH3]x[H+]y[I2]z

12-Sep-17
For value of y;
= Exp. 2 / exp 1
= 12 x 10-6 / 6 x 10-6

Dr NORAINI HAMZAH
= (0.4)y / (0.2)y
y = 1
For value of x;
=Exp 3 / exp 2
= 16 x 10-6 / 12 x 10-6 = (4)x / (3)x
x= 1
For value of z;
= Exp 3 / exp 4
= 16 x 10-6 / 8 x 10-6
= (0.4)1(0.2)z / (0.2)1(0.04)z
z = 0 87
SOLUTION

ii) rate = k [CH3COCH3][H+]

12-Sep-17
iii) overall order = 1+1 = 2 (second order)
iv) consider exp 1;

Dr NORAINI HAMZAH
6 x 10-6 = k (3.0)(0.2)
k = 1.0 x 10-5 s-1
( wrong / no unit, give them no mark)
v) Rate = (1.0 x 10-5) (0.5) ( 0.5)
= 2.5 x 10-6 mol dm-3s-1

88
ZEROTH ORDER REACTION

12-Sep-17
you will get a horizontalline,
because rate = k[A]0

Dr NORAINI HAMZAH
rate = k (a horizontal line)
rate

independent to [reactant]

[A]
89
FIRST ORDER REACTION

12-Sep-17
For first order, rate = k[A]
rate

Dr NORAINI HAMZAH
the plot is a straight line (linear)

[A]
90
SECOND ORDER REACTION

12-Sep-17
 the plot is a branch of a prabola, because
rate = k [A]2

Dr NORAINI HAMZAH
Rate

[A] 91
 DETERMINATION OF RATE CONSTANTS
USING THE INTEGRATED RATE LAWS

12-Sep-17
ln[A]t
Example;
first order integrated rate laws , ln[A]o

Dr NORAINI HAMZAH
ln [A]t = -kt + ln [A]0
y = mx + c

you should plot ln [A]t vs. t

and find a line to best fit your data.
The slope of the line is -k.
t

92
DETERMINATION OF ORDER BY LINEAR
PLOT

12-Sep-17
 For zero order; [A]0 – [A]t = kt
plot [A]t vs t , slope = -k

Dr NORAINI HAMZAH


93
DETERMINATION OF ORDER BY LINEAR
PLOT (CONT.)

12-Sep-17
 For first order; ln
[A]o /[A]t = kt
Plot ln [A] vs t , slope = - k

Dr NORAINI HAMZAH
94
DETERMINATION OF ORDER BY LINEAR
PLOT (CONT.)

12-Sep-17
 For second order, 1 1
--- - ---- = kt

Dr NORAINI HAMZAH
[A]t [A]o
 plot 1
--- vs t , slope = k
[A]

95
Figure 16.7 Integrated rate laws and reaction order

12-Sep-17
Dr NORAINI HAMZAH
1/[A]t = kt + 1/[A]0

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

ln[A]t = -kt + ln[A]0

96
Figure 16.8 Graphical determination of the reaction order for the
decomposition of N2O5.

12-Sep-17
Dr NORAINI HAMZAH
97
 Integrated Rate Laws

12-Sep-17
D[A]
rate = - = k [A] first order rate equation
Dt
[A]t

Dr NORAINI HAMZAH
ln = - kt ln [A]t = -kt + ln [A]o
[A]0
D[A]
rate = - = k [A]2 second order rate equation
Dt
1 1 1 1
- = kt = kt +
[A]t [A]0 [A]t [A]0

D[A]
rate = - = k [A]0 zero order rate equation
Dt
[A]t - [A]0 = - kt
98
Sample Problem 16.4 Determining Reaction Concentration at a Given Time

PROBLEM: At 10000C, cyclobutane (C4H8) decomposes in a first-order

12-Sep-17
reaction, with the very high rate constant of 87s-1, to two
molecules of ethylene (C2H4).
(a) If the initial C4H8 concentration is 2.00M, what is the

Dr NORAINI HAMZAH
concentration after 0.010 s?
(b) What fraction of C4H8 has decomposed in this time?

