CHEMICAL KINETICS

INTRODUCTION AND RATE OF A CHEMICAL REACTION

Chemical Kinetics is a branch of chemistry dealing with rate of chemical

reactions, the factors which affect the rate of chemical reactions.

Rate of reaction
Rate of a chemical reaction is defined as change in concentration of any reactant
or product in unit time.

For the reaction

R P

Rate of the reaction is given by,

Decrease in the concentration of rectant, R

Rate of reaction =
time interval

Increase in the concentration of Product, P

Rate of reaction =
time interval

If [R] and [R] are the molar concentrations of the reactants,

[P] and [P] are the molar concentrations of the products,
t1 and t 2 are initial and final time respectively, then

∆[R] = [R] − [R]

∆[P] = [P] − [P]

∆t = t − t

Rate of a reaction is given by,

∆[R] ∆[P]
Rate of reaction = − =
∆t ∆t

Negative sign indicates the decrease in concentration of reactant.

Rate of reaction is always positive.

Units of rate of a reaction: Mol L-1 s-1

For a reaction involving only gases, Units of rate of a reaction: atm s-1.

Average Rate and Instantaneous Rate of Reaction:

Average rate
Average rate is defined as the rate of reaction between any two intervals of time.
 ∆[R] ∆[P]
Average rate of reaction, r =− =
∆t ∆t

Instantaneous Rate of Reaction:

Instantaneous rate is defined as the rate of reaction at a particular instant of
time.

d[R] d[P]
Instantaneous rate of reaction, r =− =
dt dt

r =r as ∆t → 0

Graphical method of determination of instantaneous rate of reaction.

Concentration of products
d[P]
Concentration of reactant

r = = slope
dt

∆[R] d[P]
r =− C1 dt
C1 ∆t
∆[R] ∆[P]
C2 C2
d[R]
r =− = slope ∆[P]
dt r =
∆t
d[R]
d
∆t ∆t
t t1 t t
t1 t 2
Time
2
Time

Expression for Rate of Reaction in terms of Reactants and Products:

Example 1. For a reaction

2 N2O5 4 NO2 + O2

[ ] [ ] [ ]
Rate of reaction is given by, − = + =+

Example 2. For a reaction

Hg (l) + Cl2 (g) HgCl2 (s)

[ ] [ ] [ ]
Rate of reaction is given by, − = − =

Example 3. For a reaction

 H2 (g) + I2 (g) 2HI (g)

[ ] [ ] [ ]
Rate of reaction is given by, − = − =

Example 4. For a reaction

5 Br - (aq) + BrO3- (aq) + 6 H+(aq) 3 Br2 (aq) + 3 H2O (l)

Rate of reaction is given by,

[ − ] [ − ] [ +] [
3 2] [ 2 O]
− = − = − = + = +

Factors affecting rate of a reaction:

Rate of a reaction depends on
1. Concentration of reactants,
2. Temperature,
3. Catalyst,
4. Surface area of the reactants,
5. Intensity of light.
6. Nature of reactants.

Dependence of Rate on Concentration of Reactants – Rate law or Rate

equation or Rate expression:

Consider a general reaction,

aA+bB cC+dD

Applying law of mass action,

rate α [A] [B]

rate = k [A] [B] where k is called rate constant or velocity constant.

Above equation is called theoretical rate law or rate equation or rate expression.

If [ ] = [ ] = 1

rate = k where k is called specific rate constant or specific velocity constant.

Specific rate constant: Specific rate constant of a reaction is defined as the rate
of the reaction when the molar concentration of all the reactants are unity.

Characteristic of rate constant:

1. Higher the value of rate constant faster is the reaction.
2. Rate constant depends only on temperature. It is independent of initial
concentration.

The rate equation can also be obtained by doing the experiment.

rate = k [A] [B]
where m and n may or may not be equal to a and b.

The above equation is called experimentally determined rate equation or rate law
or rate expression.

