BOUNDLESS KNOWLEDGE TUTORIAL BY AJAY DHAKREY (9528818855)

CHEMICAL KINETICS

CONCEPT
Chemical Kinetics : The branch of physical chemistry which deals with the study
of rate of reaction and factors affecting rate.
Rate of chemical reaction : The change in concentration of any reactant or
product per unit time is called rate of reaction.
Types of Rate of Reaction :
1. Average rate of reaction : The rate of reaction measured over the long time
interval is called average rate of reaction.
x −[R] [P]
Avg rate  = =
t t t
2. Instantaneous rate of reaction : The rate of reaction measured at a particular
time is called instantaneous rate of reaction.
(Rate)i = (Instantaeous rate) dx/dt = –d[R]/dt=+d[P]/dt
Factors affecting Rate of Reaction
1. Concentration of reactant
2. Surface area
3. Temperature
4. Nature of reactant
5. Presence of catalyst
6. Radiation in photochemical reaction
Rate constant (k) : It is equal to the rate of reaction when molar concentration of
reactant is at unity.
Rate law : The rate of reaction is directly proportional to the product of
concentration of reactant and each concentration is raised to the equal to no of moles
actually participating in the reaction.

For a reaction, aA + bB → cC + dD
 Rate law = k[A]p[B]q
where powers p and q are determined experimentally.
Molecularity : The total number of reactants taking part in elementary chemical
reaction is called molecularity.
Order of reaction : The sum of powers to which the concentration terms are
raised in a rate law expression is called order of reaction.
For above case, Order = P + Q
Orders of reaction is determined experimentally.
Half-life period : The time during which the concentration of the reactant is
reduced to half of its initial concentration is called half-life period.
Activation energy : The minimum extra amount of energy absorbed by reactant
molecules so that their energy becomes equal to the threshold energy is called activation
energy.
Activation energy = Threshold energy – Kinetic energy
Temperature coefficient : The ratio of rate constant at two temperatures having
difference of 10ºC is called temperature coefficient.
Temperature coefficient = Rate constant at T + 10ºC/Rate constant at TºC
Arhenius Equation :
K = Ae−Ea/RT
where, K = Rate constant
A = Arrhenius energy (Frequency factor or pre-exponential factor)
Ea = Activation energy
R = Rate constant
T = Temperature
Ea
= Fraction of molecules having energy equal to or more than activation
RT
energy
Ea
log K = log A –
2.303RT
K2
log = Ea  1 1 
K 2.303R  T − T 
1  1 2 
 K2 Ea
log = T2 − T1 
 
K1 2.303  8.314 T2 − T1 
Where R = 8.314 JM–1 mol–1
K2 Ea T2 − T1 
log = = 0.0522E T2 − T1 
K1 19.147 T2 − T1  a 
  T2 − T1 
1. Integrated rate law equation for zero order reaction is given as below :
[R]0 − [R]t
(a) k = t
Where k is rate constant and [R]0 is initial molar concentration.
[R]o , t
(b) t1/2 = 1/2
is half-life period of zero order reaction.
2k
2. Integrated rate law equation for first order reaction :

(a) k = 2.303 log [R]0

t [R]t
where k is rate constant, [R]0 is initial molar concentration and [R], is final
concentration at time 't'.
(b) Half-life period (t1/2) for first order reaction :
0.693
t =
½
k
Pseudo chemical reaction : The chemical reaction which looks like higher order
reaction but in real it follows lower order reaction.
CH3COOC2H5+ H O
2
→ CH COOH
3
+CH OH
2 5

Rate = k[CH3COOC2H5]1
Order = 1

MULTIPLE CHOICE QUESTIONS (1 Mark)

