Easy study material for 10+2 AP chemistry students. Specially prepared for Intermediate Public Examination, Andhra Pradesh.

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Easy study material for 10+2 AP chemistry students. Specially prepared for Intermediate Public Examination, Andhra Pradesh.

Attribution Non-Commercial (BY-NC)

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Вы находитесь на странице: 1из 11

Aditya vardhan

Chemical kinetics 1 adichemadi @ gmail.com

CHEMICAL KINETICS

Chemical kinetics deals with

1) Study of rates of reactions

2) Factors affecting rate of reaction

3) Study of mechanisms of reactions

Rate of reaction : The rate of reaction is defined as the change in molar concentration of either

reactants or products in unit time.

change in concentration

rate r =

time interval

Let ‘dc’ is the decrease in concentration of reactants in a small interval of time ‘dt’ then

dc

r=- ( negative sign indicates decrease in concentration )

dt

If ‘dx’ is the increase in concentration of products in a small interval of time ‘dt’ then

N

HA

dx

r= ( positive sign indicates increase in concentration )

dt

E

E.g., For a reaction, A

B RD

EG

by

d A d B

rate r

LL

ed

dt dt

VA

AL O

ar

G C

In general for a reaction, pP + qQ rR + sS

ep

AN IOR

the relations between rates of reaction with respect to P,Q,R and S can be written as

Pr

YA

1 d P 1 d Q 1 d R 1 d S

AR N

- =- =+ =+

W U

p dt q dt r dt s dt

J

AG T

VI

2NH3 g , the relations can be expressed as

I

DE

AD

d N2 1 d H2 1 d NH 3

- -

dt 3 dt 2 dt

VA

V.

1) Nature of reactants: Rate of a reaction depends on the nature of bonding in the reactants. Ionic

compounds react faster than covalent compounds.

The reactions between ionic compounds in water occur very fast as they involve only exchange of

ions.

Eg., AgCl is precipitated out immediately when AgNO3 solution is added to NaCl solution.

AgNO 3 +NaCl AgCl NaNO 3

This reaction involves only exchange of ions as shown below and hence occurs very fast.

Ag + +NO -3 +Na + +Cl- AgCl Na + NO -3

Reactions between covalent compounds take place slowly because they require energy for the

cleavage of existing bonds.

Eg., Following esterification of acetic acid occurs slowly as the breaking of bonds require energy.

O O

H2SO4

H3C C + H O C2H5 H3C C + H2O

OH OC2H5

Prepared by V. Aditya vardhan

Chemical kinetics 2 adichemadi @ gmail.com

2) Concentration: Rate of a reaction is directly proportional to the concentration of reactants.

rate (r) cn

where c = concentration

n = order of the reaction

or r = kcn

where k = specific rate

The number of collisions increases with increase in concentration and hence the rate of the reaction

also increases.

The rate of a reaction decreases with time as the concentration of reactants is decreasing. This can

be shown graphically as follows.

concentration of reactants

N

HA

E

RDTime

EG

by

LL

ed

3) Temperature : The average kinetic energy and hence the number of collisions increase with abso-

VA

AL O

ar

G C

ep

Usually the rate of a reaction is doubled when the temperature is increased by 10oC.

AN IOR

Pr

Temperature Coefficient : The ratio of rate constants of a reaction at two different temperatures

YA

AR N

W U J

k t +10o C

AG T

VI

I

k t oC

DE

AD

The relation between rate constant and temperature can be shown by Arrhenius equation.

k = A.e-Ea/RT

VA

V.

A = Frequency factor

Ea = Activation energy

R = Universal Gas constant

T = Absolute Temperature

Multiplying by 'ln' (natural logarithm) on both sides,

Ea

ln k = ln A-

RT

Ea

or 2.303 log k = 2.303 log A-

RT

Ea

or log k = log A-

2.303 RT

When a graph is plotted by taking log k on y - axis and 1/T on x-axis, a straight line with negative slope

is obtained.

