CHM 432

FUNDAMENTAL TO
PHYSICAL CHEMISTRY
CHAPTER 4
CHEMICAL KINETICS

1
 Learning objectives
At the end of this chapter, you should be able to
1. Discuss the five factors that affect the rate of chemical reactions.
2. Determine the relative rate at which reactants are disappear and
products are appear.
3. Use the experimental initial rate data to determine the order of reaction.
4. Explain the rate of chemical reaction based on molecular view of
collisions that includes frequency, energy and orientation that make up
the collision theory.
5. Use the Arrhenius equation to determine the activation energy of a
reaction.
6. Use the concept of reaction mechanisms to recognize reasonable
mechanisms and suggest plausible mechanisms
7. Relate the properties of homogeneous and heterogeneous catalysts and
how they act to increase the reaction rates.

2
Reaction rate: the central focus of chemical kinetics
 Rates of Reactions
Rate of a chemical reaction – the change in concentration of a
designated reactant or product per unit time.
E.g.: Consider the reaction : A → B
The rate of disappearance of reactant A is given by

The rate of formation of a product B is given by

Units
Concentration = mol per dm3 (M) Time = seconds (s)
Rate = mol dm-3 s-1 or M s-1
4
 Different types of rates
1. Initial rate : the rate at the start of reaction when
infinitesimally small amount of the reactant has been used
→ given by the gradient to the curve at time t=0.
2. Instantaneous rate : the rate at particular time → given by
the tangent to the curve at that time.
3. Average rate : the average change in concentration of
reactant/product over a certain time interval.

5
 Reaction Rates
C4H9Cl(aq) + H2O(l) ⎯⎯→ C4H9OH(aq) + HCl(aq)

In this reaction, the

concentration of butyl
chloride, C4H9Cl, was
measured at various
times, t.

6
 Reaction 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.

7
 Reaction Rates
C4H9Cl(aq) + H2O(l) ⎯⎯→ C4H9OH(aq) + HCl(aq)

• The reaction slows down

with time because the
concentration of the
reactants decreases.

8
 Reaction Rates
C4H9Cl(aq) + H2O(l) ⎯⎯→ C4H9OH(aq) + HCl(aq)

The average rate of the

reaction over each
interval is the change in
concentration divided
by the change in time:

9
 Reaction Rates
C4H9Cl(aq) + H2O(l) ⎯⎯→ C4H9OH(aq) + HCl(aq)

• Note that the average rate

decreases as the reaction
proceeds.
• This is because as the
reaction goes forward,
there are fewer collisions
between reactant
molecules.

10
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
11
Reaction Rates and Stoichiometry

• What if the ratio is not 1:1?

H2(g) + I2(g) ⎯⎯→ 2 HI(g)

12
Reaction Rates and Stoichiometry

• To generalize, for the reaction

aA + bB cC + dD

Reactants (decrease) Products (increase)

13
• Consider the following reaction

8A(g) + 5B(g) → 8C(g) + 6D(g)

If [C] is increasing at the rate of 4.0 mol L-1s-1,

at what rate is [B] changing?
• -(1/5 x dB/dt) = +1/8 (dC/dt)
• -(1/5 x dB/dt) = +1/8 (4.0 mol L-1s-1)
• (dB/dt) = - 2.5 mol L-1s-1
14
 Experimental Determination of Reaction Rates
1) Spectrometric Methods
❖ These methods are used to measure the
concentration of a reactant or product that
absorbs or emit light of narrow range of
wavelengths.
❖ The reaction performed within the sample
compartment of a spectrometer that has been set
to measure a wavelength characteristic of one of
the species.

For example
NO (g, colorless) + O3 (g, colorless) → O2 (g, colorless) + NO2 (g, brown)

❖ Known volume of the reactants are injected into a

gas sample tube of known volume, and the rate of
formation of NO2 is measured by monitoring the
color over time.
❖ Reactions in aqueous solution are studied similarly.