1. The half life period of a first order reaction is 100° seconds. Its rate constant is:
(a) 0.693 sec–1 (b) 6.93 × 10–3 sec–1
(c) 6.93 × 10–2 sec–1 (d) None of these
2. In Arrehenius equation if a graph is plotted between 10 gK and 1/T, the slope
of the curve will be: −E
−Ea a
(a) (b) 2.303R
R Ea
Ea
(c) (d)
R 2.303R
3. The rate low for a reaction 2C + D ⎯→ A + E is
−d[D]
= K[C]2[D]
dt
if C is present in large excess, the order of the reaction will be:
(a) zero (b) first
(c) second (d) third
4. What is the activation energy for the reverse of this reaction?
N2O4(g) ⎯→ 2NO 2(g)
Data for the given reaction is H = 54 KJ/mol and a= 57.2 KJ.
(a) – 54 KJ (b) 3.2 KJ
(c) 60.2 KJ (d) 111.2 KJ
5. The rate constant of a reaction becomes equal to the pre exponential factor
when:
(a) the absolute temperature is zero
(b) the activation energy is infinity
(c) the absolute temperature is infinity
(d) the activation energy is zero
6. The following graph show that the reaction is:
(a) zero order [A]
(b) first order
(c) second order
(d) fractional order Time

7. A second order reaction between A and B is elementary reaction:

A + B ⎯→ Product
rate law expression of this reaction will be:
(a) Rate = K[A][B] (b) Rate = K[A]0[B]2
(c) Rate = K[A]2[B]0 (d) Rate = K[A]3/2[B]1/2

8. The order and molecularity of the chain reaction, H2(g) + Cl2(g) ⎯⎯→ HCl
h

(a) 2, 0 (b) 0, 2
(c) 1, 1 (d) 3, 0
9. Which of the following is pseudo first order reaction?
(a) 2H2O2⎯→ 2H 2O + O 2
(b) 2O3⎯→ 3O 2
(c) CH3COOC2H5+ NaOH ⎯→ CH 3COONa + C 2H 5OH
H+
(d) CH3COOC2H5 + H2O ⎯⎯→ CH3 COOH + C2H5OH
10. A large increase in the rate of reaction for rise in temperature is due to:
(a) Increase in the number of collisions
(b) Increase in the number of activated molecules
(c) Lowering of activation energy
(d) Shortening of the mean free path.
11. For a creactionj, the following data were obtained:
Concentration (mol/L) 0.1 0.05 0.025 0.0125
Half life in (sec) 30 29.9 30.1 30
the order of reaction is:
(a) 2 (b) 1
(c) 0 (d) fractional
12. For the formation of SO3 in the following reaction, it is given that
2SO2 + O2 ⎯→ 2SO3 Ea = Activation energy
SO2 + 1/2 O2 ⎯→ SO3 Ea= Activation energy
1
(a) Ea > E a (b) Ea < Ea1
(c) E a1 = E a1/2 (d) Ea = Ea1
13. A first order reaction is 20% complete in one hour. At the end of 3 hrs the
extent of the reaction is:
(a) 60% (b) 52.2%
(c) 48.8% (d) 44.4%
14. Radioactive decay is an example of:
(a) first order (b) second order
(c) zero order (d) 0.5 order
15. At 227°C, the presence of catalyst causes the activation energy of a reaction
to decrease by 4.606 KCal, the rate of the reaction will be increased by:
(a) 2 times (b) 10 times
(c) 100 times (d) 1000 times
16. The decomposition of N O occurs as, 2N O ⎯→ 4NO + O and follows first
2 5 2 5 2 2
order kinetics, hence:
(a) the reaction is bimolecular (b) the reaction is unimolecular
mol −1
(c) tyz  a° (d) unit of K = sec
L
17. Rate of which reactions increases with temperature:
(a) of any reactionj (b) of exothermic reaction
(c) of endothermic reaction (d) of none
 18. For the reaction, N2O5⎯→ 2NO 2+ O 2; Given
−d
[N O ] = K [N O ]
2 5
dt 1 2 5
d
[NO ] = K [N O ]
2 2 2 5
dt
d
[O ] = K [N O ], the relation in between of K K K is
3 2 5 1 2 3
dt 2
(a) 2K1 = K2 = 4 K3 (b) K1 = K2 = K3
(c) 2K1 = 4K2 = K3 (d) 2K1 = 2K2 = 3K3
19. Which of the following statement is/are correct about order of reaction:
(a) order of reaction is determined experimentally
(b) order of reaction can not have fractional value
(c) it does not necessarily depend on stoichiometric coefficients.
(d) it is the sum of power of concentration terms in rate low expression
20. Which one is correct for first order reaction.
t75%
(a) = 1.5 t
(b) 75% = 3
t50% t50%

