SHEET-2

TYPES OF 1ST ORDER REACTIONS , METHODS TO DETERMINATION OF

ORDER OF REACTION, EFFECT OF TEMPERATURE
(ARRHENEOUS EQUATION)

SECTION – 1
1. The rate constant of a reaction at temperature 200K is 10 times less than the rate constant at 400 K. What is
the activation energy (E a ) of the reaction (R = gas constant)
(A) 1842.4 R (B) 921.2 R (C) 460.6 R (D) 230.3 R

2. The rate constant is doubled when temperature increases from 27°C to 37°C. Activation energy in kJ is
(A) 34 (B) 54 (C) 100 (D) 50

3. Collision theory is applicable to

(A) First order reactions (B) Zero order reactions
(C) Bimolecular reactions (D) Intra molecular reactions

4. An endothermic reaction A  B has an activation energy 15 kcal/mole and energy of reaction 5Kcal/mole. The
activation energy of the reaction B  A is
(A) 20 kcal/mole (B) 15 kcal/mole (C) 10 kcal/mole (D) None of these

5. Inversion of sucrose is
(A) Zero order reaction (B) First order reaction
(C) Second order reaction (D) Third order reaction

6. The following statements(s) is incorrect

(A) A plot of log K p versus 1 / T is linear
(B) A plot of log [X ] versus time is linear for a first order reaction X  P
(C) A plot of log P versus 1 / T is linear at constant volume
(D) A plot of P versus 1 / V is linear at constant temperature

7. If ‘I’ is the intensity of absorbed light and C is the concentration of AB for the photochemical process
AB  hv  AB *, the rate of formation of AB* is directly proportional to
(A) C (B) I (C) I 2 (D) C.I

8. Which of the following statements is not true according to collision theory of reaction rates
(A) Collision of molecules is a precondition for any reaction to occur
(B) All collisions result in the formation of the products
(C) Only activated collisions result in the formation of the products
(D) Molecules which have acquired the energy of activation can collide effectively

9. Energy of activation of a reactant is reduced by

(A) Increased temperature (B) Reduced temperature
(C) Reduced pressure (D) Increased pressure

10. Activation energy is given by the formula

K2 Ea  T2  T1  K1 Ea  T2  T1 
(A) log    (B) log   
K1 2 . 303 R  T1 T2  K2 2 . 303 R  T1 T2 
K1 Ea  T1  T2 
(C) log    (D) None of these
K2 2 . 303 R  T1 T2 

11. A catalyst is a substance which

(A) Increases the equilibrium concentration of the product
(B) Changes the equilibrium constant of the reaction
(C) Shortens the time to reach equilibrium
(D) Supplies energy to the reaction.
12. A catalyst increases the rate of reaction because it
(A) Increases the activation energy (B) Decreases the energy barrier for reaction
(C) Decreases the collision diameter (D) Increases the temperature coefficient

13. In respect of the equation k = A exp (– Ea / RT), which one of the following statements is correct?
(A) R is Rydberg's constant (B) k is equilibrium constant
(C) A is adsorption factor (D) Ea is the energy of activation

14. Rate of a reaction can be expressed by Arrhenius equation as :

K = Ae–E/RT In this equation, E represents
(A) The fraction of molecules with energy greater than the activation energy of the reaction
(B) The energy above which all the colliding molecules will react
(C) The energy below which colliding molecules will not react
(D) The total energy of the reacting molecules at a temperature, T

15. Collision theory states that:

(A) all collisions lead to chemical reaction (B) most collisions lead to chemical reactions
(C) very few reactions involve particle collisions (D) effective collisions lead to chemical reactions

16. For collisions to be successful, reactants must have

(A) favourable geometry only (B) sufficient heat of reaction only
(C) sufficient potential enegy only (D) sufficient kinetic energy and favourable geometry

17. To increase the rate of a reaction, there must be

(A) a decrease in the frequency of collisions
(B) an increase in the frequency of collisions
(C) a decrease in the frequency of successful collisions
(D) an increase in the frequency of successful collisions

18. An increase in temperature increases the rate of a chemical reaction because

(A) the activation energy is lower
(B) exothermic reactions are always favoured
(C) a grater fraction of particles have sufficient kinetic energy
(D) the particles are more likely to have favourable collision geometry

19. Which of the following will decrease the number of effective collisions during a chemical reaction?
(A) adding a catalyst (B) Increasing the surface area
(C) Decreasing the temperature (D) Increasing reactant concentrations

20. The Ea values for forward and backward reactions are 50 kJ/mole and 40 kJ/mole respectively. If K 1 and K2 be
the equilibrium constants of reaction at temperature T1 and T2, respectively and T2 > T1, then
K2
(A) K1 < K2 (B) K2 = K1 (C) K1 > K2 (D)  10
K1
21. The rate constant of a reaction at 27°C is 2.3 × 103 min1 and at this temperature 0.001 % of the reactant
molecules are able to cross over the energy barrier existing between the reactants and the products. What
can the maximum value of rate constant be achieved on raising the temperature ?
(A) 23.0 min1 (B) 2.3 × 102 (C) 115.0 min1 (D) 230.0 min1

22. Consider the reaction A  2 B + C, H =  15 kcal. The energy of activation of backward reaction is 20 k cal
mol1. In presence of catalyst the energy of activation of forward reaction is 3 k cal mol 1. At 400 K the catalyst
causes the rate of the reaction to increase by the number of times equal to
3.5 2.5 2.303
(A) e (B) e (C) e2.5 (D) e
23. Consider the following potential energy diagram:

The activation energy for the forward reaction is

(A) 25 kJ (B) 50 kJ (C) 75 kJ (D) 125 kJ
24. Increasing the temperature of a reaction increases the reaction rate by:
I. increasing frequency of collisions
II. increasing the kinetic energy of collision
III. decreasing the potential energy of collision
(A) I only (B) I and II only (C) II and III only (D) I, II and III

25. Consider the following:

I. frequency of successful collisions
II. volume of the reaction vessel
III. pressure of the system
IV. mass of the system
To increase the rae of a reaction there must be an increase in
(A) I only (B) I and III only
(C) I, III and IV only (D) I, II, III and IV

SECTION-2
1. In a reaction carried out at 400 K, 0.0001% of the total number of collisions are effective. What is the energy
of activation of the reaction?

