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Chemical

Kinetics

1

SCOPE

Factors affecting Reaction Rate

Rate Law and Its Component

Integrated Rate Laws:

- Zeroth, First and Second Order

Reactions

2

LEARNING

OUTCOME

Able to apply the Arrhenius equation and rate

law in calculations.

determine step for a given reaction.

LEARNING

OUTCOMES

Calculate rate constants

Write expression for integrated rate laws

Determine half life

LEARNING

OUTCOME

constant or activation energy.

reactions

5

Expression

of a reaction

reactants disappear and products form

positive values

6

Rates

Instantaneous rate:

slope of a line tangent

to the curve at a

particular point (e)

Initial rate:

the instantaneous rate

at the moment

reactants are mixed (a)

Average rate:

slope of line joining

any two points (b, c, d)

7

Expression

of reactants or products per unit time

A B

Average rate =

t

= delta = (final - initial) concentration of

reactant/product

use [ ] to express concentration in moles/liter

A

B

Average rate = t = t

8

Expression

Consider the reaction

A B

Expression

Consider the reaction

A B

10

Expression

Consider the reaction

A B

time

rate (A) =

t2 t 1

[A]

t

time

rate (B) =

t2 t 1

11

[B]

t

Expression

Consider the reaction

A B

changes in the first 50 seconds

rate (A) =

[A]

t

([A]t=50 [A]t=0)

50 s 0 s

(0.0629 mol L-1 0.0750 mol L-1)

50 s

2.4 10 mol L s

-4

-1

-1

12

Expression

Consider the reaction

A B

instantaneous rate

This can be determined from the slope of a

tangent to the curve

For example, from plotting of [A] against time,

at t = 50 s

rate = -(slope of tangent line) =

= 2.3 10-4 mol L-1 s-1

13

-d[A]

dt

Expression

Reaction:

A B

A.

At t =0 there is 1.00 mol A, no B present.

At t =10 min, there is 0.74 mol A and 0.26

mol B

At t =40 min, there is 0.30 mol A and 0.70

(moles B)

mol B.

t

Calculate average rate from t = 0 to t = 10

(mol B at t 10 min) - (mol B at t 0)

min.

10 min 0 min

average rate 0.26 mol - 0 mol

14

0.026

mol/min

10 min - 0 min

Expression

Consider :

C4H9Cl(aq)+H2O(l)

Butyl chloride

C4H9OH(aq)+HCl (aq)

Butyl alcohol

of the disappearance of C4H9Cl.

15

Expression

Time (s) [ C4H9Cl ] (M)

0.0

0.1000

50.0

0.0905

100.0

0.0820

150.0

0.0741

200.0

0.0671

300.0

0.0549

400.0

0.0448

500.0

0.0360

800.0

0.0200

16

C4H9Cl(aq)

Expression

+ H O C H OH +HCl

2

(l)

(aq)

(aq)

17

Expression

(C4H9Cl)

t

C4H9Cl finaltime C4H9Cl initialtime

final

time

initial

time

18

C4H9Cl(aq)+ H2O(l)Expression

C4H9OH(aq)+HCl (aq)

Time (s)

0.0

50.0

100.0

150.0

200.0

300.0

400.0

500.0

800.0

0.1000

1.9 x 10-4

0.0905

1.7 x 10-4

0.0820

1.6 x10-4

0.0741

1.4x10-4

0.0671

1.22x10-4

0.0549

1.01 x10-4

0.0448

0.80x10-4

0.0360

0.56x10-4

0.0200

19

Stoichiometry

Reaction : relationship one-to-one

C4H9Cl (aq) + H2O (l)

(aq)

C4H9Cl consumed. H2O is consumed and HCl is

H2O

HCl

t

t

C4H9Cl

C4H9OH

Rate =

t

t 20

produced.

Stoichiometry

Reaction : relationship is not one-to one

2HI (g)

H2 (g) + I2(g)

appearance of H2 and I2 .

1 HI H2 I2

rate =

2 t

t

t

In general for: aA + bB

rate =

cC + dD

1 A

1 B 1 C 1 D

a t

b t

c t

d 21t

Stoichiometry

Example:

Write the rate expressions for the following

reactions in terms of the disappearance of

the reactants and the appearance of the

products.