15
 Experimental Determination of Reaction Rates
2) Conductometric Methods
❖ When nonionic reactants from ionic products, or vice versa, the change
in the conductivity over the time can be used to measure the rate.
❖ Electrodes are immersed in the reaction mixture, the increased or
decreased in conductivity correlates with the formation of product.
❖ Conductivity α [ions]
For example:
(CH3) 3C- Br(l) + H2O(l) → (CH3) 3C-OH(l) + H+(aq) + Br-(aq)

16
 Experimental Determination of Reaction Rates
3) Manometric Methods
❖ If reaction involves a change in the number of moles of a gaseous
reactant or product, the change in pressure at constant volume and
temperature over the time can be used to measure the rate of reaction.
❖ In this methods, manometer is attached to the reaction vessel reaction
vessel of known volume.
For example,
Zn(s) + 2CH3COOH(aq) → Zn2+(aq) + 2CH3COO-(aq) + H2(g)

17
 Experimental Determination of Reaction Rates
4) Direct Chemicals Methods
❖ A small portion of an aliquot is removed and concentration of reactant
or product is measured while the bulk of the reactions mixture is
continues to react and sampled later.
❖ Can be used for slow reactions or those that can be easily slowed.
Normally the reaction of the portion to be analyzed is stopped by rapid
cooling.
❖ For example, the reaction between organic halide and water.
❖ The reaction rate in an aliquot is slowed by transferring it into a chilled
flask in a ice bath. The concentration of HBr is determined by titrating
with standard NaOH. The procedure is repeated at regular intervals of
time during reaction.

18
 Rate Law and Order of Reaction
The rate law – an experimental determined equation which expresses the
rate of reaction as a function of the concentrations of the reactants.
aA + bB → cC + dD

Rate α [A]x[B]y
Rate = k[A]x[B]y
Rate Constant, k
✓ Experimentally determined value
✓ Independent of concentrations but dependent of
temperature
✓ Magnitude of k indicates the speed of a reaction
small k = a slow reaction
large k = a fast reaction

19
 Rate Law and Order of Reaction
Order of reaction – the power to which the concentration of a
reactant is raised in the rate equation.

aA + bB → cC + dD

Rate = k[A]x[B]y

x and y = integers = 0, 1, 2, 3……in most chemical reactions!

i. Order of reaction with respect to A = x

ii. Order of reaction with respect to B = y
iii. Overall order = sum of exponents of all reactants in the rate
law = x + y 20
 Rate Law and Order of Reaction
a) Zero order reaction : The rate is independent of the concentration of
the reactant as long as some is present.
2PH3 (g) → 2P (s) + 3H2 (g) (hot tungsten as catalyst and at high pressure)
Rate = k [PH3] 0 = k

PH3 decomposes at a constant rate until it has entirely been used up and the
reaction will stop abruptly

b) First order reaction : The rate depends on the reaction concentration

raised to the first power.

CH3N2CH3(g) → CH3CH3(g) + N2(g) Rate = k [CH3N2CH3]

2N2O5(g) → 4NO2(g) + O2(g) Rate = k [N2O5]

21
 Rate Law and Order of Reaction

c) Second order reaction : The rate depends on reactant concentration

raised to the power of two or on the concentrations of two different
reactants each raised to the first power.

S2O82-(aq) + 3I-(aq) → 2SO42- (aq) + I- (aq)

Rate = k[S2O82-][I-] --------> First order in both S2O82- and I-

NO2(g) + CO(g) → NO(g) + CO2(g)

Rate = k[NO2]2 ----> Second order in NO2, zero order in CO

22
 Rate Law and Order of Reaction
d) Third order reactions : The rate depends on the reactant concentration
raised to the third power or the concentrations raised to a combined power
of three.

2NO(g) + O2(g) → 2NO2(g)

Rate = k [NO]2[O2] ----> 2nd order in NO, 1st order in O2

e) Reactions of fractional order : A reaction need not have an integer order,

and many gas-phase reactions do not.

H2 (g) + Br2 (g) → 2HBr(g)

Rate = k [H2][Br2]1/2 ---> 1st order in H2, ½ in Br2

Therefore, overall order= 1½.