t99.9% t87.5%
(c) = 10 (d) =3
t50% 50%

21. Match the column and found out correct option.

L
(A) zero order reaction P. unit of K is .sec−1
mol
mol
(B) first order reaction Q. unit of K is .sec−1
L
(C) second order reaction R. unit of K is sec–1
(a) A–R, B–Q, C–P (b) A–P, B–Q, C–R
(c) A–Q, B–R, C–P (d) A–R, B–P, C–Q

Assertion and Reasoning:

22. (a) Statement 1: is true, Statement 2 is true, and Statement 2 is a correct explanation
of statement 1
(b) Both statement are true but statement 2 is not a correct explanation for
statement 1
(c) Statement 1 is true and statement 2 is false
(d) Statement 1 is false and Statement 2 is true
(e) Statement 1 the rate of reaction is accelerated by the presence of catalyst.
(f) Statement 2 The presence of catalyst makes the value of G° more negative.
 23. Statement 1: Lower the activation energy, faster is the reaction.
Statement 2 : Catalyst does not affect activation energy of the reaction.
24. Integer type Question:
t99.9
For first order reaction: = x , Here x is
t50
(a) 3 (b) 5
(c) 7 (d) 10

Fill in the blanks type Questions

25. The reactions taking place in one step is called ................ reactions.
26. The order of reaction is ................ determined.
Answers
1. (b) 2. (b) 3. (b) 4. (b) 5. (c) 6. (a) 7. (a) 8. (b) 9. (d) 10. (b)
11. (b) 12. (d) 13. (c) 14. (a) 15. (c) 16. (c) 17. (a) 18. (a)
19. (a, c, d) 20. (c, d) 21. (c) 22. (c) 23. (c) 24. (d)
25. elementary 26. experimentally

VERY SHORT ANSWER TYPE QUESTIONS (1 Mark)

Q. 1. The rate law for a reaction is
Rate = K [A] [B]3/2
Can the reaction be an elementary process ? Explain.
Ans. No, an elementary process would have a rate law with orders equal to its
molecularities and therefore must be in integral form.
Q. 2. For the reaction 3H2 + N2 → 2NH , how are the rate of reaction expressions
d H 2  d NH3 
3

− and inter-related ?
dt dt

1 d H2  1 d  NH 3 
Ans. − =
3 dt 2 dt
Q. 3. Identify the order of a reaction from the following rate constant :
k = 2.3  10−5 L mol-1 s-1
Ans. Second order
Q. 4. After five half-life periods for a first order reaction, what fraction of reactant
remains ?
1
Ans.
32
Q. 5. What is the effect of adding catalyst on the free energy of a reaction ?
Ans. No change in G.
Q.6. What value of k is predicted for the rate constant by Arrhenius equation is T
→  ? Is this value physically reasonable ?
Ans. From the equation k = Ae − E a /RT if T →  k → A so that Ea = 0. This is not
feasible.
Q.7. Determine the order of reaction :
Step 1. 2NO + H2 → N2 + H2O2 Slow
Step 2. H2O2 + H2 → 2H2O Fast
2
Ans. Rate = k [NO] [H2]
Order = 2 + 1
=3
Q.8. What is the order of reaction whose rate constant has the same units as the
rate of reaction ?
Ans. Zero order
Q.9. Why are reactions of higher order less in number ?
Ans. A reaction takes place due to collide of molecules. The chances for a large number
of molecules or ions to collide simultaneously are less. Hence, the reactions of
higher order are less.
Q.10. What will be the effect of temperature on rate constant ?
Ans. Rate constant of a reaction is nearly doubled with rise in temperature by 10º.
Q.11. State a condition under which a bimolecular reaction is kinetically first order
reaction.
Ans. A bimolecular reaction becomes first order reaction when one of the reactants is
in excess.
Q.12. Why can’t molecularity of any reaction be equal to zero ?
Ans. Molecularity of a reaction means the number of molecules of the reactants taking
place in an elementary reaction. Since at least one molecule must be present, so
that molecularity will be atleast one.
Q.13. The rate constant of a reaction is 3  102 min-1. What is its order of reaction ?
(On the basis of units of rate constant)
Ans. First order reaction.
Q.14. Three-fourth of a reaction is completed in 32 minutes. What is the half life
period of this reaction ?
Ans. 16 minutes.
Q.15. What is meant by an elementary reaction ?
Ans. A reaction which takes place in one step is called an elementary reaction. For
example : H2 + I2 → 2HI.
Q.16. Give one example of a reaction where order and molecularity are equal ?
Ans. 2HI → H2 + I2 (Order = Molecularity = 2)
Q.17. For a reaction R → P, the rate becomes 2 times when the concentration of the
reactant A is increased 4 times. What is the order of reaction ?
Ans. r = k(a)n  2r = k(4a)n  2 = 4n  n = 0.5
Q.18. The rate constant of a zero order reaction in A is 0.003 mol L-1 sec-1. How long
will it take for the initial concentration of A to fall from 0.10M to 0.075 M ?
A0 −  A  0.10 − 0.075
Ans. t = = = 8.3 sec
k 0.003
Q.19. In a reaction 2A → Products, the concentration of A decreases from 0.5 mol
L-1 in 10 minutes. Calculate the rate during this interval.
−A = − 1  0.4 − 0.5  −3 −1
Ans. Average rate = 2t 2 10  = 5 10 M min
 