Order of a reaction: Order of a reaction is defined as sum of power of molar

concentration of reactants in the experimentally determined rate equation.

Zero order reactions:

A zero order reaction is one in which rate of reaction is independent of the
concentration of reactants.

Examples:
Diffused sunlight
1. H2 + Cl2 2HCl rate = k [H ] [Cl ] ∴ order = 0
Gold
2. 2 HI H2+ I2 rate = k [2HI] ∴ order = 0
Pt
3. 2 NH3 N2+ 3H2 rate = k [NH ] ∴ order = 0

Examples for first order reaction

1. 2 H2O2 2H2O +O2 rate = k [H O ] ∴ order = 1
2. NH4NO2 N2 + 2H2O rate = k [NH NO ] ∴ order = 1
3. N2O5 NO2+ O2 rate = k [N O ] ∴ order = 1

Examples for second order reaction

1. H2+ I2 2 HI rate = k [H ] [I ] ∴ order = 2

2. CH3COOCH3 + NaOH CH3COONa + CH3OH

rate = k [CH COOH] [NaOH] ∴ order = 2

Pseudo-first order reaction

A chemical reaction of higher order can be converted into first order by taking the
all reactants except one in large excess, is called pseudo- first order reaction.
Examples:
1. CH3COOCH3 + H2O CH3COOH + CH3OH

rate = k [CH COOH] [H O] ∴ order = 1

2. C12H22O11+ H2O C6H12O6 + C6H12O6

rate = k [C H O ] [H O] ∴ order = 1

Units of Rate Constant:

rate = k [A]

rate conc (time)

k = = = (conc) (time) = (Mol L ) (sec)
[A] [conc]

Value of n Order of the reaction Unit of K = (Mol L ) (sec)

0 Zero Mol L s
1 First s
2 Second Mol L s

Molecularity of a reaction
The total number of reactant molecules taking part in a reaction is called
molecularity of reaction.

Differences between the order and the molecularity of a reaction.

Order of a reaction Molecularity of a reaction

Sum of power of molar
concentration of reactants in the
experimentally determined rate
equation.
It can be whole number, zero or
fraction.
It can be determined by experiment
The sum of reactant molecules
taking part in the elementary
reaction.
It is always a whole number.
It can be determined by balanced
chemical reaction.

Elementary reactions
The reactions which takes place in only one step without forming any
intermediate complex are called elementary reactions.

Complex reactions
The reactions which takes place in more than one step are called elementary
reactions.
I-
2 H2O2 2H2O + O2
Alkaline medium

Step1 H2O2 + I- H2O + IO- Slow

-
Step2 H2O2 + IO -
H2O + I + O2 Fast
The slowest step of the reaction is called rate determining step.
Integrated rate equation for the velocity constants of a zero order reaction.
Consider a zero order reaction,

R P

Rate of reaction is given by,

[ ]
rate = − = [ ] where k is rate constant

on rearranging ,

[ ] = −

Integrating on both sides,

we get [ ] = − + … … … … … … … … . . (1)

Where I is constant of integration.

When time = 0, [ ] = [ ] , equation becomes, = [ ]

Substitute the value of equation I in equation ( 1 ), we have

[ ]= − + [ ]

Rearranging the above equation,

=[ ] − [ ]

[ ] − [ ]
k =
t

Graph of [R] versus time (t) for a zero order reaction.

[R]o

Intercept = [R]o

Slope = -K
[R]

Time
Integrated rate equation for the velocity constant for a first order reaction
Consider a first order reaction,

R P

Rate of reaction is given by,

[ ]
rate = − = [ ] where k is rate constant

on rearranging ,

[ ]
= −
[ ]

Integrating on both sides,

we get ln[ ] = − + … … … (1) Where I is constant of integration.