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 Experimental Determination of Rate Law
1) Initial rate method - carry out a number of separate experiments with
different initial concentrations and measuring the initial rates of reaction.
The initial rate can be found by plotting [reactant] vs. time and drawing
the tangent line at t = 0.
❑ If doubling the concentration of A has no effect on the rate, the reaction
is zero order.
❑ If doubling the concentration of A doubles the rate, the reaction is 1st
order with respect to A.
❑ If doubling the concentration of A increases the rate by factor of four, the
reaction is second order with respect to A.

exp [A] [B] Rate M/s

1 0.015 0.015 0.048
2 0.030 0.015 0.192
3 0.015 0.030 0.096
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 exp [A] [B] Rate M/s
1 0.015 0.015 0.048
2 0.030 0.015 0.192
3 0.015 0.030 0.096

Solutions
A + B → products

1. Write rate law expression : Rate = k[A]x[B]y

2. Determine x, [B]must be constant, so compare 1 & 2
Double conc. of A, the rate increases by factor of 4 (quadruples).
2x = 4 → 2x = 2 2
x= 2
3. Determine y, [A] must be constant, so compare 1& 3
Double conc. of B, the rate increases by factor of 2 (doubles).
2y = 2 → 2y = 2 1
y=1
4. Rewrite rate law with the calculated orders : Rate = k[A]2[B]1
5. Find k, choose any set of data (1, 2 or 3), and insert the values in the rate law expression
Let say I choose set 2,
Rate = k[A]2[B]1
0.192 Ms-1 = k[0.030]2[0.015]1
k =14222 M-2 s-1
Rate = 14222M-2 s-1 [A]2[B]1

25
 Experimental Determination of Rate Law

Example: Rate = k[A]x[B]y ; when [A]=doubled

If x = 0; the rate remains unchanged
If x = 1; the rate doubles (21)
If x = 2; the rate quadruples/increases by factor of 4 (22)
If x = 3; the rate increases eightfold/factor of 8 (23)

26
 Experimental Determination of Rate Law
Consider the following reaction and the data given in the table, determine the rate law for the reaction and
also calculate the rate constant, k.

NH4+ (aq) + NO2 (aq) → N2 (g) + 2H2O (l)

Exp Initial [NH4+] Initial [NO2 ] Initial rate(moldm-3s-1)

1 0.10 0.005 1.35 x 10-7

2 0.10 0.01 2.70 x 10-7
3 0.20 0.01 5.40 x 10-7

1) Write rate law expression for reaction :

Rate = k[NH4+]x[NO2]y
2) Determine x, compare experiments which concentration NO2 constant, i.e. 1&2
2x = 2 → 2x = 21
x=1
3) Determine y, compare experiments which concentration NH4+ constant, i.e. 2&3

2y = 2 → 2y = 21
y =1
4) Rewrite rate law with the calculated orders : Rate = k[NH4+]1[NO2]1
5) Find k, choose any set of data (1, 2 or 3), and insert the values in the rate law expression
Let say I choose set 1,
1.35×10-7 mol dm-3 s-1= k [0.10][0.005]
k = 2.7×10-4 mol-1 dm3 s-1 27
 Experimental Determination of Rate Law

The order of reaction can also be determined by using the

following formula

Where
r1 and r2 = initial rates for experiments 1 and 2
c1 and c2 = initial concentrations of A for experiments 1 and 2
n = order of reaction

28
1) Write rate la expression 3.2 × 10−5 𝑘 0.164 𝑥 0.15 𝑦
=
Rate = k[Hg2Cl2]x[C2O42-]y 4.8 × 10−5 𝑘 0.164 𝑥 0.45 𝑦