Q.20. In some cases large number of colliding reactant molecules have energy more
than threshold energy even then the reaction is slow. Why ?
Ans. Because resultant molecules do not collide in proper orientation.
Q.21. Give an example of a reaction having fractional order.
Ans. Decomposition of acetaldehyde (order = 1.5).
CH CHO ⎯7⎯
23K
⎯→ CH + CO
3 4

Q.22. Decomposition reaction of ammonia on Pt surface has rate constant = 2.5 

10-1 mol L-1 sec-1. What is order of reaction ?
Ans. Unit of k explain that it is zero order reaction.
Q.23. What is order of radioactive decay ?
Ans. First order
Q.24. For a reaction A + B → Product, the rate law is given by r = k[A]½ [B]2. What
is the order of the reaction ?
Ans. Order of reaction = ½ + 2 = 2.5
SHORT ANSWER-I TYPE QUESTIONS (2 Marks)
Q. 1. The rate of a particular reaction quadruples when the temperature changes
from 293 K to 313 K. Calculate activation energy.
Ans. K2/K1 = 4
T1 = 293 K, T2 = 313 K
K2 Ea
log =− 1 1
K1 2.303R  T1 − T2 
 

Thus, on calculating and substituting values, we get :

Ea = 52.86 KJ mol-1
Q. 2. If the decomposition of nitrogen oxide as
2N2 O5 → 4NO 2 + O 2
follows a first order kinetics.
(a) Calculate the rate constant for a 0.05M solution if the instantaneous rate
is 1.5  10−6 mol/l/s ?
Ans. Rate = K[N2O5]
Rate
K =
N2O5 
1.5 10−6
=
0.05
K = 3.0  10−5

(b) What concentration of N2O5 would give a rate of 2.45  10−5 mol L-1 s-1 ?

Ans. Rate = 2.45  10−5 mol L-1 s-1

Rate 2.45 10−5

[N2O5] = =
K 3.0 10−5

= 0.82 M
Q. 3. Write the difference between order and molecularity of reaction.
Ans.
Order Molecularity
1. It is the sum of the powers of concentration It is the number of reacting species
terms in the rate law expression. undergoing simultaneously collision in
a reaction.
2. It is determined experimentally. 2. It is a theoretical concept.

3. Orderofreactionneednottobeawholenum 3. It is whole number only.

ber.