PLAN: Find the [C4H8] at time, t, using the integrated rate law for a 1st order
reaction. Once that value is found, divide the amount decomposed by
the initial concentration.
SOLUTION: [C4H8]0 2.00
ln = kt ; ln = (87s-1)(0.010s)
(a) [C4H8]t [C4H8]

[C4H8] = 0.83mol/L

(b) [C4H8]0 - [C4H8]t 2.00M - 0.87M

= = 0.58 99
[C4H8]0 2.00M
EXERCISE:
1. The decomposition of dinitrogen pentoxide is a first-order
reaction with a rate constant of 5.1x10-4s-1 at 450C.
given: 2N2O5(g) → 4NO2(g) + O2(g)
a) If the initial concentration of N2O5 was 0.25 M, what is the
concentration after 3.2 min ? ( 0.227 M)
b) How long will it take for the concentration of N2O5 to
decrease from 0.25 M to 0.15 M ? (16.7 min)
c) How long will it take to convert 62% of the starting material?
(31.62min)
2. The conversion of cyclopropane to propane in the gas phase is
a first-order reaction with a rate constant of 6.7 x 10-4s-1 at
5000C. Calculate the half-life of the reaction. (17.24 min)
3. Given : 2A →B
The above reaction is first order in A with a rate constant of 2.8
x 10-2s-1 at 800C. How long will it take for A to decrease from
0.88 M to 0.14 M ? (65.65 seconds)
EXERCISE
1. The recombination of iodine atoms to form
molecular iodine in the gas phase :
I(g) + I(g) → I2(g)
follows second order kinetic and has the high
rate constant of 7.0 x 10-9 M-1s-1at 230C.
a) If the initial concentration of I was 0.086 M,
calculate the concentration after 2.0 min.
(
b) Calculate the half-life of the reaction if the
initial concentration of I is 0.60 M.
 HALF LIVES , T1/2

12-Sep-17
 Definition

The half-life (t1/2) of a reaction is the

Dr NORAINI HAMZAH
time period required to reduce the
reactant to half of its original value.

Example:
8M t1/2 4M t1/2 2M

102
HALF LIFE OF FIRST ORDER REACTION

12-Sep-17
 constant, independent of the initial concentration.
 Thus , first half-life(t’1/2) = second half-life(t’’1/2 ).

Dr NORAINI HAMZAH
 The rate constant and half-life has the relationship:

t1/2 = ln(2) = 0.693

k k
First - order rate law : ln [A]o / [A]t = kt

At t= t1/2, [A]t = ½ [A]o; subtituting

ln ([A]o / ½[A]o) = kt1/2 or t1/2 = (ln 2)/k

103
or t1/2 = 0.693/k
Figure 16.9 A plot of [N2O5] vs. time for three half-lives.

for a first-order process

12-Sep-17
ln 2 0.693
t1/2 = =
k k

Dr NORAINI HAMZAH
104
 Sample Problem 16.5 Determining the Half-Life of a First-Order Reaction

PROBLEM: Cyclopropane is the smallest cyclic hydrocarbon. Because its

12-Sep-17
600 bond angles allow poor orbital overlap, its bonds are weak.
As a result, it is thermally unstable and rearranges to propene at
10000C via the following first-order reaction:

Dr NORAINI HAMZAH
CH2
D
H2C CH2 (g) H3C CH CH2 (g)

The rate constant is 9.2s-1, (a) What is the half-life of the reaction? (b) How
long does it take for the concentration of cyclopropane to reach one-quarter of
the initial value?
0.693
PLAN: Use the half-life equation, t1/2 = , to find the half-life.
k
One-quarter of the initial value means two half-lives have passed.

