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CHAPTER 2

Chemical Kinetics

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CHAPTER 2
Rates of Reaction
Factors affecting rates of reaction
Rates law and order of reaction
Methods to determine order of
reaction
Relation between rate and
temperature
Reaction Mechanism
Catalytic kinetics
INTRODUCTION
 Chemical kinetics - is the study of chemical
rxns/processes with respect to reaction rates, effect
of various variables
INTRODUCTION
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RATEs of REACTION
Definition:
A measure of the change in the concentration of a
reactant or product in a given time.

[ x]
rate 
t
Unit = mole / liter = mol / L
second s
= Mol L-1 s-1
Reaction Rates(cont.)
depending on the experimental conditions :
 average rate: rate measured between long time
interval
 instantaneous rate: rate measured between very
short interval
 initial rate: instantaneous rate at the beginning of
an experiment
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RATEs of REACTION
Reactant Product
When the reactants change into products
 the concentration of reactants decreases
 the concentration of products increases
with time.
A B

[A]
rate = -
t

[B]
rate =
t

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Measuring Reaction Rate
 To measure a reaction rate, we usually monitor
either a product or a reactant for its change.
 Some of the characteristics to be monitored are:

-changes in pressure
-changes in color (use spectrofotometer )
-temperature for exothermic or
endothermic reaction, and
-presence of certain key substance
Reaction Rates and Stoichiometry
2A B

Two moles of A disappear for each mole of B that is formed.

1 [A] rate =
[B]
rate = -
2 t t

aA + bB cC + dD

1 [A] 1 [B] 1 [C] 1 [D]


rate = - =- = =
a  t b t c t d t
Reaction Rates and Stoichiometry
Example : Write the rate expression for the following reaction:

CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (g)

[CH4] 1 [O2] [CO2] 1 [H2O]


rate = - =- = =
t 2 t t 2 t

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TRY
2N2O5(g)  4NO2(g) O2(g)
Write the Differential rate equation for
above equation.

Solution

1  d[N 2 O 5 ]  1  d[NO 2 ]   d[O 2 ] 


Rate         
2 dt  4  dt   dt 
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TRY

2O3 ( g )  3O2 ( g )

1 d [O3 ] 1 d [O2 ]
rate   
2 dt 3 dt
TRY
TRY
Consider the reaction for the combustion
of methane, CH4 ,
CH4(g) + 2O2(g)  CO2(g)+ 2H2O(g)

If the methane is burning at a rate of 0.16 molL-1s-1 , at


what rates are CO2 and H2O being formed?
Solution
CH4(g) + 2O2(g)  CO2(g)+ 2H2O(g)
Given d[CH4] = - 0.16 molL-1s-1
dt

so; -d[CH4] = d[CO2] = d[H2O]


dt dt 2 dt
Solution
To calculate rate of N2;

d[CO2] = - d[CH4]
dt dt

= -(-0.16 molL-1s-1 )
= 0.16 molL-1s-1
Solution
To calculate rate of H2O;

d[H2O] = 2x -d[CH4]
dt dt

= 2 x –(-0.16 molL-1s-1 )
= 0.32 molL-1s-1
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TRY : Calculate the rate of reaction of C2H4 converted to C4H8


from t=0 to t=40s

2C2H4 (g) C4H8(g)


Time(s) 0 10 20 40 60
[C2H4]/mol L-1 0.884 0.621 0.479 0.328 0.169

Answer :
At t = 0s, [C2H4] = 0.884 M
At t = 40s, [C2H4] = 0.328 M

Rate = (0.884 – 0.328)M


40s
= 0.0139 Ms-1
= 0.014 Ms-1 so, the rate of reactions at 40s is 0.014 Ms-1
The Rate Law

THE RATE LAW  Expresses the relationship of the rate of a reaction to the rate
constant and the concentration of the reactants raised to some powers.

aA + bB cC + dD
Rate = k [A]a[B]b

k = rate constant
a&b = reaction order with
respect to A & B
a+b = overall reaction order

13.2
• Rate laws are always determined experimentally unless
you have been told a rate-limiting or slow step.