4. Order of reaction can be zero. 4. It can’t be zero or fractional.

Q. 4. Consider the decomposition reaction :

− −
2H 2 O 2 ⎯O⎯ ⎯→ 2H 2 O + O 2
H /I

This reaction takes place in two steps as given below :

Step 1. H2O2+ I− → H 2O + IO− (slow)
Step 2. H2O2+ IO− → H 2O + I− + O 2(fast)
(a) Determine rate law expression.
(b) Determine the order of reaction.
Ans. (a) Rate = K[H 2O 2][I-] because second step is rate determining step.
(b) Order = 1 + 1 = 2
Q. 5. The decomposition of hydrocarbon follows the equation K = (4.5  1011 s-1)
e-28000k/T. Calculate Ea .
Ans. K = (4.5  1011 s-1) e-28000k/T
Comparing the equation with Arrhenius equation,
K = Ae−Ea/RT
E
− a = −28000 K
R

Ea = 28000  8.314
= 232192 J mol-1
Q. 6. A reaction is of second order with respect to a reactant. How is the rate of
reaction affected if the conc. of the reactant is reduced to half. What is the
unit of rate constant for such a reaction ?
Ans. Rate = k[A]2
mol L−1
Unit of k = = k(mol-1)2
S
k = mol-1 L S-1
Q.7. For a first order reaction time taken for half of the reaction to complete is t1
and ¾ of the reaction to complete is t2. How are t1 and t2 related ?
Ans. t2 = 2t1 because for 3/4th of the reaction to complete time required is equal to two
half lives.

Q. 8.

(a) What is the order of the reaction ?

(b) What is the slope of the curve ?
Ans. (a) Zero order reaction.
(b) [R] = [R0] – kt  Slope = – k
Q.9. Derive an expression to calculate time required for completion of zero order
reaction.
Ans. For a zero order reaction,
R = [R]0 – kt
For completion of the reaction [R] =0
 kt = [R]0
 R 0
Or t=
k
Q.10. For the reaction N2(g) + 3H 2(g) → 2NH 3(g)
How is the rate of formation of ammonia related to the rate of disappearance
of H2 ?
1   H 2  1   NH 3 
Ans. Rate of reaction = − = Or   NH 3  2  H2 
=−
3 t 2 t t 3 t
Q.11. The rate of a gaseous reaction becomes half when volume of the vessel is
doubled. What is the order of reaction ?
Ans. Suppose, order of reaction is n and the reaction is A (g) → Products
Rate = k[A]n ...(i)
When volume is doubled, molar conc. becomes half and rate of reaction gets
halved.
n
Rate A
= k  ...(ii)
2 2
Dividing equation (i) by equation (ii),
(2)1 = (2)n
Or n=1
Q.12. A reaction which is first order with respect to A has rate constant 6 min-1. If
we start with [A] = 0.5 mol L-1, when would [A] reach the value of 0.05 ML-1 ?
2.303 A0
k = log
Ans.
t A
k = 6 min-1, [A]0 = 0.5, [A] = 0.05, t = ?
2.303 0.5 = 2.303 log10 = 0.3838 min
t= log
6 0.05 6
Q.13. The conversion of the molecules X to Y follows second order kinetics. If the
concentration of X is increased to three times, how will it affect the rate of
formation of Y ?
Ans. 9 times
Q.14. A first order reaction has a rate constant 1.15  10-3 s-1. How long will 5 gram
of this reactant take to reduce to 3 grams ?
Ans. t = 444 seconds
Q.17. 4NH3 + 5O2 → 4NO + 6H2O. If rate of formation of NO is 6  10−4 atm min-1,
calculate the rate of formation of H2O.
Ans. 9.0  10−4 atm min-1
Q.18. Consider a certain reaction A → Product with K = 2.0  10-2 s-1. Calculate the
concentration of A remaining after 100 s, if the initial concentration of A is
1.0 mol L-1.
Ans. [A] = 0.135 M
Q.19. Explain with an example, what is a pseudo first order raction ? The graphs (A
and B) given below are plots of rate of reaction Vs concentration of the reactant.
Predict the order from the graphs.