4NH3 (g) + 5O2 (g)

22

Stoichiometry

Solution:

1 NH3

1 O 2 1 NO

rate

4 t

5 t

4 t

1 H 2 O

6 t

23

Stoichiometry

Example :

If the butane concentration is decreasing at a

rate of 0.20 mol L1 s1, at what rate is the

oxygen concentration decreasing?

Solution:

0.20 mol C4H10

13 mol O2

rate (O2) =

x

Ls

2 mol C4H10

1.3 mol O2

Ls

Rate

Principal factors influence reaction rates:

2. Ability of the reactants to come in contact with

each others

3. Concentrations of the reactants

4. Temperature

5. Availability of rate-accelerating agents called

catalysts

25

Rate

Chemical nature of the reactants

During reactions, bonds break and new

bonds form

Some reactions are fast by nature and

others are slow

26

Rate

Most reactions involve two or more reactants

whose particles (atoms, ions or molecules)

must collide for the reaction to occur

In a homogeneous reaction, all of the reactants

are in the same phase

In a heterogeneous reaction, the reactants are

present in different phases

Surface area , Rate

27

Rate

Surface area

determines the reaction rate

28

surface area)

29

Rate

Concentration of the reactants

The rates of both homogeneous and

heterogeneous reactions are affected by the

concentrations of the reactants

For example, red-hot steel wool bursts into flame

when thrust into pure oxygen

Concn , Rate

30

Rate

Almost all chemical reactions occur

faster at higher temperatures

Temperature , rate

a: energetic collision - lead to

product

b,c,d: molecules just bounce off!!

31

Rate

Presence of catalysts

Catalysts are substances that increase

the rate of chemical reactions without

being used up

For example, enzymes that direct our

body chemistry are all catalysts

32

Rate

Presence of catalysts

33

A rate law is an equation in which the rate is

given as a function of reactant concentrations

for example, rate = k[HI]n

k is the rate constant of the reaction

n is the order of the reactant

Both rate constant and order must be

experimentally determined

34

The value of the rate constant, k depends

on the particular reaction being studied

and the temperature at which the

reaction occurs

an integer or a fraction

balanced equation

35

Types of rate laws:

A differential rate law expresses the rate as a

function of concentration

d[A]

rate =

= k[A]

dt

An integrated rate law expresses the

concentration as a function of time

[ A]0

ln

kt or [ A]t [ A]0 e kt

[ A]t

36

Consider the hypothetical reaction:

A + B products

The rate law for the reaction is:

rate = k[A]m[B]n

The values of m and n can be discovered by

looking for patterns in the rate data (experimental

data)

Order cannot be deduced from the balanced

equation

37

H 2 SeO3 6 I 4 H

Se 2 I 3H 2O

(determined from initial rates) is

3

rate k[ H 2 SeO3 ] [ I ] [ H ]

1

equation !!!!!!!!

38

A + B product (C)

Suppose that the data in the table below has

been obtained in a series of five experiments:

39

A + B product (C)

For experiments 1, 2 and 3 [B] is held constant. Any

changes in the rate must be due to the change in [A]

The rate law says that at constant [B] the rate must

be proportional to [A]m

rateexp 2

rateexp 1

[A]exp 2

[A]exp 1

rateexp 2

rateexp 1

0.20 mol L s

-1

-1

=2

and

[A]exp 2

[A]exp 1

0.10 mol

L

40

-1

=2

A + B product (C)

So doubling [A] from experiment 1 to experiment 2

doubles the rate

The relationship reduces to:

2.0 = 2.0m

The only value of n that makes this equation true is

m=1

The reaction must be first order with respect to A

41

A + B product (C)

In the final three experiments, the concentration

of B changes while the concentration of A is held

constant

This time it is [B] that affects the rate

rateexp 4

rateexp 3

[B]exp 4

[B]exp 3

4.0 = 2.0n

Therefore, n must equal 2

42

A + B product (C)

We now know that the rate law for the

reaction must be:

rate = k[A]1[B]2

The overall order is the sum of the orders for

each reactant in the rate law = 3

What is the value of k?

