19. Half of the substance ‘A’ following first order kinetic is 5 days.

Starting with 100 g of A,

amount left after 15 days is
a) 25 g b) 50 g
c) 12.5 g d) 6.25 g
20. The ratio t1/8 : t1/2 for the first order reaction is
a) 3 b) 5
c) 2 d) 7
21. A first order reaction has a half life period of 34.65 second. Its rate constant is
a) 0.2 × 10-2 sec-1 b) 4 × 10-2 sec-1
c) 20 sec-1 d) 2 × 10-2 sec-1
22. The first order rate constant for the decomposition of N2O5 is 6.2 × 10-3 sec-1. The t1/2 of the
decomposition
a) 117.7 sec b) 111.7 sec
c) 228.4 sec d) 168.9 sec
23. The rate of a chemical reaction doubles for every 10° C rise to temperature. If the
temperature is raised by 50° C the rate of reaction increased by about
a) 10 times b) 24 times
c) 32 times d) 64 times
24. For a reaction 2N2O5 → 4NO2 + O2 rate and rate constant are 1.02 × 10-4 and 3.4 × 10-5 sec-1
respectively, if rate law is rate = k[N2O5] then concentration of N2O5 at that time will be
a) 1.732 b) 3
-4
c) 1.02 × 10 d) 3.4 × 10-5
25. Activation energy of a chemical reaction can be determined by _____________.
(a) determining the rate constant at standard temperature.
(b) determining the rate constants at two temperatures.
(c) determining probability of collision.
(d) using catalyst.
26. Consider the Arrhenius equation given below and mark the correct option.
k = A e–Ea/RT
(a) Rate constant increases exponentially with increasing activation energy and decreasing
temperature.
(b) Rate constant decreases exponentially with increasing activation energy and decreasing
temperature.
(c) Rate constant increases exponentially with decreasing activation energy and decreasing
temperature.
(d) Rate constant increases exponentially with decreasing activation energy and increasing
temperature.
27. During decomposition of an activated complex
(a) energy is always released (b) energy is always absorbed
(c) energy does not change (d) reactants may be formed
28. Which of the following statements are in accordance with the Arrhenius equation?
(a) Rate of a reaction increases with increase in temperature.

37
 (b) Rate of a reaction increases with increase in activation energy.
(c) Rate constant decreases exponentially with increase in temperature.
(d) Rate of reaction decreases with decrease in activation energy.
29. The role of a catalyst is to change
(a) gibbs energy of reaction. (b) enthalpy of reaction.
(c) activation energy of reaction. (d) equilibrium constant
30. Which of the following statements is not correct about order of a reaction.
(a) The order of a reaction can be a fractional number.
(b) Order of a reaction is experimentally determined quantity.
(c) The order of a reaction is always equal to the sum of the stoichiometric coefficients of
reactants in the balanced chemical equation for a reaction.
(d) The order of a reaction is the sum of the powers of molar concentration of the reactants in
the rate law expression.

Answers:
1-c 2-c 3-a 4-a 5-c
6-d 7-b 8-a 9-a 10-d
11-b 12-c 13-b 14-b 15-a
16-b 17-c 18-c 19-c 20-a
21-d 22-b 23-c 24-b 25-b
26-d 27-a 28-a 29-c 30-c

ASSERTION AND REASON TYPE

In the following questions a statement of assertion followed by a statement of reason is
given. Choose the correct answer out of the following choices.
(a) Both assertion and reason are correct and the reason is correct explanation of assertion.
(b) Both assertion and reason are correct but reason does not explain assertion.
(c) Assertion is correct but reason is incorrect.
(d) Assertion is incorrect but reason is correct.
1. Assertion : Order of the reaction can be zero or fractional.
Reason : We cannot determine order from balanced chemical equation.
2. Assertion : Order and molecularity are same.
Reason : Order is determined experimentally and molecularity is the sum of the
stoichiometric coefficient of rate determining elementary step.
3. Assertion : The enthalpy of reaction remains constant in the presence of a catalyst.
Reason : A catalyst participating in the reaction, forms different activated complex and lowers
down the activation energy but the difference in energy of reactant and product remains the
same.
4. Assertion : All collisions of reactant molecules lead to product formation.
Reason : Only those collisions in which molecules have correct orientation and sufficient
kinetic energy lead to compound formation.
5. Assertion : Rate constants determined from Arrhenius equation are fairly accurate for simple
as well as complex molecules.
38
 Reason : Reactant molecules undergo chemical change irrespective of their orientation during
collision.
Answers:
1-b 2-d 3-a 4-d 5-a