Q.20. Differentiate between :

(a) Average rate and instantaneous rate of a chemical reaction.
(b) Molecularity and order of reaction.
Q.21. Show that in case of first order reaction, the time required for 99.9% of the reaction
to take place is about ten times than that required for half the reaction.
Q.22. For the reaction NO2 + CO → CO2 + NO, the experimentally determined rate
expression below 400 K is rate = k[NO 2]2. What mechanism can be proposed for
this reaction ?
Q.23. The half life period of a first order reaction is 60 min. What % will be left
after 240 mins. ?
Ans. 6.25%
Q.24. Time for half change for a first order reaction is 25 min. What time will be
required for 99% reaction ?
Ans. 166.16 mins.

SHORT ANSWER TYPE-II QUESTIONS

Q. 1. The rate constant for first order reaction is 60/s. How much time will it take
to reduce the concentration of the reaction to 1/10 of its initial value ?
2.303 R0 
t= log
R
Ans.
K

t=
2.303 R 0 
log
1 R
10
2.303
t= log10
60
 2.303
t=
60
= 3.38  10-2 s-1

Q. 2. The rate of most of reaction double when their temperature is raised from
298 K to 308 K. Calculate the activation energy of such a reaction.
K2
log = Ea  1 1 
2.303R  T − T 
Ans.
K
1  1 2

2.303 8.314  298  308  0.3010

Ea =
1000
Ea = 52.89 KJ/mol
Q. 3. A first order reaction takes 69.3 min for 50% completion. Set up on equa-
tion for determining the time needed for 80% completion.
0.693 0.693
Ans. K= = min
t1/ 2 69.3
= 10-2 min-1
2.303 R 0 
T= log
K R
2.303
= log 5
10−2
= 160.9 min
Q. 4. The activation energy of a reaction is 94.14 KJ/mol and the value of rate
constant at 40º C is 1.8  10-1 sec-1. Calculate the frequency factor A.
Ans. Given, Ea= 94.14  103 J mol-1, T = 40 + 273 = 313 K, K = 1.8  10-1 sec-1
Ea
By using, K = Ae − E a / RT  ln K = ln A −
RT
Ea
Or log K = log A −
2.303RT
94.19 103
(1.8 10 ) + 2.303  8.314  313 = log A
−1
Or log

Or A = antilog (10.9635) = 9.194  1010 sec-1

Q. 5. The rate constant of a reaction at 500 K and 700 K are 0.02 s-1 and 0.07 s-1
respectively. Calculate the value of Ea and A.
Ans. 18.23 KJ mol-1, 1.603
Q. 6. The rate constant of a reaction at 700 K and 760 K are 0.011 M-1 s-1 and
0.105 M-1 s-1 respectively. Calculate the value of Arrhenius parameters.
Ans. 2.824  1010
Q. 7. The initial concentration of N O in the first order reaction N O → 2NO
2 5 2 5 2
+ ½O was 1.24  10-2 mol L-1 at 318 K. The concentration of N O after 60
2 2 5
minutes was 0.20  10-2 mol L-1. Calculate the rate constant of the reaction
at 318 K.
2.303 log A0 = 2.303 log N2O5 0 = 2.303 log 1.24 10
−2
Ans.
K=
t A t N2O5 t 60 0.2 10−2
2.303 2.303
= log 6.2 =  0.7924 min−1
60 60
= 0.0304 min-1
Q. 8. The following data were obtained during the first order thermal decompo-
sition of N2O5 at constant volume :
2N2 O5 → 2N 2O 4 + O 2
S. No. Time per second Total pressure (atm)
1 0 0.5
2 100 0.512
Calculate rate constant.
Ans. 4.98  10−4 sec-1
Q. 9. A first order reaction is 20% complete in 20 minutes. Calculate the time
taken for the reaction to go to 80% completion.
Ans. 144.3 minutes
Q. 10. For a first order reaction, calculate the ratio between the time taken to com-
plete ¾ of the reaction and the time taken to complete half of the reaction.
Ans. Two
Q. 11. The following results have been obtained during the kinetics studies of the
reaction :
2A + B → C + D
 Experiment [A] mol L-1 [B] mol L-1 Initial rate of formation
of D mol L-1 min-1
I 0.1 0.1 6.0  10-3
II 0.3 0.2 7.2  10-2
III 0.3 0.4 2.88  10-1
IV 0.4 0.1 2.40  10-1