2) Determine x, compare exp which conc. 0.11 = 0.33y

C2O42- constant i.e. exp 1 & 4 log 0.11 = log 0.33y
−
𝑅𝑎𝑡𝑒 1 𝑘 𝐻𝑔2𝐶𝑙2 𝑥 𝐶2𝑂42 𝑦 log 0.11 = y log 0.33
= −
𝑅𝑎𝑡𝑒 4 𝑘 𝐻𝑔2𝐶𝑙2 𝑥 𝐶2𝑂42 𝑦 y = log0.11 / log0.33 = 2
3.2 × 10−5 𝑘 0.164 𝑥 0.15 𝑦
= 4) Rewrite the rate law
4.8 × 10−5 𝑘 0.246 𝑥 0.15 𝑦
0.67 = (0.67)x → 0.671 = (0.67)x Rate = k [Hg2Cl2][C2O42-]2
x=1 5) To find k, choose any set of experiment
3) Determine y, compare exp which conc. and substitute the values in the rate law
Hg2Cl2 constant i.e. exp 1 & 2
−
𝑅𝑎𝑡𝑒 1 𝑘 𝐻𝑔2𝐶𝑙2 𝑥 𝐶2𝑂42 𝑦 3.2×10-5 = k [0.164][0.15]2
= − k = 8.67×10-3 M-2 s-1
𝑅𝑎𝑡𝑒 2 𝑘 𝐻𝑔2𝐶𝑙2 𝑥 𝐶2𝑂42 𝑦

29
 Experimental Determination of Rate Law
2) Method of integration – method involves trial and error.
We start with a rate equation that we may think applicable.
For example
A → product
Rate = k[A]x

• The rate of reaction, r, is given by

• Let say, this reaction obeys a zero-order rate law: rate= k[A]O = k

• Therefore,
30
 Experimental Determination of Rate Law

• Rearrange

• The integrated rate law is

[A]t – [A] 0 = -kt
[A]t = - kt + [A]0
Y = mX + C
• Plot [A] versus t will give a straight line
• Slope = -k
• Y - intercept = [A]0

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 Experimental Determination of Rate Law
Half-life – the time required for concentration of respective
reactant to reach a value that is halfway between its initial
and final values.

Half-life (t1/2) for zero order reaction is derived by rewriting the

integrated rate law as

[A]t = - kt + [A]0
At t = t1/2 , [A]t = ½ [A]0
½[A] 0 = -k t1/2 + [A]0

32
2) Method of integration – method involves trial and error.
We start with a rate equation that we may think applicable.
For example
A → product
• The rate of reaction, r, is given by

• Let say, this reaction obeys a first-order rate law: rate = k[A]

• Therefore,

33
 Experimental Determination of Rate Law

• Rearrange

• The integrated rate law is thus

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

• Plot ln[A]t versus t will give a straight line

• Slope = -k

34
 Experimental Determination of Rate Law

Half-life (t1/2) for first-order reactions is derived by rewriting the

integrated rate law as

ln [A]t = - k t + ln [A]0
At t = t1/2 , [A]t = ½ [A]0
ln ½ [A] 0 = - k t1/2 + ln [A]0

35
 Experimental Determination of Rate Law
2) Method of integration – method involves trial and error.
We start with a rate equation that we may think applicable.
For example
A → product
• The rate of reaction, r, is given by

• Let say, this reaction obeys a second-order rate law: rate = k[A]2

• Therefore,

36
 Experimental Determination of Rate Law

• Rearrange

• The integrated rate law is thus

• Plot 1/[A]t versus t will give a straight line

• Slope = k

37
 Experimental Determination of Rate Law
Half-life (t1/2) for second-order reactions is derived by rewriting
the integrated rate law as

At t = t1/2 , [A]t = ½ [A]0

38
 Summary of Rate Law
A → product

Reaction Rate Integrated Half Life Unit of

Order Law Rate Rate
Law Constant

Zero rate = k [A]t = - kt + [A]0 Mol L-1 s-1

First rate = k[A] ln[A]t = - k t + ln[A]0 s-1

Second rate = k[A]2 L mol-1 s-1

39
 Questions
Q1 : The decomposition of N2O5 in gas phase was studied at
constant temperature
2N2O5 (g) → 4N02 (g) + O2 (g)

[N2O5] (mol dm-3) Time (s)

0.1000 0
0.0707 50
0.0500 100
0.0250 200
0.0125 300
0.00625 400

Using these data, verify (graphically) that the reaction is first-

order and calculate the rate constant.
40
 Solution
• First order → ln[A]t = - k t + ln[A]0
• Plot ln[A]t against time (sec) will gives straight line graph
• -0.007 = -k
• k=0.007 s-1 0

-1

ln [N2O5] (mol dm-3)