• Reaction order is always defined in terms of reactant


(not product) concentrations.
• The order of a reactant is not related to the
stoichiometric coefficient of the reactant in the balanced
chemical equation.

F2 (g) + 2ClO2 (g) 2FClO2 (g)

rate = k [F2][ClO2] 1

13.2
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THE ORDER OF REACTION


 The number of concentration factors in the
rate equation.
 Can only be determined experimentally.
 It shows the exact dependence of rate on
concentration.
 not from the number of moles as written in
the stoichiometric equation.
 The units of the rate constant depend on the
overall reaction order.
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First order reaction:
- A reaction with a single reactant A
- Rate is directly proportional to [A]

rate= k[A]

Second order reaction:


- Rate is directly proportional to the square of [A]

rate= k[A]2

Zero order reaction:


- the rate is not dependent on [A]

rate= k[A]0 = k (1) = k


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THE OVERALL REACTION


ORDER

Rate = k [ A ]m [ B ]n

 The overall order of reaction = sum


of the individual orders = m+n.

 with respect to each reactant in the


rate law.
Rates as Functions of Reactant
Concentrations
In a general reaction,

a A + b B +  products
Rate = k[A]x[B]y

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

Initial rate

Integrated Rate Law

Half life
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1. Initial Rate Method


To find the reaction orders by initial
rate method,
 Run a series of experiments,
 Each of the experiments have a
different set of reactant
concentration,
 From each experiments, obtain an
initial rate.
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Example 1
The results shown below are obtained for the
reaction between A and B. Determine the
rate equation for the reaction between A
and B.

Experiment Concentration Initial rate


(mol L-1) (mol L-1 s-1)
[A] [B]
1 0.0575 0.0216 8.21x10-3
2 0.0713 0.0216 1.26x10-2
3 0.0575 0.0333 1.26x10-2
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Calculating m in [A]m; we take the ratio of


the rate laws for two experiment 1 and 2, in
which [A] varies but [B] is constant:
m n
rate1  k [A] [B] 8.2110 3
 0.0575 
m

m n  
rate2  k [A] [B] 1.26 10 2
 0.0713 
That is, 0.652 = 0.806m
log 0.652 = m x log 0.806
m = 1.98  2
Thus, the reaction is
second order with respect to A
Calculating n in [B]n; we37take the ratio of the
rate laws for two experiment 1 and 3, in which
[B] varies but [A] is constant
m n
rate1  k [A] [B]
n
3
8.2110  0.0216 
m n  
rate 3  k [A] [B] 1.26 10 2
 0.0333 
That is, 0.652 = 0.649n
log 0.652 = n x log 0.649
n ≈ 1
 Hence, the reaction is first order with respect to
B.
 The rate equation is

rate  k[A]2[B]
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Example 2
The reaction between C and D is represented as
follows :
CD E
The experiment results are shown in the table below.
Determine the rate equation for the reaction
between C and D.
Initial concentration Time The change in
Experiment (M) interval concentration
(minutes) of C (M)
[C] [D]
1 0.05 1.0 30 2.5 x 10-3
2 0.05 2.0 30 1.0 x 10-2
3 0.1 1.0 120 5.0 x 10-3
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m n
rate1  k [C] [D] 2.5 10 3
 1.0 
n

m n  
rate 2  k [C] [D] 1.0 10 2
 2.0 

That is, 0.25 = (0.5)n


log 0.25 = m x log 0.5
n=2
Thus, the reaction is second order
with respect to D
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
solution
Assume: rate = k [A]x [B]y [C]z
From experiment 1 and 2, we have:
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
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m
rate1  k [C]m [D]n 2.5 10 3
 0.05 
 
rate 3  k [C]m [D]n 5.0 10 3
 0.1 

That is, 0.5 = (0.5)m


log 0.5 = m x log 0.5
m=1
Thus, the reaction is first order
with respect to C

The rate equation is

rate  k [C][D]2
TRY
The following data refers to the following
reaction:
CH3COCH3 + I2 + H+  CH3COCH2I + HI