43

Laws

function of time

Consider the hypothetical reaction:

A products

The (differential) rate law has the form:

rate =

d[A]

dt

= k[A]n

44

laws

Zero-order rate laws, n=0

The differential rate law is:

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

The integrated rate law is:

[C]t = kt + [C]0

A plot of [C] versus time gives a straight

45

line of slope k

laws

Zero-order rate laws

46

First-order reactions

Assume A products is first order, n=1

The differential rate law has the form:

dt

The integrated rate law would be:

[ A]0

kt

ln

kt or [ A]t [ A]0 e

[ A]t

[A]0 is [A] at t (time) = 0

[A]t is [A] at t = t

47

e = base of natural logarithms = 2.71828

First-order reactions

rate =

d[A]

dt

= k[A]

A k t dt

A A

0

ln A t ln A 0 k t

At d

0

ln A t k t ln A 0

ln

[A]0

[A]t

= kt

or

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

48

Laws

For first order reactions a plot of the natural

logarithm of concentration versus reaction time

always gives a straight line

49

Laws

Example

decomposition of N2O5 in CCl4 at 45oC is 6.32 10-4 s-1

2N2O5 4NO2 + O2

a. What is the concentration of N2O5 remaining after

2.00 hr if the initial concentration of N 2O5 was

0.500 M ?

b. How much time required for 90% of N2O5 to

50

decompose ?

Laws

Solution

ln [ A ]t = -kt + ln [ A ]o , ln [N2O5]t = -kt + ln [N2O5]o

ln [N2O5]t = -( 6.32 10-4 s-1) x

(2.00 hr 3600 s/1 hr) + ln (0.500)

ln [N2O5]t = -4.55 + ( -0.693) = -5.24

[N2O5]t = exp (-5.24) = 5.3 10-3 M

51

Laws

Solution

concentration.

90% of N2O5 has decomposed, so only 10% remains

[N2O5] = (0.1)(0.500 M N2O5)= 0.0500 M N2O5

ln [ 0.0500 ] = - (6.32 10-4 s-1) t + ln [ 0.500 ]

- 2.996 = - ( 6.93 10-4 s-1) t + (-0.693)

t = 3.64 103 s

The time it takes for 90% of N2O5 to disappear is

3604 s or 1.01 hrs

52

Laws

Second-order reactions, n=2

Assume B products is second order

The differential rate law is:

rate =

d[B]

dt

= k[B]2

1

[B]t

= kt +

1

[B]0

53

Laws

Second-order reactions

B

2

Rate

k B

t

At d B

t

B

k t ,

k dt

2

2

A 0 B

0

B

1

1

1

1

kt ,

kt

B t B 0

Bt

B 0

54

Laws

When a reaction is second order, a plot of 1/[B]

55

Half life

The amount of time required for half of a

reactant to disappear is called the half-life, t1/2

The half-life of a first-order reaction is not

affected by the initial concentration

[ A]0

First - order rate law : ln

kt

[ A]t

1

at t t1/ 2 , [ A]t [ A]0 , substituti ng

2

[ A]0

ln 2

ln 1

kt1/ 2 or t1/ 2

k

[ A]0

56

2

Half life

initial concentration is represented by [I]

570.

Half life

The half-life of a second-order reactions

does depend on the initial concentration

1

1

Second - order integrated rate law :

kt

[ B ]t [ B ]0

1

at t t1/ 2 , [ B]t [ B ]0 , substituting

2

1

1

kt1/ 2

1

[ B]0 [ B]0

2

1

l

kt1/ 2 or t1/ 2

[ B ]0

k[ B ]0

58

SUMMARY

59

Example

Carbon-14 (14C) is a radioactive isotope

with a half-life of 5.73 x 103 years. It

decays following the first order reaction.

The amount of 14C present in an object can

be used to determined its age. Calculate

the rate constant for decay of 14C and

determine how long is required for 90% of

the 14C in a sample to decompose.

60

Solution

t1

0.693

,

k

0.693

5.73 103 yr

0.693

t1

2

1.21 10 4 yr 1

ln A 0 kt ln A t ,

ln

A 0

0.10 A 0

kt ln

A 0

A t

ln

A 0

A t

k

ln 10

1

.