TWO MARKS QUESTIONS

1. a) Define the half life period of a reaction.
b) For a reaction R → P half Life (t1/2) is observed to be independent of the initial
concentration of reactants.What is the order of reaction?
Ans 2 a) The half Life period of a reaction is the time in which the concentration of a reactant is
reduced to one-half of its initial concentration.
b) Since half life (t1/2) is independent of the initial concentration of the reactant, the reaction
is of first order.
2. Observe the following graph in diagram and answers of following questions.

i) If slope is equal to -2.0 × 10-6, what will be the value of rate constant.
ii) How does the half-life of zero order reaction relate to its rate constant.
Ans. i) the given graph is of first order reaction there for
Slope = - k / 2.304
k = -2.303 × slope
k= -2.303 × (-2.0×10-6 )s-1
k= 4.606 ×10-6 s-1
ii) t1/2 = [R]o. /2k
3. a) For a given reaction A+B → P: the rate law is given by,r =k[A]½[B]2 . What is the order of the
reaction?
b) What is the rate of reaction? Write two factors that affect the rate of reaction.
Ans 3 a) The order of reaction= sum of powers of concentration terms = ½ + 2= 5/2 = 2.5
b) The rate of a reaction or the speed of a reaction is defined as the change in concentration
of a reactant or product in unit time.
R→P
Rate = - ∆[R] /∆t
Rate = ∆[P] /∆t
Two factors affecting rate of reaction are:
i) Concentration of reactants
ii) Temperature
4. A first order reaction takes 40 minutes for 30% decomposition. Calculate half Life t1/2 .
Given: log10= 1, log7 = 0.8451
39
Ans. k= 2.303/t. log[R]o/[R] ,t= 40 min.
=2.303/40. log100/100-30; k=2.303/40.log10/70; =2.303/40(log10-Log7)
k=2.303/40.log10/7; 2.303/40×.1549= 0.00891
k =8.91 ×10-3 min-3
t1/2= .693/k; .693/8.91×10-3 ;=.693×10+3 / 8.91 = 77.78 minutes
5. The thermal decomposition of an acid is a first order reaction with a rate constant of 2.3×10-3
s-1 at a certain temperature. Calculate how long it will take for three-fourth of the initial
quantity of acid to decompose.
(log 4 = 0.6021, log 2 = 0.301)
Ans:

6. For a reaction A + B→P, the rate is given by rate= k[A] [B]2

i) How is the rate of a reaction affected if the concentration of B is double?
ii) what is the overall order of the reaction if a is present in large excess?
Ans. i) A + B→P
Rate= k[A] [B]2 ;
Rate r’= k[A] [2B]2
Rate=4×k[A] [2B]2 = 4r’
If concentration of B is double the rate of reaction becomes 4 times.
ii) If A is present in large excess, the rate law becomes
r = k’ [B]2 where k’ = k [A]
Thus the overall order of reaction is two.
7. Write two difference between order of reaction and molecularity of reaction
Ans. (any two)

8. The rate constant for a first order reaction is 60 s-1. How much time will it take to reduce the
40
 initial concentration of the reactant to 1 /10 th of its initial value?
Ans. t= 2.303/k log[R]o / [R]
as [R] = [R]o/ 10
t= 2.303/k log[R]o / [R]o/10
t= 2.303/60. log10
t = 2.303 /60×1 =3.838 × 10-2 s
9. i) Explain why H2 and O2 do not react at room temperature.
ii) write the rate equation for the reaction A2 + 3B3 → 2C, if the overall order of the reaction is
zero.
Ans. i) Due to high activation energy for the reaction.
ii) Rate = k[A2]0 [B]0 or Rate= k
10. For a certain chemical reaction variation in the concentration ln[R] vs time plot is given
below:

i) What is the order of the reaction?

ii) What are the units of rate constant k?
iii) Give the relationship between K and t1/2 (half life period)
iv) What is the slope of the curve?
Ans: i) First order
ii) time-1 or s-1
iii) k= 0.693 / t1/2
iv) slope = -k (rate constant)

THREE MARKS QUESTIONS

1. i) A first order reaction is 75% completed in 40 minutes. Calculates its half life t1/2 .
ii)Predict the order of the reaction in the given plots:
Where [R]o is the concentration of reactant (Given log2= 0.3010,log 4= 0.6021)

Ans:

41
2. The decomposition of A into product has value of k as 4.5 × 103 s-1 at 10° C and energy of
activation is 60 kJ mol-1. At what temperature would KB 1.5 ×104 s-1? (Given log 3.333 =0.5228
Ans: log k2 / k1=Ea/2.303R [T2-T1/T2 T1)
log1.5 ×104 / 4.5 × 103
=60000 J mol-1/2.303×8.314(T2 -283/283 T2
log 3.333= 3.13363 (T2-283/283T2 )
=0.5228/313363 = T2-283/283 T2
0.0472 T2=T2 - 283
T2=283/0.9528 = 297k=297-273°C= 24°C.
3. a) Explain pseudo first order reaction with example.
b) Answer the following questions on the basis of the given plot of potential energy vs
reaction coordinate

i) What is the threshold energy for the reaction?

ii) What is the activation energy for the forward reaction?
iii) What is the activation energy for the backward reaction?
iv) what is the enthalpy change for the forward reaction?
Ans. a) Chemical reaction which are Biomolecular but due to negligible change in the
concentration of one of the reactant, the reaction behaves as first order reaction.Such
reactions are called pseudo first order reactions.example:
Inversion of cane sugar: C12H22O11. + H2O → C6H12O6. + C6H12O6
b)

42
4. a) for the reaction
2N2O5 (g) → 4NO2(g) + O2(g) at 318 K calculate the rate of reaction if rate of disappearance of
N2O5(g) is 1.4 × 10-3 ms-1
b) for a first order reaction derive the relationship t99% = 2t90%
Ans.

5. Define half life of a reaction. Write the expression for i) half life for zero order reaction and
ii) first order reaction.
Ans: The half Life (t1/2) of reaction is that time in which the concentration of a reactant is reduced
to one half of its initial concentration.
i) t1/2 for zero order reaction = [R]o / 2k. [R]=initial concentration, k = rate constant
ii) t1/2 for first order reaction = 0.693/k
6. Following data are obtained for the reaction:
N2O5 + → 2NO2 + ½ O2

t/s 0 300 600

[N2O5] / molL-1 1.6 × 10-2 0.8×10-2 0.4×10-2

i) Show that it follows a first order reaction.
ii) Calculate the half life.
(Given log 2= 0.3010; log4 =0.6021)
Ans:

43
7. A first order reaction is 50% completed in 40 minutes at 300 K and in 20 minutes at 320 K.
Calculate the activation energy of the reaction.
(Given log2 =0.3010, log 4 = 0.6021, R = 8.314 J K-1 mol-1)
Ans. For a first order reaction
k= 0.693 / t1/2
k1= 0.693 / 40 min-1
k2= 0.693 / 20 min-1
k2 / k1 = 0.693/ 20 / 0.693/40 = 2
log k2 / k1=Ea / 2.303×8.314(T2 -T1/T1T2)
log2=Ea / 2.303×8.314 (320-300/300×320)
0.3010=Ea×20/19.147×300×320
Ea=0.3010×19.147×300×320/20
Ea=27663.58 J mol-1 = 27.66 kJ mol-1
8. i) What will be the effect of temperature on rate constant?
ii) The rate of a chemical reaction doubles for an increase of 10 K in absolute temperature from
298 K. Calculate activation energy.
Ans. i) The rate constant of a reaction is nearly doubled with rise in temperature by 10° degree
Celsius. The exact dependence of the rate constant on temperature is given by Arrhenius
equation, k =Ae-Ea/RT where A is called called frequency factor and Ea is the activation energy of
the reaction.
ii)

44
9. For the hydrolysis of methyl acetate solution the following result were obtained:
t/s 0 30 60
[CH3COOCH3]/mol-1 0.60 0.30 0.15
i) Show that it follows pseudo first order reaction, as the concentration of water remains
constant.
ii) Calculate the average rate of reaction between the time interval 30 to 60 seconds. (Given
log 2=0.3010, log 4= 0.6021)
Ans.

10. A reaction is first order in A and second order in B

i) Write the differential rate equation?
ii) How is the rate affected by increasing the concentration of B three times?
iii) How is the rate affected when concentration of both A and B are doubled?
Ans. i) Rate = -d[R] /dt Rate = k [A] [B]2
ii) if the concentration of B is tripled then rate = k[A] [3B]2
= 9k[A][B]2
The rate of reaction becomes 9 times.
iii) If the concentration of both A and B are doubled,then
rate = k[2A] [2B]2 =8k [A][B]2
The rate of reaction becomes 8 times.