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


M M 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
Based on the above information,
 Calculate the order with respect to
CH3COCH3 , I2 and H+.
 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.
zero order reaction
you will get a horizontalline,
because rate = k[A]0
rate = k (a horizontal line)
rate

independent to [reactant]

[A]

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first order reaction
 For first order, rate = k[A]
rate

the plot is a straight line (linear)

[A]
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second order reaction
 the plot is a branch of a prabola, because
rate = k [A]2
Rate

[A]
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The Rate Law &
Order Of Reaction
Summary of the Kinetics of Zero-Order, First-Order
and Second-Order Reactions

Integrated rate
Order Rate Law Unit law Half-Life
[A]0
0 rate = k Ms-1 [A] = [A]0 - kt t½ =
2k

1 rate = k [A] s-1 ln[A] = ln[A]0 - kt t½ = ln 2


k
1 1 1
2 rate = k [A]2 M-1s-1 = + kt t½ =
[A] [A]0 k[A]0
Exercise 1 - Initial rate method
The reaction of nitric oxide with hydrogen at 1280o C is

2NO(g) + 2H2(g) N2(g) + 2H2O(g)

From the following data collected at this temperature, determine :


a) The rate law
b) The rate constant
c) The rate of the reaction when [NO] = 1.2 x 10-3M and [H2] = 6.0 x 10-3 M

experiment [NO] (M) [H2] (M) Initial rate(M/s)

1 5.0 x 10-3 2.0 x 10-3 1.3 x 10-5

2 10.0 x 10-3 2.0 x 10-3 5.0 x 10-5

3 10.0 x 10-3 4.0 x 10-3 10.0 x 10-5


Exercise 2 - Half - Life Method
.
What is the half-life of N2O5 if it decomposes with a rate
constant of 5.7 x 10-4 s-1?
t½ = ln 2 = 0.693
= 1200 s = 20 minutes
k 5.7 x 10 s-4 -1

How do you know decomposition is first order?


units of k (s-1)
Exercise 3 – Integrated rate -law
The reaction 2A B is first order in A with a rate
constant of 2.8 x 10-2 s-1 at 800C. How long will it take for A
to decrease from 0.88 M to 0.14 M ?

[A]0 = 0.88 M
ln[A] = ln[A]0 - kt
[A] = 0.14 M
kt = ln[A]0 – ln[A]f
[A]0 0.88 M
ln ln
ln[A]0 – ln[A]t [A]t 0.14 M
t= = = = 66 s
k k 2.8 x 10-2 s-1
TRY
1. 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 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 ?
The Collision Theory
 In a chemical reaction, bonds are broken and
new bonds are formed.
 Molecules can only react if they collide with
each other.
 Furthermore, molecules must collide with the
correct orientation and with enough energy to
cause bond breakage and formation.
The Collision Theory

Effective
collision

Ineffective
collision

..but how do we define it as an effective??


The Collision Theory
 EFFECTIVE COLLISION - Collision with sufficient
amount of energy for reactant molecules to form
products.
 Collision theory:
I. Molecules must collides
II. Right orientation
III. Collision Energy > Ea
The Collision Theory :
Activation Energy
• In other words, there is a minimum amount of energy
required for reaction: the activation energy, Ea.
• Just as a ball cannot get over a hill if it does not roll up the
hill with enough energy, a reaction cannot occur unless the
molecules possess sufficient energy to get over the
activation energy barrier.

The activation energy (Ea ) is the minimum amount


of energy required to initiate a chemical reaction.
Activation energy (cont.)

The activation energy


is represented on a
reaction profile
(reaction energy
diagram) as the
energy barrier
between reactants
and products.
Activation energy(cont.)
The height of the activation barrier influences the
rate:

 IfEa is large, then few molecules possess enough


energy to get over the barrier; few products are
formed and the rate is slow.