Determine the rate law and the rate constant for the reaction.
Ans. Rate = K[A][B]2
Q. 12. The rate of reaction triples when the temperature changes from 293 K to
313 K. Calculate the energy of activation of the reaction assuming that it
does not change with temperature.
Q. 13. The decomposition of A into product has value of K as 4.5  103 sec-1 at 10º
C and energy of activation 60 kJ/mol. At what temperature would K be
1.5  104 sec-1.
Ans. 24º C
Q. 14. (a) Write rate law and order of the following reaction :
AB + C2→ AB 2C + C (slow)
AB2+ C → AB 2C (fast)
(b) Define energy of activation of a reaction.
(c) What is the relationship between rate constant and activation energy of
a reaction ?
Ans. (a) Rate = K[AB][C2], Order = 1 + 1 = 2
− E a / RT
(c) K = Ae
Q. 15. For a chemical reaction R → P, the variation in the concentration (R) vs time (t)
plot is given :

(a) Predict the order of reaction.

(b) Write down its rate law.
(c) What is the slope of the curve ?
Q. 17. What do you understand by a first order reaction ? Show that for a first
order reaction time required to complete a definite fraction of the reaction
is independent of initial concentration.
Q. 18. In a pseudo first order reaction of hydrolysis of an ester in H2O, the follow-
ing results were obtained :

t/s 0 30 60 90
Ester (M/L) 0.55 0.31 0.17 0.085

(a) Calculate the average rate of reaction between the time interval 30 to
60 sec.

(b) Calculate the pseudo first order rate constant for the hydrolysis of
ester.

0.17 − 0.31
Ans. (a) Average rate during 30-60 sec. = = 4.67 10−3 mol L−1 sec−1
60 − 30

2.303 A0 2.303 0.55

(b) K30 = log = log
t A 30 0.31
2.303 0.55
K60 = log
60 0.17
2.303 0.55
K = log
90
90 0.085

Average K = 1.98  10-2 sec-1

Q. 19. The decomposition of NH3 on platinum surface is a zero order reaction.
What are the rate of production of N2 and H2 ? [K = 2.5  10−4]

Ans. 2NH3 → N2 + 3H2

1 d  NH 3  d  NH 2  1 d H2 
− = +
2 dt dt 3 dt
d  NH 3  0
= rate = k   NH 
3
dt
= 2.5  10−4 mol L-1 sec-1
d  N2  1 d  NH3 
=−
dt 2 dt
 1 −4 −1 −1
=  2.5 10 mol L sec
2

3 d  NH 3  3
 2.5 10−4
d H2 =− =
2 dt 2

= 3.75  10−44 mol L-1 sec-1

d  NH3  0

Rate = − = k NH3 
dt

= 2.5  10−4 mol L-1 sec-1

Rate of production of N 2 = 2.5  10−4 mol L-1 sec-1

LONG ANSWER TYPE QUESTIONS

Q. 1. (a) Define order of reaction.
(b) Rates of reaction double with every 10º rise in temperature. If this
generalization holds for a reaction in the temperature ranges 298 K to
308 K, what would be the value of activation energy for their reaction ?
R = 8.314 J K-1 mol-1.
Ans. (a) Order of Reaction : It is the sum of powers to which the conc. terms are
raised in rate law expression.
K Ea
(b) log 2 =  1 1 
K 2.303R T − T
1  1 2 
Here, T = 298 K, T = 308 K, R = K-1 mol-1
1 2
K
2
=2
K1
Ea
log 2 =  1 − 1 
2.303E 8.314  298 308
0.3010 = a
 10 
2.303  8.314  298  308 
0.3010  2.303  8.314  298  308
Ea =
10
-1
= 52898 J mol
= 52.898 KJ mol-1
Q. 2. (a) What are pseudo order reaction ? Give example.
(b) Rate constant K of a reaction varies with temperature ‘T’ according to
the equation :
Ea  1 
log K = log A −
 