-2
[N2O5] (mol ln [N2O5] Time (s)
y = -0.007x - 2.303
dm-3) (mol dm-3) -3

0.1000 -2.303 0
-4

0.0707 -2.649 50
-5
0.0500 -2.996 100
-6
0.0250 -3.689 200 0 100 200 300 400 500 600

Time (seconds)
0.0125 -4.382 300
0.00625 -5.075 400 41
Q2 : A certain first order reaction has a half life of 20 min. Calculate
a) The rate constant for this reaction
T1/2 = ln 2/k
a) The time required for this reaction to be 75% completed.
ln A = -kt + lnA0
A0 = 100%
A = 100-75 = 25
ln 25 = -0.035 min-1 (t) + ln100
t = 40 mins

Q3: The decomposition of N2O5 is a first-order reaction with rate constant of

5.1 x 10-4 s-1 at 45 0C.
2N2O5 (g) → 4N02 (g) + O2 (g)
a) If initial concentration of N2O5 is 0.25 M, what is the concentration after
3.2 min? - integrated
b) How long will it take for the concentration of N2O5 to decrease from
0.25 to 0.15 M? – integrated,
c) How long will it take to convert 62% of the starting material? INTEGARTE

42
Q4 : The following data were obtained on the reaction 2A→B

Time, s 0 5 10 15 20

[A], mol L-1 0.100 0.0141 0.0078 0.0053 0.004

(a) Plot the data and determine the order of the reaction.

Second order reaction. Plot of 1/[A] against time (t) gives a straight line graph

(b) Determine the rate constant.

Rate constant is equal to slope of the straight line graph. k = 11.96 L mol-1 s-1

43
44
 Factors affecting reaction rate
Any change in conditions (concentration, pressure, temperature
and catalysts and size particle) which increase either frequency
or the fraction of molecules with enough energy will increase
the reaction rate.
a) Concentration – when concentration increases, the frequency
of collision also increases. The probability of collisions with
sufficient energy for reaction to occur also increase. Therefore,
the rate of reaction increases.
b) Pressure (gases) – At low pressure, the gas molecules are
spread far apart. At high pressure, the molecules are close
together. Increasing the pressure of the gas increase total
collision frequency. The probability of collisions with sufficient
energy for reaction to occur also increase. Therefore, the rate
of reaction increases.
45
 Factors affecting reaction rate
c) Temperature – increase in temperature raises molecular velocity
and so increases the frequency of collisions between molecules.
the Maxwell-Boltzmann distribution represents the distribution
of the kinetic energy of collisions at a given temperature.
d) Catalysts – substance that speed up reaction without itself being
chemically changed or consumed in the process. Catalyst speeds
up of a reaction by providing alternative pathway (mechanism)
with lower activation energy. Therefore the reaction is faster
with catalyst.
e) Size of particle – if a solid is broken down into smaller pieces, its
surface area gets larger. Extra surfaces are exposed for other to
attack, and total collision frequency will increase. Hence
powdered solids reacts more quickly than larger lumps.
46
 Collision Theory
This theory developed from kinetic theory to account for the
effects of concentration and temperature on reaction rates.

Collision theory is based on the 3 ideas

1) Molecules must collide to react.
2) Molecules must possess a certain minimum kinetic energy,
called activation energy (Ea) to initiate a chemical reaction.
3) Molecules must collide in the right orientation for the
collisions to result in a reaction. This is sometimes called the
steric factor.

47
 Collision Theory
Activation energy, (Ea) – minimum amount of energy required to
initiate a chemical reaction
Ea enables breakage of chemical bonds and rearrangement of
atoms and valence electrons as reaction proceeds.

48
 Collision Theory
Molecular orientation
Consider the following reaction
CH2= CH2 + HCl → CH3CH2Cl

49
Nature of the transition state in the reaction between CH3Br and OH-.

CH3Br + OH- CH3OH + Br -

transition state or activated complex

Figure 16.19 Reaction energy diagram for the reaction of CH3Br and OH-.
 Collision Theory
Effective collision – reactants molecules which collide
successfully and lead to the formation of products.