 If
Ea is small, then many molecules possess
enough energy to get over the barrier; more
products are formed and the rate is faster.
What factors affect the rate of
reactions?

 increased concentration of
dissolved reactants
 increased pressure of gaseous
reactants
 increased temperature
 use of a catalyst

 increased surface area of solid


reactants
Effect of temperature on rate
The higher the temperature, the faster the rate of a reaction.
In many reactions, a rise in temperature of 10 °C causes the
rate of reaction to approximately double.
Why does increased temperature
increase the rate of reaction?
At a higher temperature, particles
have more energy. This means
they move faster and are more
likely to collide with other particles.
When the particles collide, they
do so with more energy, and so
the number of successful
collisions increases.
Effect of concentration on rate of reaction
The higher the concentration of a dissolved reactant, the
faster the rate of a reaction.
Why does increased concentration increase the rate of
reaction?
At a higher concentration, there are more particles in the
same amount of space. This means that the particles are
more likely to collide and more effective collision will
happen.

lower concentration higher concentration


Slower and slower!
Reactions do not proceed at a steady rate. They start off at a
certain speed, then get slower and slower until they stop.
As the reaction progresses, the concentration of reactants
decreases.
This reduces the frequency of collisions between particles
and so the reaction slows down.

0% 25% 50% 75% 100%


reactants
percentage completion of reaction
product
Effect of pressure on rate of reaction
Why does increasing the pressure of gaseous reactants
increase the rate of reaction?
As the pressure increases, the space in which the gas
particles are moving becomes smaller.
The gas particles become closer together, increasing the
frequency of collisions. This means that the particles are more
likely to react each other thus increase rate of reaction.

lower pressure higher pressure


Effect of surface area on rate of reaction
Any reaction involving a solid can only take place at the
surface of the solid.
If the solid is split into several pieces, the surface area
increases. What effect will this have on rate of reaction?

low surface area high surface area


This means that there is an increased area for the reactant
particles to collide with.
The smaller the pieces, the larger the surface area. This
means more collisions and a greater chance of reaction.
How catalysts increase rate of rxn?
Speeds up a reaction but is chemically unchanged at the
end of the reaction.
Adding a catalyst has exactly effect on EA.
provides an alternative route for the reaction  with
lower activation energy.
Ea without Different catalysts work in
catalyst different ways, but most
energy (kJ)

lower the reaction’s


activation energy (Ea).

Ea with
catalyst
reaction (time)
Type of catalysis
a) Homogeneous
 The catalyst is in the same phase as
the reactants.

b) Heterogeneous
 The catalyst is in a different phase
than the reactants – often a solid
catalyst and liquid or gaseous
reactants.
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How temperature and Catalysts Affect Reaction Rates

The Arrhenius’ Equation


Temperature in K
k= A e-Ea/RT

Activation Gas constant


Frequency
of collisions energy 8.314 J/mol • K
Determination of the values of
A and Ea
linearizing the Arrhenius equation;
Determination of the values of
A and Ea
A plot of ln k versus 1/T will have a slope of -Ea/R
and an intercept of ln A.

70
Example:
A plot of ln(k) vs. 1/T(K)
Rate vs. Temperature
y = -7330.4x + 25.417
2

1.6
ln rate

1.2

0.8

0.4

0
3.1E-03 3.2E-03 3.3E-03 3.4E-03 3.5E-03 3.6E-03

1/T, Kelvin

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Example: (cont.)

Q1Calculate the activation energy for this


reaction?
Q2 Calculate rate would be expected for this
reaction at 30C?
Q3 Determine temperature is needed to
double this rate?
Solution for Q1:
First, correlate the actual equation of the line with
the Arrhenius Equation:

ln k = - Ea/R(1/T) + ln A
y = mx + c
y = -7330.4x + 25.417

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Solution for Q1:

Slope = Ea

R
Ea = - (Slope) x (R)
Ea = - (-7330.4 K) x (8.314 J/molK)
Ea = 60.9 kJ/mol

So the activation energy for this reaction


is 60.9 kJ/mol

74
Solution for Q2:
The rate at 30°C is …
( 30 + 273 = 303K)

ln(k) = -7330.4(1/T) + 25.417 (given)


ln(k) = -7330.4(1/303K) + 25.417
ln(k) = 1.22
k = e 1.22
k = 3.40 Ms-1

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Solution for Q3:
The temperature needed to double this
rate….( 3.4 x 2 = 6.8)

ln(rate) = -7330.4(1/T) + 25.417 (given)


ln(6.8) = -7330.4(1/T) + 25.417
1.91 = -7330.4(1/T) + 25.417
-23.50 = -7330.4(1/T)
T = 312K
= 312 – 273 = 39°C