When time = 0, [ ] = [ ] , equation becomes, I = [ ]

Substitute the value of equation I in equation ( 1 ), we have

ln[ ] = − + [ ]

Rearranging the above equation,

[ ] − ln[ ] =

1 [ ]
k =
t [ ]

2.303 [ ]
k =
t [ ]

Graph of ln[R] versus time (t) for a first order reaction

ln[R]o

Intercept = ln[R]o

Slope = -K
ln[R]

Time
Integrated rate equation for the velocity constant for a first order gas phase
reaction.
Consider a first order gaseous phase reaction,
Let the initial pressure = Pi atm
Let the total pressure = Pt atm

A(g) B (g) + C (g)

At time t = 0 Pi atm 0 atm 0 atm

At time ‘t’ sec (Pi - x )atm x atm x atm

Total pressure, Pt = (Pi - x ) + x + x = (Pi + x )

x = (Pt - Pi )

Partial pressure of A is by PA = (Pi - x ) = Pi - ( Pt - Pi ) = 2 Pi - Pt

2.303
k =
t

2.303
k =
t 2 −

Half-life period.
Half-life period is defined as the time required to reduce the concentration of
reactant to half of its initial value.
That is, it is the time required for the 50% completion of the reaction. It is
denoted by t1/2 or t0.5 or t50% .

Expression for half-life period of zero order reaction OR

Show that the half-life period of a zero order reaction is directly
proportional to initial concentration of reactant
For zero order reaction rate expression is given by,
[R] − [R]
k=
t
[ ]
ℎ = [ ]=
2
[ ]
[R] −
k= 2

[R]
=
2k

[R]
Expression for half-life period of a first-order reaction. OR
To Show that the half life period of a first order reaction is independent of
the initial concentration of the reactant

For first order reaction rate expression is given by,

2.303 [R]
k= log
t [R]
[ ]
ℎ = [ ]=
2

2.303 [R]
k= log
[ ]
2

2.303
k= log 2

2.303
= x 2.303
k

0,693
=
k

Effect of Temperature on rate of reaction

When the temperature increases the rate of chemical reaction increases.

Temperature coefficient of a reaction

The ratio of rate constant of a reaction at a given temperature to its rate constant
at ten degree lower temperature is called temperature coefficient of a reaction.
Mathematically it is given by,
K( )
= 2 or 3
K

where K ( ) and K are the velocity constant at (T+10) K and T K respectively.

Factors affecting effective collisions

According to collision theory, The effective collisions depends on,
i. Energy Barrier ( Threshold energy or activation energy )
ii. Proper Orientation of molecules.

Threshold energy.
Threshold Energy: The minimum energy required by reactant molecules to make
effective collision is called threshold energy.

Activation energy.
Energy of activation: The minimum excess energy required by the reactant
molecules to attain threshold energy so that they can collide effectively and form
products is called energy of activation.
 ET Threshold energy

Energy

Ea

Reactants ∆H
Products

Reaction Co-ordinate
Energy distribution curve showing temperature dependence of rate of
reaction.
Fraction of molecules

(T + 10)K

ET A

Energy of molecules

When the temperature increases by ten degrees, the number of reactant

molecules attaining threshold energy becomes double. Thereby the number of
collisions becomes double. Hence the rate of the reaction also doubles.

Arrhenius equation.

K= Ae

Where
A = frequency factor or Arrhenius factor and it gives the number of collisions per
second per litre.
Ea = energy of activation.
R = gas constant
T = temperature in Kelvin

Graph of ln K v/s 1/T

ln K = ln A −

ln A
Intercept = ln A

E
ln k Slope = −
R

1/T

Graph of log K v/s 1/T

log K = log A − .

log
A Intercept = lg A

E
log k Slope = −
2.303 R

1/T

Arrhenius equation can also be written as,

K E T − T
log =
K 2.303 R TT

Collision frequency
It is the number of collisions per second per unit volume of the reaction mixture.

Effect of catalyst rate of a reaction

Ea Without Catalyst
Energy

Ea’ with Catalyst

Reactants
Products

Reaction progress
A positive catalyst increases the rate of reaction by taking an alternative path to
the reaction which involves lower energy of activation.
Consider a uncatalysed reaction,

A + B Products

Let C be the catalyst.