90

10

yr

3

1

3

1

1.21 10 yr

1.21 10 yr

61

kinetics

Collision theory

One of the simplest models to explain

reaction rates is collision theory

Collision theory says that the rate of a

reaction is proportional to the number of

effective collisions per second among the

reactant molecules

An effective collision is one that actually

gives product molecules

kinetics

Concentration can influence the number of

effective collisions per second

As reactant concentrations increase, the

number of effective collisions increases

Not every collision between reactant

molecules actually results in a chemical

change

Only a very small fraction of all the collisions

can really lead to a net change

Why is this so?

kinetics

Molecular orientation

When two reactant molecules collide they must

be oriented correctly for a reaction to occur

(see next slide)

kinetics

kinetics

Activation energy

The activation energy (Ea) is the minimum

energy required for a reaction to occur

The activation energy determines the rate of

a reaction

At a given temperature, only a certain fraction

of the collisions possess enough energy to be

effective and form products

66

kinetics

67

kinetics

The arrangement found on the top of the

potential energy hill is called the activated

complex or transition state

Once the transition state is reached, the

reaction proceeds to give products, with the

release of energy

A reaction intermediate corresponds to an

energy minimum between two transition

states

68

Transition State

Theory

The activated complex is unstable species and what exists

is neither reactant nor product but a transitional species

with partial bonds. Consider reaction between:

CH3Br + OH- CH3OH + Br-

69

kinetics

Temperature effects

temperature

70

kinetics

The activation energy is related to the rate

constant by the Arrhenius equation

k = Ae

-Ea/RT

k = rate constant

Ea = activation energy

R = universal gas constant

T = temperature (in Kelvin)

A = pre-exponential or frequency factor

71

kinetics

The activation energy can also be obtained

from two rate components measured at

different temperatures

Most reactions obey the Arrhenius equation

to a good approximation

ln

k2

k1

Ea

T2

1

T1

72

Example

An alteration in the structure of a certain virus follows firstorder kinetics with Ea = 587 kJ/mol .The half-life at 29.6oC is

1.62 104 s ( 1 yr = 3.154 107 s ). What are the rate

constants at 29.6oC and the half-life at 32oC for the alteration

of the virus ?

Solution

For a first order rxn: k1 = 0.693 / t1/2

Rate constant at 29.6oC = 0.693 / (1.62 104 s)

= 4.28 10-5 s-1

73

Solution (cont.)

Ea is given, so k2 can be calculated using the Arrhenius

equation.The t 1/2 at 32.0oC can be obtained from k2.

Ea

k1

ln

k2

R

1

1

T1 T2

4.28 10 -5 s -1

(587

kJ/mol)(10

00

J/kJ)

ln

k

8.314 J/mol.K

2

1

1

305.0 K 302.6 K

k 2 2.68 10 - 4 s -1

74

Solution (cont.)

o

t1/2 0.693/ k2

0.693

2.68 10 4 s-1

2.58 103 s

75

2.6 Reaction

mechanisms

Most reactions do not occur in a single

step

series of simple reactions

process

the reaction mechanism

76

2.6 Reaction

mechanisms

The rate law of an elementary process can

be written from its chemical equation

processes

mechanism must agree with the

observed rate law for the overall

reaction

77

Example

The following two reactions are proposed as elementary steps in the

mechanism for an overall reaction:

(1) NO2Cl (g) NO2 (g) + Cl (g)

(2) NO2Cl(g) + Cl (g) NO2(g) + Cl2(g)

Overall reaction: (1) + (2)

Overall rxn: 2NO2Cl(g) 2NO2 (g) + Cl2

Reaction intermediate is a substance that is formed and used up in

the overall reaction, does not appear in the overall reaction: Cl (g)

Rxn(1) : Unimolecular, Rate = k1[NO2Cl]

Rxn(2): Bimolecular, Rate = k2[NO2Cl][Cl]

78

2.6 Reaction

mechanisms

The rate-determining step

Consider the gaseous reaction:

2NO2Cl 2NO2 + Cl2

following two-step sequence of elementary

processes:

NO2Cl NO2 + Cl

(slow)

(fast)

79

2.6 Reaction

mechanisms

In any multistep mechanism, one step is

usually much slower than the others

the rate-determining step

step is directly related to the rate law

for the overall reaction

80

2.5 Reaction

mechanisms

Rate laws for elementary

steps

expression of rate laws.

Eg:

Step 1: NO (g) + Br2 (g) NOBr2

(fast)

Rate law

: Rate=k[NOBr2] [NO]

81

Example

NO catalyzes the decomposition of N2O possibly

through the following mechanism:

NO(g) + N2O(g) N2(g) + NO2(g)

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

What is the overall reaction?

(1) 2 2NO (g) + 2N2O (g) 2N2 (g) + 2NO2

(g)

(2)

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

_________________________________

2N2O (g) 2N2 (g) +O2(g)

NO = catalyst;

NO2=intermediate 82

The End

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