2.303R  T 
where Ea is the activation energy. When a graph is plotted for log K vs 1/T,
a straight line with a slope of − 4250 K is obtained. Calculate Ea for the
reaction.
Ans. (a) The chemical reaction which look like higher order reaction but in real they
follow lower order kinetics.
For example,
+
CH3COOC2H5 + H2O ⎯ ⎯→ CH5COOH + C2 H5OH
H

excess
Rate = K[CH3COOC2H5]
Order = 1
Ea
(b) Slope = = − 4250 K
2.303R

So, Ea = − 2.303  R  Slope

= − 2.303  8.314 J K-1 mol-1  4250
= 81375.3 J mol-1
= 81.375 KJ mol-1
Q. 3. (a) Determine the units of rate constant for first and zero order reaction.
(b) Show that time required for the completion of 99% of the first order
reaction is twice the 90% of completion of the reaction.
Ans. (a) K = (mol)1 – n Ln – 1 S–1
For zero order, n = 0
So, K = (mol)1 – 0 L0 – 1 S–1 = S–1 mol L–1
For first order, n = 1
K = (mol)1 – n Ln – 1 S–1
So, K = (mol)1 – 1 L1 – 1 S–1
= S–1
 (b) For a first order reaction,
2.303 A
t= log 0

K  A
a  99
[A]0 = a, A = a − = 0.01 a
100
2.303 a
t (99%) = log
K 0.01a

2.303
= log100
K

2.303
= 2
K ...(i)
For 90% completion of reaction,

A = a − a  99 = 0.1a
100
2.303 a
t (90%) = log
K 0.1a

2.303
= 1
K ...(ii)
Dividing equation (i) by equation (ii), we get
t(99%) = 2  t(90%)
Q. 4. (a) Define rate constant of reaction.
(b) A first order reaction takes 40 mins for 30% decomposition. Calculate
t½.
Ans. (a) Rate constant : It is the rate of chemical reaction when the concentration of
reactant taken as unity at a given temperature.
(b) Let initial conc. = a
a  30
Conc. after 40 mins. = a −
100
= 0.70 a

2.303 A0
K= log
t A
 2.303 a
= log
40 0.70a
2.303 1
= log
40 0.70
2.303
=  0.1549
40
= 8.92  10–3 min–1
0.693
t1/ 2 =
K
0.693
=
8.92 10−3 = 77.7 min

Q. 5. (a) Determine the order of reaction and also determine the units of rate
constant.

(b) The following data were given for thermal decomposition of SO2Cl2 at
a constant volume :
SO2Cl2(g) → SO 2(g) + Cl 2(g)

Exp. Time/s Total p/atm

1 0 0.5
2 100 0.6
Calculate the rate of the reaction when total pressure is 0.65 atm.
Ans. (a) First order reaction
K = mol1 – n Ln – 1 S–1
n=1
K = (mol)1 – 1 L1 – 1 S–1
= S–1
 2.303 Pi
(b) k= log
t (2Pi − Pt )
2.303 0.5
= log
100 ( 2  0.5 − 0.6)
2.303 0.5
= log
100 0..4
2.303
=  0.969 = 2.23 10−3 s−1
100
Now, Rate = PSO Cl
2 2
Pressure of SO2Cl2 when total pressure = 0.65 atm
PSO2Cl2 = 2Pi – Pt
= 2  0.5 – 0.65
= 0.35 atm
Rate = 2.23  10–3  0.35
= 7.8  10–4 atm S–1
Q. 6. (a) The activation energy of a reaction is 100 kJ/mol. In the presence of
catalyst the activation energy is decreased by 75%. What is the effect on
rate constant of the reaction at 20º C ?
(b) A + 2B → 3C + 2D
The rate of disappearance of B is 1  10–2 mol L–1 sec–1. What will be
(i) rate of reaction (ii) rate of change in the concentration of A and C ?
Ans. (a) 2.35  1013 times
K2 Ea − E p K2 75  103
= 2.303RT  log K = 2.303  8.314  293 ]
[Hint : log 1 1
K
(b) (5  10–3, 5  10–3, 15  10–3) M L–1 sec–1