Ea E

slope = - =- a where R = 1.987 cal / K / mole

2.303 R 4.576

Prepared by V. Aditya vardhan

Chemical kinetics 3 adichemadi @ gmail.com

log A

Ea

slope = -

2.303 R

log k

1

T

Relation between two rate constants at two different temperatures can be given as

k2 Ea 1 1

log = -

k1 2.303R T1 T2

N

k2 E a T2 -T1

HA

or log =

k1 2.303R T1T2

E

RD

EG

4) Catalyst: Catalyst is a substance which alters the rate of reaction without being consumed or without

by

LL

ed

A catalyst increases the rate of reaction by providing a new path with lower activation energy for the

VA

AL O

ar

reaction. In case of reversible reactions, catalyst lowers the activation energies of both forward and

G C

ep

backward reaction to the same extent and helps in attaining the equilibrium quickly.

AN IOR

Pr

YA

AR N

W U

without catalyst

Potential energy

J

AG T

VI

in presence of catalyst

I

DE

AD

VA

V.

Reaction coordinate

Problems :

1) Write the relations between the rates with respect to reactants & products in the following reaction.

2N2O 2N2 + O2

Rate Equation or Rate Expression or Rate Law: Equation that describes mathematical dependance

of rate of reaction on the concentration terms of the reactants is called Rate Equation.

x y z

r = k A B C

where k= rate constant or specific rate

x,y and z are orders with respects to A,B and C respectively.

Order of reaction :Sum of the powers of the concentration terms in the rate equation is called order

of reaction.

For a general reaction, xA + yB + zC products.

Prepared by V. Aditya vardhan

Chemical kinetics 4 adichemadi @ gmail.com

x y z

if the rate expression is r = k A B C

Then the order of this reaction is equal to x + y + z

Note: Order of a reaction is to be determined experimentally. It may have positive or negative or zero

or a fractional values.

In case of simple reactions, the order of reaction and hence the rate equation can be written

according to stoichiometric equation. But the actual rate law should be written by conducting experi-

ments.

Depending on the order of reaction, chemical reactions can be divided into zero, first, second &

third order reactions as follows.

Example:

1) Decomposition of NH3 on metal surfaces such as gold and molybdenum.

Au

N 2 g +3H 2 g 2NH 3g

N

r = k[N2]0[H2]0

HA

First order reaction: Total order of the reaction is one.

E

Examples: RD

EG

by

LL

ed

VA

AL O

ar

r = k[N2O5]

G C

ep

AN IOR

Pr

SO2Cl2 SO2+Cl2

YA

AR N

r = k [ SO2Cl2]

W U J

AG T

VI

I

DE

AD

r = k[H2O2]

4) All radioactive disintegrations

VA

V.

Examples:

1) Thermal decomposition of N2O

2N2O 2N2 + O2

r= k [N2O]2

2) Decomposition of Cl2O

2Cl2O 2Cl2 + O2

r= k [Cl2O]2

Examples:

1) Reaction between NO and O2 to give NO2

2NO + O2--------> 2NO2

r = k[NO]2[O2]

2) Reaction between NO and Cl2 to give NOCl

2NO + Cl2 2NOCl

r = k[NO]2 [Cl2]

Prepared by V. Aditya vardhan

Chemical kinetics 5 adichemadi @ gmail.com

Problems :

1) What is the order of the reaction if the rate law for the reaction A + 2B products is

r = k [A]1/2[B]2

Rate constant (k): The rate of a reaction at the unit concentrations of all the reactants of the reaction is

called specific rate (or) rate constant.

rate = k when [reactants] = 1

For a general reaction, A products

Rate expression can be written as

dc n

rate = k A

dt

where n = order of the reaction

dc 1

N

k= x

dt A n

HA

mole / litre 1

Units of k = x n

sec mole / litre

E

RD

EG

by

1-n

mole / litre

LL

ed

=

VA

AL O

ar

sec

G C

ep

= Ln-1 .mole

- n-1

.sec-1

AN IOR

Pr

YA

-1

AR N

W U

L.mole sec

-1

J

AG T

VI

L .mole sec

-1

I

DE

AD

-1 -1

For zero order reaction mole .L sec

Molecularity

VA

V.

Elementary reactions: The chemical reactions which occur in one single step are called elementary

reactions.

But most of the reactions occur in more than one step. The sequence of elementary steps that occur

during a reaction is referred to as mechanism of that reaction.

Rate determining step: The elementary step or reaction with slowest rate is called rate determining step

or rate limiting step. The rate of overall reaction depends on this step.

Molecularity: Total number of atoms or molecules or ions taking part in an elementary reaction is called

molecularity of that elementary reaction (or step).

It is only possible to define the molecularity of an elementary step. But the molecularity of the overall

reaction which involves more than one step cannot be defined.