In presence of catalyst, activated complex with low energy is formed.

A+B+C [A…C…B]* Products + C

Thus, in the presence of catalyst the reaction takes place faster because it takes

alternate path which involves lower energy of activation.

 CHEMICAL KINETICS

Questions carrying ONE marks each

1. Define collision frequency. ( March 2017)

Ans. It is the number of collisions per second per unit volume of the reaction
mixture.

2. In a zero order reaction the time taken to reduce the concentration of

reactant from 50 % to 25 % is 30 minutes. What is the time required to
reduce the from 25% to 12.5 % ? ( June 2015 )
Ans. 15 minutes.

3. What happens to the half-life period for a first order reaction if the initial
concentration of the reactions is increased? ( March 2015, 2016)
Ans. Remains constant.

4. Rate constant of a reaction is K = 3.4 x 10-4 Mol-1 L s-1 . What is the order
the reaction? ( June 2016 )
Ans. Second.

5. The rate equation for the reaction A + B P, r = k [A]½ [B]2 . What is

the order of the reaction? ( March 2016 )
Ans. 2.5

6. Give an example of a zero-order reaction. ( July 2014 )

Ans.
Diffused sunlight
1. H2 + Cl2 2HCl rate = k [H ] [Cl ] ∴ order = 0
Gold
2. 2 HI H2+ I2 rate = k [2HI] ∴ order = 0
Pt
3. 2 NH3 N2+ 3H2 rate = k [NH ] ∴ order = 0

7. For the reaction 2 HI H2 +12, Write its molecularity. ( March 2014 )

Ans. Molecularity is 2

8. By how many times does the t1/2 of a zero order reaction increase if the
initial concentration of the reaction is doubled?
Ans. increases by 2 times

9. The unit of rate constant of a reaction is mol-1Ls-1. What is the order of

the reaction?
Ans. Second order.

10. Unit of rate constant of a reaction is same as the unit of rate of reaction.
What is the order of the reaction?
Ans. Zero order reaction.
11. What is collision frequency?
Ans. It is the number of collisions per second per unit volume of the reaction
mixture.

12. Give an example for Unimolecular reaction.

Ans.
1. H2O2 H2O + ½ O2
2. NH4NO2 N2 + 2H2O
13. Give the SI unit of rate constant of a second order reaction.
Ans. mol-1 L s-1

14. What is the effect of temperature on the rate of a reaction?

Ans. Rate of reaction increases with the increase in temperature.

15. What happens to the energy of activation of a reaction when positive

catalyst is added?
Ans. Decreases.

16. Give an example for a second order reaction.

Ans.

1. H2+ I2 2 HI rate = k [H ] [I ] ∴ order = 2

2. CH3COOCH3 + NaOH CH3COONa + CH3OH

rate = k [ H ] [NaOH] ∴ order = 2

17. Express the rate of reaction in terms of different reactants and products.
2 N 2 O5 4 NO2 + O2
[ ] [ ] [ ]
Ans. − = + =+

Questions carrying TWO marks each

18. From the following graph, identify order reaction and mention the unit
of its rate constant. ( March 2017 )
 ln [ R ]o

k = - slope
ln [ R ]

Time

Ans. First Order reaction. Units: S-1

19. Write i) Arrhenius equation, ii) The formula to calculate half-life period of
zero order reaction. ( March 2017 )
Ans. i. k = A e- Ea/RT

[ ]
ii. =

20. The rate constant of a reaction is 200 s-1. What is the half life period ? (
March 2016 )
, ,
Ans. = = = 0.003465 seconds

21. Draw a graph of potential energy versus reaction coordinate to show the
effect of catalyst on activation energy. ( March 2016 )
Ans.