SOLUTION:
(a) t1/2 = 0.693/9.2s-1 = 0.075s (b) 2 t1/2 = 2(0.075s) = 0.150s
105
HALF LIVE FOR 2ND ORDER
REACTIONS

12-Sep-17
 depends on the initial concentration, [A]o, and the rate
constant k .
 Thus second half-life (t’’1/2 ) = 2t’1/2

Dr NORAINI HAMZAH
 The rate constant and half-life has the relationship:

t1/2 = 1
k [A]o

106
HALF LIVE FOR ZERO ORDER
REACTIONS

12-Sep-17
 The rate constant and half-life has the
relationship:

Dr NORAINI HAMZAH
t1/2 = [A]0
2k
 depends on the initial concentration, [A]o, and the
rate constant k .

107
 DETERMINATION OF ORDER BY
HALF LIFE METHOD

12-Sep-17
Plot [reactant] vs time

Dr NORAINI HAMZAH
[A]o NOTE :
If t’1/2 =t”1/2 , first order

But if t”1/2 = 2t’1/2 , second order

[A]o/2

[A]0/4

time 108
t’1/2 t”1/2
 Table 16.4 An Overview of Zero-Order, First-Order, and
Simple Second-Order Reactions

12-Sep-17
Zero Order First Order Second Order

Dr NORAINI HAMZAH
Rate law rate = k rate = k [A] rate = k [A]2

Units for k mol/L*s 1/s L/mol*s

Integrated rate law in [A]t = ln[A]t = 1/[A]t =

straight-line form k t + [A]0 -k t + ln[A]0 k t + 1/[A]0

Plot for straight line [A]t vs. t ln[A]t vs. t 1/[A]t = t

Slope, y-intercept k, [A]0 -k, ln[A]0 k, 1/[A]0

Half-life [A]0/2k ln 2/k 1/k [A]0

109
EXAMPLE

12-Sep-17
The rate constant for the decomposition of
N2O5 to NO2 and O2 at 70C is 6.82 x 10-3 s-1.
Suppose we start with 0.300 mol of N2O5(g) in

Dr NORAINI HAMZAH
a 0.500 L container.

 How many moles of N2O5 will remain after 1.5 min?

 How many minutes will it take for the quantity of N2O5 to drop to
0.030 mol?
 What is the half-life of N2O5 at 70C ?

110
SOLUTION

12-Sep-17
Using; ln [A]o /[A]t = kt

(1.5 min x 60 saat) = 90s

Dr NORAINI HAMZAH
ln 0.300 mol = 6.82 x 10-3 s-1 x 90 s
(N2O5)
= 0.6138
0.300 = e0.6138 =1.847
( N2O5 )

(N2O5 ) = 0.162 mol

111
SOLUTION
ln [A]o /[A]t = kt
ln 0.300 = 6.82 x 10-3 s-1 x t
0.030

2.303 = 6.82 x 10-3 s-1 x t

t = 337.6 second = 5.6 min

12-Sep-17 Dr NORAINI HAMZAH 112

SOLUTION

12-Sep-17
For first order;

Dr NORAINI HAMZAH
t1/2 = 0.693
k
= 0.639
6.82 x 10-3 s-1
=
101.6 seconds

113
 HOMEWORK

12-Sep-17
 In a first-order decomposition reaction, 50.0% of
a compound decomposes in 10.5 min.

Dr NORAINI HAMZAH
(a) What is the rate constant of the reaction?
(k = 0.066 min-1)

(b) How long does it take for 75.0% of the

compound to decompose?
(21.0 min)

114
 SUMMARY:

12-Sep-17
 Method to determine order of reaction:

Dr NORAINI HAMZAH
- Initial rate method
- Half-life method
- Graph rate vs concentration (pattern)
- Linear plot (pattern)

115
The Effect of Temperature on Reaction Rate

12-Sep-17
The Arrhenius Equation

Ea where k is the kinetic rate constant at T

 RT

Dr NORAINI HAMZAH
k  Ae Ea is the activation energy

R is the energy gas constant

T is the Kelvin temperature
ln k = ln A - Ea/RT
A is the collision frequency factor

k2 Ea 1 1
ln = - -
k1 RT T2 T1
116
Figure 16.10 Dependence of the rate constant on temperature