Molecularity is an integer. It cannot be zero or fractional. The maximum value observed is 3. It can be

deduced theoretically from the proposed mechanism

Prepared by V. Aditya vardhan

Chemical kinetics 6 adichemadi @ gmail.com

Differences between Order and Molecularity

Order Molecularity

1) Sum of the powers of concentration terms 1) Total number of atoms or molecules or

in rate expression is called order. ions taking part in an elementary reaction is

called molecularity

2) It may have zero or positive or negative or 2) It can only have integral values (1,2 or 3).

integer or fractional values. Its value cannot be zero or fractional.

3) It is determined experimentally 3) It is deduced theoretically from the

mechanism of the reaction.

Zero order rate equation:

Reactions in which the rate is independent of the concentrations of reactants are called Zero order

reactions. The integrated rate equation for zero order reactions is derived as follows.

N

dc dx

HA

- = =kco

dt dt

dx

E

o

or =k a-x k RD

EG

by

dt

LL

ed

or dx = k dt

VA

AL O

ar

G C

or x = kt

ep

AN IOR

Pr

x

YA

or k=

t

AR N

W U

J

AG T

VI

I

DE

AD

P

Let

VA

V.

Amount of reactant decomposed in 't' sec = x mol. dm-3.

The concentration of reactant after 't' sec = (a - x ) mol. dm-3.

dx

The rate at time 't' is proportional to the concentration of reactant (a - x) at that time. Since the

dt

reaction is a first order reaction,

dx

a-x

dt

dx

k a-x

dt

dx

=k.dt [where k = specific rate]

a-x

On integration

Prepared by V. Aditya vardhan

Chemical kinetics 7 adichemadi @ gmail.com

dx

a-x k .dt

-ln (a-x) = k.t + c

when t = 0 then x = 0

-ln a = c

a

or kt = ln

a-x

1 a

or k= ln

t a-x

2.303 a

or k= log

t a-x

N

Where a = initial concentration of reactant

HA

x = concentration reacted in an interval of time 't'

(a-x) = concentration of reactant after time 't'

E

RD

EG

by

Half life (t1/2) of a reaction :The time required for initial concentration of reactants to become half is

LL

ed

VA

AL O

ar

G C

ep

AN IOR

Pr

YA

AR N

a

a-x = a-

W U

Then = a/2

2

J

AG T

VI

2.303 a 2.303

log2 = 2.303 x 0.3010 ( log2 = 03010)

I

DE

k= log t

AD

2

VA

0.693

V.

or t1/2

k

1) Integrated equation method or Trial and error method

* The initial concentration (a) and the concentrations at various intervals of time (a - x) are measured

during the progress of reaction by suitable analytical methods. These values are substituted in the rate

equations of different rate orders. The order corresponding to the rate equations, which gives constant 'k'

values is taken as the order of reaction.

Rate equations

For a Zero order reaction R

P

x = kt

x a- a-x R o -R t

or k= = =

t t t

Prepared by V. Aditya vardhan

Chemical kinetics 8 adichemadi @ gmail.com

For first order reaction R

P

2.303 a 2.303 R

k= log = log o

t a-x t Rt

P

1 x 1 R o -R t

k= = .

at a-x R o t R t

P

2.303 b( a x )

k= log

t(a-b) a (b x )

The order can also be ascertained graphically as follows

For a zero order reaction, the graph of 'x' versus 't' must be a straight line parallel to time (t) axis.

N

HA

x

E

RD t

EG

by

LL

ed

a

VA

For a first order reaction, the graph of log

AL O

versus 't' should be a straight line with positive slope

ar

a-x

G C

ep

AN IOR

Pr

YA

AR N

W U J

a

AG T

VI

log

a-x

I

DE

AD

t

VA

V.

x

For a second order reaction, the graph of a a-x vs 't' must be a straight line passing through the

x OR b(a-x)

a(a-x) log

a(b-x)

t t

is inversely proportional to a

Half life t 1

2

n-1

Prepared by V. Aditya vardhan

Chemical kinetics 9 adichemadi @ gmail.com

1

t1

2 a n -1

where a = initial concentration

n = order

The order 'n' of a reaction can be calculated by comparing two half lives - t 1 & t 1 with initial

2 2

t 1 n -1

2 a

=

t 1 a

2

dc dc n

The rate - for a reaction of nth order is given by the equation, - =kc

N

dt dt

HA

For two initial concentrations c1,c2, we have

dc1 dc 2

- =kc1n ; - =kc n2

E

dt dt RD

EG

by

dc

LL

log - 1 log k + nlogc1

ed

dt

VA

AL O

ar

G C

ep

dc

AN IOR

Pr

dt

YA

AR N

W U

dc dc

log - 1 - log - 2 n log c1 nlogc 2 n log c1 logc 2

J

or

AG T

dt dt

VI

I

DE

AD

dc dc

log - 1 - log - 2

n dt dt

VA

log c1 logc2

V.