76
If we have two different k values at different
temperatures, you can combine the two
reactions to give:

ln k2 = Ea 1 1
k1 R T1 T2

Where T1 < T2
Example
The rate constant for the formation of HI at 600K and 650K
are measured and found to be 2.7x10-4 M-1s-1 and 3.5x10-3
M-1s-1, respectively. Determine the activation energy and
the rate constant at 800 K.
H2+I2  2HI
Solution

ln k2 = Ea 1 1
k1 R T1 T2
ln (3.5x10-3 ) = Ea 1 - 1
(2.7x10-4 ) 8.314 Jmol-1 600K 650K

ln (13.0 ) = Ea (1.28x10-4)
8.314 Jmol-1

Ea = 2.56 x 8.314 Jmol-1 = 1.66x105 Jmol-1


(1.28x10-4)
= 166 kJmol-1
Example
Solution
To determine rate constant at 800K.

ln k2 = Ea 1 - 1
(3.5x10-3 ) R 650 800

= 1.66 x 105 Jmol-1 (2.88 X 10-4 K-1)


8.314 Jmol-1

= 5.75
Taking the anti ln:
k2 = 314
3.5x10-3

The rate constant at 800 K, k2 = 314 (3.5x10-3 ) = 1.10 M-1s-1


81

TRY
 Therate constant of a reaction is 1.2 x 10-3 sec-1 at
300 C and 2.1 x 10-3 sec-1 at 400 C. Calculate the
energy of activation of the reaction.

ln k2 = Ea 1 1
k1 R T1 T2

 Answer: Ea = 44.168 kJ mol-1


Reaction Mechanism
Elementary reactions
Elementary reactions
+ Uni-
molecular
Bi-
molecular
Elementary reactions
Trimolecular

REACTION
MECHANISM

Reaction
intermediate
Fast
Slow

Rate –determining step


Reaction Mechanisms

The overall progress of a chemical reaction can be represented


at the molecular level by a series of simple elementary steps
or elementary reactions.

The sequence of elementary steps that leads to product


formation is the reaction mechanism.

2NO (g) + O2 (g) 2NO2 (g)

Elementary step: NO + NO N2O2


+ Elementary step: N2O2 + O2 2NO2
Overall reaction: 2NO + O2 2NO2
Intermediates are species that appear
84 in a reaction
mechanism but not in the overall balanced equation.
An intermediate is always formed in an early elementary step
and consumed in a later elementary step.

Elementary step: NO + NO N2O2


+ Elementary step: N2O2 + O2 2NO2
Overall reaction: 2NO + O2 2NO2

The molecularity of a reaction is the number of molecules


reacting in an elementary step.
• Unimolecular reaction – elementary step with 1 molecule
• Bimolecular reaction – elementary step with 2 molecules
• Termolecular reaction – elementary step with 3 molecules
Rate Laws and Elementary Steps
85

Writing reaction mechanisms:


• The sum of the elementary steps must give the overall
balanced equation for the reaction.
• The rate-determining step should predict the same rate
law that is determined experimentally.
The rate-determining step is the slowest step in the
sequence of steps leading to product formation.
The experimental rate law for the reaction between NO2
and CO to produce NO and CO2 is rate = k[NO2]2. The
reaction is believed to occur via two steps:
Step 1: NO2 + NO2 NO + NO3
Step 2: NO3 + CO NO2 + CO2
What is the equation for the overall reaction?
NO2+ CO NO + CO2

What is the intermediate?


NO3

What can you say about the relative rates of steps 1 and 2?
rate = k[NO2]2 is the rate law for step 1 so
step 1 must be slower than step 2
13.5
Thank you!