Ea Without Catalyst
Energy

Ea’ with Catalyst

Reactants
Products

Reaction progress

22. Draw a graph of [R] versus time (t) for a zero order reaction. Give the
relationship between rate constant and slope of the curve. (March 2016)
Ans.
 [R]o

Intercept = [R]o

Slope = -K
[R]

Time

] − [ ] [
k =
t
23. 75% of the first order reaction is completed in 30 minutes. Calculate the
rate constant of the reaction. (June 2016 )
Ans.
[ ] = 100 [ ] = 100 − 75 = 25 t = 30 minutes k = ?

2.303 [ ]
k =
t [ ]
2.303 100
k = log
30 25

2.303
= log 4
30

2.303
= x 0.6020
30

= 0.046 min

24. Write the energy distribution curve showing temperature dependence of

rate of reaction. (June 2016 )
Ans.
Fraction of molecules

(T + 10)K

Energy of molecules
25. Calculate the half-life period of a first order reaction, if the rate constant
of the reaction as 6.93 x 10-3 s-1 ( July 2015 )
, ,
Ans. = = . = 100 seconds

26. A reaction is first order with respect to the reactant A second order with
respect to the reactant B in a reaction
A+B product.
i. Write the differential rate equation.
ii. How is the rate of the reaction effected in increasing the
concentration of B by two times? (March 2015)
Ans. i. = k [A][B]
ii. rate Increases by 4 times.

27. Write any two differences between the order and the molecularity of a
reaction. ( July 2014 )
Ans.
Order of a reaction Molecularity of a reaction
Sum of power of molar The sum of reactant molecules
concentration of reactants in the taking part in the elementary
experimentally determined rate reaction.
equation.
It can be whole number, zero or It is always a whole number.
fraction.
It can be determined by experiment It can be determined by balanced
chemical reaction.

28. Derive an expression for half-life period of a first-order reaction. ( July

2014 ) OR
Show that the half life period of a first order reaction is independent of
the initial concentration of the reactant. ( March 2014 )
Ans. For first order reaction rate expression is given by,
2.303 [R]
k= log
t [R]
[ ]
ℎ = [ ]=
2

2.303 [R]
k= log
[ ]
2

2.303
k= log 2

2.303
= x 2.303
k

0,693
=
k
29. Mention the factors affecting the rate of a reaction.
Ans.
Concentration of reactants
Temperature
Catalyst

30. Define collision frequency. Give an example for a Pseudo first-order

reaction. ( March 2014 )
Ans. Collision Frequency: It is the number of collisions per second per unit
volume of the reaction mixture.
Example for pseudo first-order reaction.
CH3COOCH3 + H2O CH3COOH + CH3OH

rate = k [ H ] [H ] ∴ order = 1

31. Given 2NO(g) + O2(g) 2NO2(g); rate=k[NO]2[O2]1. By how many times

does the rate of the reaction change when the volume of the reaction
vessel is reduced to 1/3rd of its original volume? Will there be any
change in the order of the reaction?
Ans. 27 times. No change in the order.

32. What are the two criteria for effective collisions according to collision
theory?
Ans.
i. Energy Barrier ( Threshold energy or activation energy )
ii. Proper Orientation of molecules.

33. Write Arrhenius equation. What is Ea in the equation called?

Ans. i. k = A e- Ea/RT
Ea is called energy of activation.

34. Calculate the activation energy if the rate of the reaction doubles when
the temperature increases from 27° C to 37° C ( R = 8.314 J/K/mol )
Ans.
K E T − T
log =
K 2.303 R TT

E 310 − 300
log 2 =
2.303 x 8.314 300x310

E = 53598.5 53.6

35. A first order reaction is found to have a rate constant 5.5x10-14 s-1. Find
the half life period of the reaction.
, ,
Ans. . = = = 1.26 x 10 seconds
.

