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You are on page 1of 92

Chemical Kinetics

1

2

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

6

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

12

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

13

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

1 [A] rate =

[B]

rate = -

2 t t

aA + bB cC + dD

rate = - =- = =

a t b t c t d t

Reaction Rates and Stoichiometry

Example : Write the rate expression for the following reaction:

rate = - =- = =

t 2 t t 2 t

16

17

TRY

2N2O5(g) 4NO2(g) O2(g)

Write the Differential rate equation for

above equation.

Solution

Rate

2 dt 4 dt dt

18

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)

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

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

24

from t=0 to t=40s

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

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.

(not product) concentrations.

• The order of a reactant is not related to the

stoichiometric coefficient of the reactant in the balanced

chemical equation.

rate = k [F2][ClO2] 1

13.2

27

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.

28

First order reaction:

- A reaction with a single reactant A

- Rate is directly proportional to [A]

rate= k[A]

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

rate= k[A]2

- the rate is not dependent on [A]

29

ORDER

Rate = k [ A ]m [ B ]n

of the individual orders = m+n.

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.

33

Initial rate

Half life

34

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.

35

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.

(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

36

the rate laws for two experiment 1 and 2, in

which [A] varies but [B] is constant:

m n

rate1 k [A] [B] 8.2110 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

8.2110 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]

38

Example 2

The reaction between C and D is represented as

follows :

CD 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

39

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

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

overall order = 3+2+1 = 6

42

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

log 0.5 = m x log 0.5

m=1

Thus, the reaction is first order

with respect to C

rate k [C][D]2

TRY

The following data refers to the following

reaction:

CH3COCH3 + I2 + H+ CH3COCH2I + HI

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]

45

first order reaction

For first order, rate = k[A]

rate

[A]

46

second order reaction

the plot is a branch of a prabola, because

rate = k [A]2

Rate

[A]

47

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

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

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

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

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 70C 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 70C ?

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

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.

of energy required to initiate a chemical reaction.

Activation energy (cont.)

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:

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

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.

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.

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.

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?

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)

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.

67

How temperature and Catalysts Affect Reaction Rates

Temperature in K

k= A e-Ea/RT

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

71

Example: (cont.)

reaction?

Q2 Calculate rate would be expected for this

reaction at 30C?

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

73

Solution for Q1:

Slope = Ea

R

Ea = - (Slope) x (R)

Ea = - (-7330.4 K) x (8.314 J/molK)

Ea = 60.9 kJ/mol

is 60.9 kJ/mol

74

Solution for Q2:

The rate at 30°C is …

( 30 + 273 = 303K)

ln(k) = -7330.4(1/303K) + 25.417

ln(k) = 1.22

k = e 1.22

k = 3.40 Ms-1

75

Solution for Q3:

The temperature needed to double this

rate….( 3.4 x 2 = 6.8)

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

(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

8.314 Jmol-1

= 5.75

Taking the anti ln:

k2 = 314

3.5x10-3

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

Reaction Mechanism

Elementary reactions

Elementary reactions

+ Uni-

molecular

Bi-

molecular

Elementary reactions

Trimolecular

REACTION

MECHANISM

Reaction

intermediate

Fast

Slow

Reaction Mechanisms

at the molecular level by a series of simple elementary steps

or elementary reactions.

formation is the reaction mechanism.

+ 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: N2O2 + O2 2NO2

Overall reaction: 2NO + O2 2NO2

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

• 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

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!

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