12-Sep-17
Dr NORAINI HAMZAH
117
Figure 16.11 Graphical determination of the activation energy

12-Sep-17
Dr NORAINI HAMZAH
ln k = -Ea/R (1/T) + ln A

118
Sample Problem 16.6 Determining the Energy of Activation

PROBLEM: The decomposition of hydrogen iodide,

12-Sep-17
2HI(g) H2(g) + I2(g)

has rate constants of 9.51x10-9L/mol*s at 500. K and 1.10x10-5

Dr NORAINI HAMZAH
L/mol*s at 600. K. Find Ea.

PLAN: Use the modification of the Arrhenius equation to find Ea.

SOLUTION: -1
k2 Ea 1 1 k2 1 1
ln = - - Ea = - R ln -
k1 R T2 T1 k1 T2 T1

1.10x10-5L/mol*s 1 1
Ea = - (8.314J/mol*K) ln -
9..51x10-9L/mol*s 600K 500K

Ea = 1.76x105 J/mol = 176 kJ/mol 119

EXAMPLE:

12-Sep-17
Dinitrogen tetraoxide, N2O4, decomposes to
nitrogen dioxide, NO2, in a first-order process.
N2O4 → 2NO2

Dr NORAINI HAMZAH
If k = 2.5x103 s-1 at -5°C and
k = 3.5x104 s-1 at 20°C,

what is the activation energy for the

decomposition?
120
SOLUTION:

12-Sep-17
Using ln ( ) =k 2 ( E)a 1 1
 -
k1 R T2 T1

Dr NORAINI HAMZAH
for condition 1:
k1 = 2.5x103 and T1 = -5°C = 268 K

for condition 2:
k2 = 3.5x104 and T2= 25°C = 298 K

121
SOLUTION(CONT.):

12-Sep-17
ln( 3.5x10
4
) = ( Ea )1 1
2.5x10 3  -

Dr NORAINI HAMZAH
R 298 268
ln(14) = Ea (0.00335 – 0.00373)

R
Ea
2.63 =  (– 0.00037)
R
E
= -7108  a
R
Ea = 59 kJmol-1 122
REACTION MECHANISMS

12-Sep-17
Definition;

Dr NORAINI HAMZAH
A reaction mechanism is a collection of
elementary processes or steps
(also called elementary steps)
that explains how the overall
reaction proceeds.

123
 REACTION MECHANISMS

12-Sep-17
Table 16.6 Rate Laws for General Elementary Steps

Elementary Step Molecularity Rate Law

Dr NORAINI HAMZAH
A product Unimolecular Rate = k [A]

2A product Bimolecular Rate = k [A]2

A+B product Bimolecular Rate = k [A][B]

2A + B product Termolecular Rate = k [A]2[B]

124
 Sample Problem 16.8 Determining Molecularity and Rate Laws for
Elementary Steps
PROBLEM: The following two reactions are proposed as elementary steps in

12-Sep-17
the mechanism of an overall reaction:
(1) NO2Cl(g) NO2(g) + Cl (g)
(2) NO2Cl(g) + Cl (g) NO2(g) + Cl2(g)

Dr NORAINI HAMZAH
(a) Write the overall balanced equation.
(b) Determine the molecularity of each step.
(c) Write the rate law for each step.

PLAN: (a) The overall equation is the sum of the steps.

(b) The molecularity is the sum of the reactant particles in the step.
SOLUTION: (b) Step(1) is unimolecular.
(a) (1) NO2Cl(g) NO2(g) + Cl (g) Step(2) is bimolecular.
(2) NO2Cl(g) + Cl (g) NO2(g) + Cl2(g) (c) rate1 = k1 [NO2Cl]
rate2 = k2 [NO2Cl][Cl]125
2NO2Cl(g) 2NO2(g) + Cl2(g)
TYPES OF MOLECULARITY

12-Sep-17
 is the number of molecules reacting in an
elementary step. These molecules may be

Dr NORAINI HAMZAH
of the same or different types.
 Unimolecular reaction – an elementary
step that involves one molecules
 Bimolecular reaction – an elementary step
that involves two molecules
 Termolecular reaction – an elementary
step that involves three molecules
126
INTERMEDIATES SPESIES

12-Sep-17
 is always formed in an early elementary step but
not in the overall balance equation.