36. What is a pseudo first order reaction? Give an example.

 Ans. A chemical reaction of higher order can be converted into first order by
taking the all reactants except one in large excess, is called pseudo- first order
reaction.
Example:
1. CH3COOCH3 + H2O CH3COOH + CH3OH

rate = k [ H ] [H ] ∴ order = 1

2. C12H22O11+ H2O C6H12O6 + C6H12O6

rate = k [C H O ] [H ] ∴ order = 1
37. From the graph given below, what does the slope and intercept
indicates?

ln k

1/t

Ans. Slope = − Intercept = ln A

38. Show that the rate of first order reaction is doubled when the
concentration of the reactant is doubled.
Ans. For a reaction
A Products Rate r1 = k [A]

When the concentration is doubled, Rate r2 = k [2A]

r k [2A] r
= ∶ = 2 ∶ ∴ r =2r
r k [A] r

39. A reaction is 50% complete in 2hours and 75% complete in 4hours. What
is the order of the reaction? Give reason.
Ans. For first order reaction, t75 % = 2 x t50%
Hence First order reaction

40. Draw a graph of concentration of R versus time for a zero order reaction
: R products. What is the intercept of the line?
Ans.
 [ R ]o

k = - slope

[R]

Time

Intercept is [ R ]0

41. Define the terms ,

a. Temperature co-efficient of a reaction.
b. Half life period of a reaction.
Ans.
Temperature co-efficient of a reaction.
The ratio of rate constant of a reaction at a given temperature to its rate
constant at ten degree lower temperature is called temperature coefficient
of a reaction.
K( )
= 2 or 3
K
Half life period of a reaction: Half-life period is defined as the time required
to reduce the concentration of reactant to half of its initial value.

42. What is a zero order reaction? Give an example.

Ans. If the rate of reaction does not depend on the concentration of any of
reactants, then it is called zero order reaction.
Diffused sunlight
1. H2 (g) + Cl2 (g) 2HCl rate = k [H ] [Cl ] ∴ order = 0

Gold
2. 2 HI H2+ I2 rate = k [2HI] ∴ order = 0

Pt
3. 2 NH3 N2+ 3H2 rate = k [NH ] ∴ order = 0
43. Define the terms,
a. Average rate.
b. Instantaneous rate.
Ans. Average rate is the rate of reaction between any two intervals of time.
Instantaneous rate is the rate of reaction at any instant of time.

Questions carrying THREE marks each

44. The rate of a particular reaction doubles when the temperature of the
reaction is raised from 300K to 310K. Calculate the energy of activation
of the reaction. Given R=8.314 J/K/mol. ( March 2014 )
OR
The rate of a reaction increases by 2 times when the temperature of the
reaction is raised from 300K to 310K. Calculate the energy of activation
of the reaction. Given R=8.314 J/K/mol. ( July 2014 )
Ans.
K E T − T
log =
K 2.303 R TT

E 310 − 300
log 2 =
2.303 x 8.314 300x310

E = 53598.5 53.6

45. Derive an integrated rate equation for the velocity constant for a first
order reaction.( March 2015, March 2016 )
Ans. Consider a first order reaction,

R P

Rate of reaction is given by,

[ ]
rate = − = [ ] where k is rate constant

on rearranging ,

[ ]
= −
[ ]

Integrating on both sides,

we get ln[ ]= − + … … … … … … … … . . (1)

Where I is constant of integration.

When time = 0, [ ] = [ ] , equation becomes, I = [ ]

Substitute the value of equation I in equation ( 1 ), we have

ln[ ]= − + [ ]

Rearranging the above equation,

[ ] − ln[ ]=

1 [ ]
k =
t [ ]
 2.303 [ ]
k =
t [ ]

46. Derive the integrated rate equation for the velocity constants of a zero
order reaction. ( March 2016, June 2016, March 2017 )
Ans. Consider a zero order reaction,

R P

Rate of reaction is given by,

[ ]
rate = − = [ ] where k is rate constant

on rearranging ,

[ ] = −

Integrating on both sides,

we get [ ] = − + … … … … … … … … . . (1)

Where I is constant of integration.