2. Consider the following potential energy diagram for a reversible reaction:

Find activation energy of forward and backward reaction and H?

3. Consider the following potential energy diagram:

Which energy interval that represents the activation energy for the reverse reaction?

4. A forward reaction has an activation energy of 50 kJ and a H of –100 kJ. Draw potential energy diagram for
the reaction?

5. A B + C
Time t 
Total pressure of ( B+C) P2 P3
Find k.

6. A B + C
Time 0 t
Volume of reagent V1 V2
The reagent reacts with A, B and C. Find k. [Assuming n-factor of A, B & C are same]

7. Consider the following reaction:

1/2H2(g) + 1/2I2(g)  HI(g)
The activation energy for the formation of HI is 167 kJ and for the decomposition of HI is 139 kJ. What is H
for the formation of HI?
8. The decomposition of N2O5 according to the equation 2N2O5 (g)  4 NO2(g) + O2(g) is a first order
reaction. After 30 min. from start of decomposition in a closed vessel the total pressure developed is found to
be 284.5 mm Hg. On complete decomposition, the total pressure is 584.5 mm Hg. Calculate the rate constant
of the reaction.
9. In a pseudo first order hydrolysis of ester in water the following results were obtained:
t/s 0 30 60 90
[ester]/M 0.55 0.31 0.17 0.085
i) Calculate the average rate of reaction between the time intervals 30 to 60 seconds.
ii) Calculate the pseudo first order rate constant for the hydrolysis of ester.
10. A first order reaction is 50% completed in 20 minutes at 27°C and in 5 min at 47°C. What is the energy of
activation of the reaction?
11. For the first order reaction A — B + C, carried out at 27 ºC if 3.8  10–16 % of the reactant molecules exists
in the activated state, What is the Ea (activation energy) of the reaction [log 3.8 = 0.58]

12. The energy of activation of a first order reaction is 104.5 kJ mole–1 and pre – exponential factor (A) is 5  1013
–1
sec . At what temperature, will the reaction have a half life of 1 minute?
13. Consider the following potential energy diagram:

Is the reaction endothermic or exothermic ? Calculate H.

14. The specific rate constant for a reaction increases by a factor of 4, if the temperature is changed from 27°C to
47°C. Find the activation energy for the reaction.

15. The first order rate constant for the decomposition of C2H5I by the reaction.
C2H5I(g)  C2H4(g) + HI(g)
–5 –1 –1
at 600 K is 1.60  10 s . Its energy of activation is 209 kJ mol . Calculate the rate constant at 700 K.
16. Consider the following potential energy diagram

Answer the following

i) Which interval represents H of reaction
ii) Which interval represents Ea of forward reaction
13 –1
17. In the Arrhenius equation for a certain reaction, the value of A and E a (activation energy) are 4  10 sec
–1
and 98.6 kJ mole respectively. If the reaction is of first order, at what temperature will its half life period be
10 minutes?
–1 –1
18. The rate constants of a reaction at 500 K and 700 K are 0.02 s and 0.07 s , respectively. Calculate the
values of Ea and A at 500 K.
19. Consider the following reaction:
CO + NO2  CO2 + NO H = –234 kJ
The activation energy of the forward reaction is 134 kJ. What is the activation energy for the reverse reaction?
 ANSWER KEY
SHEET-1
SECTION-1
1. B
2. B
3. C
4. C
5. B
5. Rate = K (Sucrose )(H 2 O )o
6. C
d ln k H o
6. By Vant’s Hoff equation, 
dt RT 2
H o
or ln k p    I . Hence (A) is correct (B) is also correct as plot of log (X) vs time is linear. (C) is wrong
RT
because p  T at constant volume. (D) is correct by Boyle’s law.
7. B
7. In photochemical reaction the rate of formation of product is directly proportional to the
intensity of absorbed light.
8. B
8. All collisions are not effective and does not result in the formation of the products
9. A
9. Energy of activation reduced by increasing temperature.
10. A
11. C
12. B
13. D
14. C
15. D
16. D
17. D
18. C
19. C
20. A
21. D
22. B
23. C
24. B
25. A
SECTION-2
1. 11.05 k cal/mol
2. Ea(f) = 30kJ
Ea(b) = 10 kJ
H = +20 kJ
3. III
4.

l P3
5 k = ln
t (P3  P2 )
l V1
6 k = ln
t (2V1  V2 )
7. endothermic and the H = +28 kJ
8 k1 = 5.2 × 10–3 min–1
–3 –1 –2 –1
9. i) 4.67  10 M s ; ii) 1.9  10 s
10. 55.14 kJ/mol
11. 100 kJ/mole
12. 349.1 K
13. endothermic and the H = +50 kJ
 –1
14. 55.14 kJ mole
–3 –1
15. 6.36  10 s
16. i) 1
ii) 2
17. 311.3 K
–1
18. Ea = 18.23 kJ, A = 1.60 s
19. 368 kJ