Two requirements for effective collisions

1. The reacting molecules must collide with energy which must
be equal or greater than activation energy of the reaction
2. The relative orientation of the reactants must allow
formation of any new bonds necessary to produce products.

52
 Collision Theory
• The rate of a reaction is directly proportional to the
number of effective molecular collisions per second
or the frequency of effective collisions.
Rate α zfp
z = collision frequency
f = fraction of collisions having energy > Ea
p = steric factor or fraction of collision that occur in
reactant molecules properly orientated.

53
Maxwell–Boltzmann Distributions
• Temperature is defined
as a measure of the
average kinetic energy
of the molecules in a
sample.

• At any temperature there is a wide distribution of kinetic energies.

• As the temperature increases, the curve flattens and broadens.
• Thus at higher temperatures, a larger population of molecules has
higher kinetic energy.

54
Maxwell–Boltzmann Distributions

• If the dotted line represents the activation energy, as the

temperature increases, so does the fraction of molecules that
can overcome the activation energy barrier.
• As a result, the reaction rate increases.
55
 Maxwell–Boltzmann Distributions

Two important observations

I. At both temperatures, relatively small fraction of collision
have sufficient kinetic energy ≥ the activation energy to result
in a reaction
II. As the temperature increases, the fraction of collisions with
sufficient energy to cause a reaction also increases .
56
 Arrhenius Equation
❑ Temperature dependence of reaction rates
❑ Svante Arrhenius developed a mathematical relationship
between k and Ea:
Ln k = ln (A x e -Ea/RT)
Ln k = ln A + ln e -Ea/RT
Ln k = ln A –Ea/RT ln e
Ln k = -Ea/RT + ln A
where A is the frequency factor, a number that represents the
likelihood that collisions would occur with the proper
orientation for reaction.
❑ This type of relationship is called an exponent relationship
which means that small rise in temperature results in a large
increase in the fraction of molecules collide with energy equal
to or greater than the activation energy.
57
 Arrhenius Equation
Taking the natural
logarithm of both
sides, the equation
becomes
Ea 1
ln k = − ( ) + ln A
R T
y = mx + C

When k is determined experimentally at several

temperatures, Ea can be calculated from the slope of a plot of
ln k vs. 1/T.
58
 Arrhenius Equation
❑ Arrhenius equation can be put into another form if the rate
constants k1 and k2 respectively for two different
temperatures T1 and T2 are given.
Ea 1 Ea 1
ln k1 = − ( ) + ln A ln k2 = − ( ) + ln A
R T1 R T2

❑ Subtracting ln k1 from ln k2 gives

k2 − Ea  1 1 
ln( ) =  − 
k1 R  T 2 T1 

59
 Working With The Arrhenius Equation
Q1 : HI can be formed from the reaction of H2 and l2. At 326 °C, the rate constant of this
reaction is 5.4 x 10-4 M-1 s-1. Calculate the rate constant at 377 °C if activation
energy of this reaction is 160 kJ mol-1.
ln(5.4e-4/k650) = -160000/8.314 (1/599-1/650)
K650 = 6.72 x 10-3 M-1 s-1

Q2 : Acetaldehyde, CH3CHO decomposes when heated. The rate constant for

decomposition reaction is 1.05 x 10-3 M-1/2 s-1 at 759 K and 2.14 x 10-2 M-1/2 s-1 at
836K. What is the activation energy for this reaction? What is the rate constant at
865 K?
CH3CHO (g) → CH4 (g) + CO (g)

ln(1.05 x 10-3 / 2.14 x 10-2) = -Ea/8.314 (1/759-1/836)

Ea = 206537 J mol

60
 Working With The Arrhenius Equation

Given the following data, predict k (M/s) T °C

the Ea for this reaction and k
at 75°C using the graphical 0.000886 25
approach 0.000894 50
0.000908 100
-6.99

0.000918 150
-7.00

E 1
ln k = − a  + lnA
-7.01
R T
1
ln k

ln k = -36.03 x 1/T - 6.91

-7.02 ln k = −36.03  - 6.91
T
-7.03
k75 = 8.99 x 10 M/s
-4

Lnk = -7.015
-7.04
0.0022 0.0024 0.0026 0.0028 0.0030
-1
1/ T (K )
0.0032 0.0034 0.0036
K= Ea = 299.55 J/mol

61
 Working With The Arrhenius Equation

Given that k at 25°C is

4.61×10-1 M/s and that at k2 − Ea  1 1 
50°C it is 4.64×10-1 M/s, ln( ) =  − 
k1 R  T 2 T1 
what is the activation
energy for the reaction?