For two different initial concentrations c1 and c2, the rates are determined at any given time from c-t graph.

These are substituted in the above equation and 'n' is calculated.

concentration of reactants

concentration of reactants

c1

c2

In this method, order with respect to each reactant is determined separately by taking other reactants

in larger quantity.

For example, for the given reactions A + B products, the order is determined as follows:

1) First the concentration of 'B' is taken in larger excess and the order (nA) with respect to 'A' is deter-

mined by any of the other three methods.

Prepared by V. Aditya vardhan

Chemical kinetics 10 adichemadi @ gmail.com

2) In the second experiment the order (nB) with respect to 'B' is determined by taking 'A' in large excess.

The order of the overall reaction is taken as nA + nB.

This theory was proposed by Arrhenius. The main postulates of this theory are

1) Chemical reactions occur due to collisions between reactant molecules.

2) But all the collisions do not lead to the formation of products.

3) Only those collisions taking place between molecules possessing certain minimum amount of energy

can form the products. This minimum amount of energy is called Threshold Energy (ET).

4) The energy possessed by the normal molecules under STP conditions is called 'Average Energy'. The

difference between threshold energy and average energy of the reacting molecules is called Activation

energy (Ea).

Ea = Threshold energy (ET) - Average energy (ER)

5) Some molecules will get threshold energy during collisions and are called activated molecules and

denoted by asterick(*).

N

6) The collisions taking place between activated molecules are called activated collisions. The reaction

occurs only during the activated collisions.

HA

Activated molecules constitute a small fraction of total molecules. Similarly activated collisions consti-

tute small fraction of total collisions. Hence all the chemical reactions do not occur in fraction of second.

E

RD

EG

A+A A* + A

by

A* + A* products

LL

ed

VA

AL O

ar

G C

ep

AN IOR

A* = Activated molecule

Pr

YA

AR N

W U

8 kT

J

2

Z AB .n A .n B

AG T

VI

I

DE

AD

= reduced mass

VA

V.

8) The relation between specific rate (k), temperature (T) and activation energy Ea can be given as follows

k = A.e -Ea /RT

or

k = p.Z.e-Ea /RT

where p = probability factor

The concept of activation energies of both forward and backward reactions (Ea and Ea') can be

shown graphically as follows.

Prepared by V. Aditya vardhan

Chemical kinetics 11 adichemadi @ gmail.com

Energy barrier

ET

Ea E1a

ET

ER

H

Ep

EP = Energy of products

ET = Threshold energy

Ea = Activation energy of forward reaction

Ea1 = Activation energy of backward reaction

N

H = Enthalpy of reaction

HA

Problems :

1) The rate constant of a first order reaction is 1.386 sec-1. What is it's half life.

E

RD

2) The initial concentration of A is 0.5 moles/litre. If the concentration becomes 0.25 mole/litre in 5 sec.

EG

by

LL

ed

VA

AL O

ar

G C

ep

AN IOR

Pr

YA

AR N

W U

1) The rate of a reaction increases with time as the concentration of reactants decreases.

J

AG T

VI

3) The units of rate constants for the following reaction are (L / mol /sec).

I

DE

AD

4) The half life of zero order reaction is proportional to the initial concentration.

VA

5) The rate of consumption of hydrogen gas is thrice of formation of Ammonia in the following reaction.

V.

6) In Ostwald isolation method, the reactant for which the order is going to be determined is taken in

excess when compared to the concentrations of other reactants.

7) A positive catalyst increases the activation energy of both forward and backward reactions.

8) In exothermic reaction the activation energy of forward reaction is always greater than that of back

ward reaction.

a

9) For a second order reaction, a straight line is obtained when log is plotted against time (t)

ax

10) Rate of reaction increases with increasing temperature as the threshold energy increases.

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