45
CASE BASED QUESTIONS:
1. The rate of reaction is concerned with decrease in concentration of reactant or increase in the
concentration of products per unit time. It can be expressed as an instantaneous rate at a
particular instant of time the average rate over a large interval of time. Mathematical
representation of rate of reaction is given by rate law.Rate constant and order of a reaction
can be determined from rate law or its integrated rate equation.

a) What is the average rate of reaction?

b) Write two factors that affect the rate of reaction.
c) i) What happens to the rate of reaction for zero order reaction?
ii) What is the unit of k for zero order reaction?
OR
c) i) for a reaction P + 2Q →Product
Rate = k[P]½ [Q]1; What is the order of the reaction?
ii) Define pseudo first order reaction with an example.
Ans. a) The rate of reaction measured over a long interval of time is called average rate of
reaction
Average rate of reaction =
- ∆ [R] / ∆t = ∆[P]/∆t
b) Two factors that affect the rate of reaction are the concentration of reactants and
temperature.
c) i) the rate of reaction for a zero order reaction is always constant.
ii) unit of k for a zero order reaction is mol L-1s-1
OR
c) i) order of the reaction= ½ +1 =3/2 = 1.5
ii) A reaction that appears to be higher order but follows first order kinetics under certain
conditions is called pseudo first reaction. For example hydrolysis of ester is a pseudo first
order reaction.When water is taken in large excess.
CH3COOC2H5 + H2O(excess) → CH3COOC2H5 + C2H5OH
Rate= k [H2O] [CH3COOC2H5
The term [H2O] can be taken as constant. The equation becomes
Rate= k [CH3COOC2H5]
Where k = k’[H2O]
2. The biological processes taking place in our body are nothing but simply chemical reactions
which impact our day to day activities directly therefore understanding how chemical
reactions work and what affect the rates of reaction is really important. An example is the
decomposition of hydrogen peroxide. Due to high solubility of hydrogen peroxide the reaction
is quite slow but it gets catalyzed in presence of an enzyme catalase found in liver cells. By
enzyme action, hydrogen peroxide gets decomposed to form hydrogen and water, which
unlike hydrogen peroxide are completely harmless.

Answer the following questions are multiple choice questions choose the appropriate answer
:
i) the change in concentration of any reactant or product for unit time is called :
a) Rate of reaction b) Order of reaction
46
c) Molecularity of reaction d) Activation energy
Ans i) a) Rate of reaction
ii) the reaction of decomposition of hydrogen peroxide is a:
a) Pseudo first order reaction b) First order reaction
c) Second order reaction d) Zero order reaction
Ans ii) b) Order of reaction
iii) The rate of decomposition of hydrogen peroxide is increased in presence of catalyst
because:
a) catalyst provides an alternative pathway by reducing activation energy of the reacting
molecules.
b) Catalyst provide an alternative pathway by increasing activating activation energy of the
reacting molecules.
c) Catalyst is not consumed in the reaction.
d) Catalysts take part in the reaction.
Ans iii) a) Catalyst provides and alternative pathway by reducing activation energy of the
reacting molecules

47
 UNIT-IV
d- & f-BLOCK ELEMENTS

Multiple choice questions (1Mark each)

1. The electronic configuration of gadolinium (At. No. = 64)
a. 4f8 5d0 6s2 b. 4f7 5d1 6s2
c. 4f3 5d5 6s2 d. 4f6 5d2 6s2
2. Which one of the following elements shows maximum no. of different oxidation states in its
compounds
a. Eu b. La
c. Gd d. Am
3. Lanthanoid contraction is due to increase in :
a. Effective shielding of 4f electrons b. Atomic no
c. Effective nuclear charge d. Atomic radius
4. Which of the following oxidation state is most common among the lanthanoid is:
a. +3 b. +4
c. +2 d. +5
- -
5. The product of oxidation of I with MnO4 in alkaline medium is
a. IO3- b. I2
-
c. IO d. IO4-
6. The formula of pyrolusite is
a. Mn3O4 b. MnO2
c. MnO d. Mn2O7
7. Which of the following statements is not correct
a. La(OH)3 is less basic than Lu(OH)3
b. La is actually an element of transition series rather than lanthanoids
c. Atomic radius of Zr and Hf is same
d. In lanthanoid series the ionic radius of Lu3+ is the smallest
8. The basic character of the transition metal monoxide follow the order
a.CrO > VO > FeO > TiO b.TiO > FeO > VO > CrO
c.TiO > VO > CrO > FeO d. VO > CrO > TiO > FeO
9. Which of the following ion has the electronic configuration is 3d6
a.Ni3+ b.Mn3+
c.Fe3+ d.Co3+
10. The colour of light absorbed by a aqueous solution of CuSO4
a.Orange red b.Blue green
c.Yellow d. Violet
11. Which one of the following statement is correct when SO2 is passed through acidified K2Cr2O7
solution.
a.SO2 is reduced b.Green Cr2(SO4)3 is formed
c.The solution turns blue d. The solution is decolourised
12. Which of the following statement about the interstitial compound is incorrect
48