 4.64 10 − 1M/s  − Ea  1 1 

ln =  − 
 4.6110 − 1M/s  8.314 J/mol • K  323K 298 K 

208 J/mol = Ea

62
 Reaction Mechanisms
• Reaction mechanism - a series of simple step that ultimately
lead from initial reactants to the final products of reaction.
• Tell what happens on the molecular level, and in what order
• Tell us which steps in a reaction are fast and slow
• The rate determining step is the slowest step of the reaction
that accounts for most of the reaction time
• Catalysts are species that are consumed in an early step and
regenerated in a subsequent step.
• Intermediates are temporary products. Intermediates are
formed in an early step and consumed in a later step

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 Molecularity
Elementary Reactions Molecularity Rate Law (for mechanism
only)
A→Products Unimolecular Rate=k[A]
A + A → Products Bimolecular Rate=k[A]2
A + B → Products Rate=k[A][B]
A + A + B → Products Termolecular Rate=k[A]2[B]
3A → Products Rate=k[A]3
A + B + C → Products Rate=k[A][B][C]

Elementary reactions – a single molecular event , such as collision or dissociation

of molecules in the progress of the overall reaction.
Molecularity – refers to the numbers of species that must collide or dissociates to
produce the reaction indicated by a particular elementary step.
Rate law can be written for each elementary reaction based on their molecularity,
that is , the exponents in the rate law are the same as the stoichiometric
coefficients in the chemical equation for the elementary reaction.
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 Learning Check
The reaction mechanism that has been proposed for the
decomposition of H2O2 is

1. H2O2 + I- → H2O + IO- (slow)

2. H2O2 + IO- → H2O + O2 + I- (fast)

• Which is the rate determining step?

• Are there any intermediates?
• Are there any catalyst ?

65
 Rate Laws And Mechanisms
• The majority of the reaction time is taken by the rate determining step i.e.
the slowest step.
• The substances that react in this step have the greatest effect on the
reaction rate.
• The observed rate law usually matches the rate law based on the rate
determining step where the order of each reactant is its stoichiometric
coefficient.
For example:
The reaction mechanism that has been proposed for the decomposition of
H2O2 is
k1
1. H2O2 + I → H2O + IO- (slow)
-
k
2. H2O2 + IO- →2 H2O + O2 + I- (fast)
What is the expected rate law?
rate=k1[H2O2][I-]
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 Learning Check
The reaction: A + 3B → D + F was studied and the following
mechanism was finally determined

k1
1. A + B→C (fast)
2. C + B k→ D + E
2
(slow)
k
3. E + B→ 3
F (very fast)

What is the expected rate law?

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 A mechanism with a slow step followed by fast step

• A mechanism never be proved absolutely correct . We can say

that a mechanism which satisfy the requirements is possibly
correct or acceptable.
• A proposed reaction mechanism must satisfy two
requirements
1. The sum of the elementary steps must give the overall
balanced equation for the reaction.
2. The mechanism must agree with the experimentally
determined rate law.

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 Case 1: A mechanism with a slow step followed by fast step

• The balanced equation for the reaction of NO2 and F2 is

2NO2 (g) + F2 (g) → 2NO2F (g)

• The experimentally rate law is

Rate = k [NO2][F2]

• A proposed mechanism for the reaction is

k
1. NO2 + F2 → NO2F + F (slow)
1

k
2. F + NO2 → NO2F
2
(fast)

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Reaction energy diagram for the two-step reaction of NO2 and F2

70
 Case 2: Mechanism which involve a fast reversible step

2NO + 2H2 → N2 + 2H2O

One possible mechanism:
k1
1. 2 NO N2O2 (fast)
k -1
k2
2. N2O2 + H2 →N2O + H2O (slow)
k3
3. N2O + H2 → N2 + H2O (fast)