When time = 0, [ ] = [ ] , equation becomes, = [ ]

Substitute the value of equation I in equation ( 1 ), we have

[ ]= − + [ ]

Rearranging the above equation,

=[ ] − [ ]

[] − [ ]
k =
t
47. The rate of a reaction increases by 4 times when the temperature of the
reaction is raised from 340K to 360K. Calculate the energy of activation
of the reaction. Given R=8.314 J/K/mol.
Ans.
K E T − T
log =
K 2.303 R TT

E 360 − 340
log 4 =
2.303 x 8.314 360x340

E = 70542.6 J or 70.55 KJ
48. Rate constant of a first order reaction is 0.0693min-1 . Calculate the
percentage of the reactant remaining at the end of 60 minutes.
Ans.
[ ] = 100 [ ] = ? t = 60 minutes k = 0.0693

2.303 [ ]
k =
t [ ]

2.303 100
0.0693 =
60 [ ]

[ ] = 1.56 %

49. Show that the half-life period of a zero order reaction is directly
proportional to initial concentration.
Ans. For zero order reaction rate expression is given by,
[R] − [R]
k=
t
[ ]
ℎ = [ ]=
2
[ ]
[R] −
k= 2

[R]
=
2k

[R]

50. A reaction is first order in reactant ‘A’ and second order in reactant ‘B’ .
i) Write differential rate equation.
ii) How is the rate affected when concentration of ‘B’ alone is increased
to three times?
iii) How is rate affected when concentration of both ‘A’ and ‘B’ are
doubled?
Ans.
i. Rate r = k [A]1 [B]2
ii. Rate increases by three times.
iii. Rate increases by eight times.

51. A certain first order reaction is half completed in 46 min. Calculate the
rate constant and also the time taken for 75% completion of the
reaction.
Ans.
0,693
=
k
 0,693 0,693
= = = 0.0150
46

[ ] = 100 [ ] = 100 − 75 = 25 t = 30 minutes k = ?

2.303 [ ]
k =
t [ ]
2.303 100
0.0150 = log
% 25

2.303
% = log 4
0.0150

% = 92.42 min

52. For a certain chemical reaction, variation in the concentration ln[R] vs

time(min) , the plot is shown below.

ln[ R ]

Time

i)What is the order of the reaction?

ii) What does the slope of this line indicate?
iii) If the initial concentration for this reaction becomes half, how will
t1/2 vary?
Ans.
i. First order reaction.
ii. Slope is equal to –k
iii. No Change in Half-life period because it is independent of initial
concentration.
53. Show that in case of a first order reaction, the time taken for completion
of 99.9% reaction is ten times the time required for half change of the
reaction.
Ans. To show that , t99.9 % = 10 x t50%
 2.303 [ ]
log
. % k [ ]
=
% 0.693
k

2.303 100
log 0.1
. %
= k
% 0.693
k

. % 2.303 3
= = 9.96 = 10
% 0.693

. % = 10 %

54. Derive an integrated rate equation for the velocity constant for a first
order gas phase reaction.
Ans.
Consider a first order gaseous phase reaction,
Let the initial pressure = Pi atm
Let the total pressure = Pt atm

A(g) B (g) + C (g)

At time t = 0 Pi atm 0 atm 0 atm

At time ‘t’ sec (Pi - x )atm x atm x atm

Total pressure, Pt = (Pi - x ) + x + x = (Pi + x )

x = (Pt - Pi )

Partial pressure of A is by PA = (Pi - x ) = Pi - ( Pt - Pi ) = 2 Pi - Pt

2.303
k =
t

2.303
k =
t 2 −

55. The rate constant of a zero order reaction in ‘A’ is 0.0030 mol L-1 S-1.
How long it will take for the initial concentration ‘A’ to fall from 0.10M
to 0.075M.
Ans.
[ ] − [ ]
k =
t

0.10 − 0.075
0.0030 =
t
0.10 − 0.075
t = = 8.33 s
0.0030