Dr NORAINI HAMZAH
 Very low concentration.

127
 The Rate-Determining Step of a Reaction Mechanism

12-Sep-17
The overall rate of a reaction is related to the rate of the slowest, or
rate-determining step.

Dr NORAINI HAMZAH
Correlating the Mechanism with the Rate Law

The elementary steps must add up to the overall equation.

The elementary steps must be physically reasonable.

The mechanism must correlated with the rate law.

128
DERIVING RATE LAWS FROM MECHANISMS

12-Sep-17
2 methods:
a) mechanisms with slow initial step

Dr NORAINI HAMZAH
b) Mechanisms with a fast initial step

129
MECHANISMS WITH SLOW INITIAL STEP

If several steps are involved in an overall chemical

12-Sep-17

reaction, the slowest step limits the rate of the
reaction.

Dr NORAINI HAMZAH
 Thus, a slow step is called a rate determining step.

 The slowest step has the highest Ea

130
EXAMPLE:

12-Sep-17
If the reaction
2NO2 + F2  2NO2F

Dr NORAINI HAMZAH
follows the mechanism,
i. NO2 + F2  NO2F + F (slow)
ii. NO2 + F  NO2F (fast)
Propose the rate law for the reaction?

131
SOLUTION
Since step (i) is the rate-determining step, the rate law

12-Sep-17
is
So rate of overall reaction = rate of first step

Dr NORAINI HAMZAH
rate1 = k [NO2] [F2]

Check!
Since both NO2 and F2 are reactants, this is the rate
law for the reaction.

132
Figure 16.21
Reaction energy diagram for the two-step reaction of NO2 and F2.

12-Sep-17
Dr NORAINI HAMZAH
133
TO GET OVERALL REACTION AND
INTERMEDIATE SPECIES

12-Sep-17
 Addition of (i) and (ii) will gives the overall reaction ;
i. NO2 + F2  NO2F + F (slow)
ii. NO2 + F  NO2F (fast)

Dr NORAINI HAMZAH
2NO2 + F2  2NO2F

 Intermediate species is atom F

 Note that the rate law is not derived from

the overall equation.
134
MECHANISMS WITH A FAST INITIAL STEP

12-Sep-17
Consider the reaction below:
2NO(g) + O2(g) → 2NO2(g)

Dr NORAINI HAMZAH
The experimentally determined rate law is
rate = k[NO]2[O2]
And a proposed mechanism is
(1) NO(g) + O2(g) ⇌NO3(g) [fast, ⇌]
(2) NO3(g) + NO(g) → 2NO2(g) [slow]

135
 Write rate laws for both direction of the fast step and
for the slow step;
step 1:
rate1(fwd) = k1[NO][O2]

12-Sep-17
rate1(rev) = k-1[NO3]
step 2 :

Dr NORAINI HAMZAH
rate2=k2[NO3][NO]

 Then check rate determining step with overall

reaction:
2NO(g) + O2(g) → 2NO2(g)

species NO3 is not a reactant but intermediate species

 Eliminate NO3
136
 Then set forward and reverse rates are equal:
rate1(fwd) = rate1(rev)
k1[NO][O2]= k-1[NO3]

12-Sep-17
 Solve for intermediate;

Dr NORAINI HAMZAH
[NO3] = k1[NO][O2]
k-1

137
 Substituting for [NO3] in the rate law for step
2

12-Sep-17
rate2=k2[NO3][NO]
= k2 k1[NO][O2] [NO]

Dr NORAINI HAMZAH
k-1
= k2 k1 [NO]2[O2]
k-1
= k [NO]2[O2]

 So, this rate law is identical to overall rate law

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