Rate law = rate of slow step

= k2 [N2O2][H2]

• But N2O2 is NOT a reactant or a product!! (refer to overall reaction)

• We should try to eliminate it from the rate law

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• Rates of forward and backward reactions will quickly become
equal
rate forward = k 1[NO] 2
rate backward = k-1[N2O2]

Set these two equal:

• k 1[NO] 2 = k -1[N2O2]
• From this:
• [N2O2] = k 1 [NO]2
k-1
• Therefore, rate = k2[N2O2][H2] = k2k1 [NO]2[H2]
k-1
rate = k [NO]2[H2]

72
 Learning Check
Q1: Consider the following reaction
2O 3(g) → 3O2(g)

The experimentally rate law is Rate = k[O 3]2

[O 2]

The mechanism proposed for the reaction is

k
1
1. O3 k O2 + O (fast equilibrium)
-1
k
2. O + O 3 → 2O 2
2
(slow)
Is this an acceptable mechanism for reaction?

73
Q2: The reaction of Cl2 with CHCl3 is given by equation
Cl2 (g) + CHCl3 (g) → HCl (g) + CCl4 (g)

The rate law determined experimentally is

Rate = k [Cl2]1/2[CHCl3]

A proposed mechanism for the reaction is

k 1
1. Cl2 K -1
2Cl fast
k
2. Cl + CHCl3 → HCl + CCl3
2
slow
k
3. CCl3 + Cl → CCl4
3
fast

Is this an acceptable mechanism for the reaction?

74
Q3: The equation for the reaction is
Tl3+ + Hg22+ → Tl+ + 2Hg2+

The experimental determined rate law is

Rate = k [Tl3+][Hg22+]
[Hg2+ ]

Verify the acceptability of the proposed mechanism below

1k
1. Hg2 k Hg0 + Hg2+
2+
-1
(fast)
k
2. Tl3+ + Hg0 → Tl+ + Hg2+
2
(slow)

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 Case 3 : Approximation to steady state

o In simple reaction mechanism, there is usually 1 step which is

the rate determining step.
o But in complex multistep reaction mechanisms, it is not
unusual for different steps to be rate determining under
different sets of conditions.
o Steady-state approximation is often used in cases where a
specific rate determining step cannot be chosen.
o The central feature of this method is the assumption that the
concentration of any intermediate is so low that it remains
constant as the reaction proceeds.

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 Catalysts

• Speed a reaction, but are not consumed by the reaction

• Provide alternative reaction pathway with a lower the Ea
• May be heterogeneous or homogeneous
77
 Catalytic Actions
• May serve to weaken bonds through induction
• May serve to change polarity through amphipathic/surfactant
effects
• May reduce geometric orientation effects
• Heterogeneous catalyst: reactant and catalyst exist in
different states.
• Homogeneous catalyst: reactants and catalyst exist in the
same physical state

78
Catalytic Actions

79
 Homogeneous catalysts
• Example : lead chamber process for manufacturing sulfuric acid.
1. S + O2 → SO2
2. SO2 + ½ O2 → SO3
3. SO3 + H2O → H2SO4
Uncatalyzed second reaction, oxidation occurs slowly. NO2 can serve as
catalyst by being oxygen carrier and providing low energy path for
oxidation of SO2 to SO3.
SO2 combined with the mixture NO, NO2, air and steam in the large lead-lined
reaction chambers.
2*. NO2 + SO2 → NO + SO3
NO + ½O2 → NO2
NO2 is regenerated , it has not been permanently changed.

80
 Heterogeneous catalysts
In general, the mechanism of a heterogeneous catalysis involve 4
steps.

1. Adsorption (chemisorption) on the surface and activation of

the reactants
2. Migration of the adsorbed reactants on the surface
3. Reaction among the adsorbed reactants
4. Escape or desorption of the products from the surface.

81
 Heterogeneous catalysts
Example : Haber process – the synthesis of ammonia from hydrogen and nitrogen

3H2 + N2 → 2NH3

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83
Thank You!

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