DL12CBKSCK2806

CHEMICAL KINETICS
1. The rate law for a reaction between the substances A and B is given by rate = k [A]n [B]m. On doubling the
concentration of A and halving the concentration of B, the ratio of the new rate to the earlier rate of the
reaction will be as [AIEEE- 2003]
1
(A) mn (B) (m + n) (C) (n – m) (D*) 2(n – m).
2
Sol. Rate1 = k [A]n [B]m
On doubling the concentration of A and halving the concentration of B
Rate2 = k [2A]n [B/2]m
m
k [2A]n [B/2]m  1
Ratio between new and earlier rate.  2n     2nm
n m 2
k [A] [B]

2. For the reaction system: 2NO(g) + O2(g)  2NO2(g), volume is suddenly reduced to half its value by
increasing the pressure on it. If the reaction is of first order with respect to O2 and second order with respect
to NO, the rate of reaction will : [AIEEE- 2003]
(A) diminish to one-fourth of its initial value (B) diminish to one-eighth of its initial value
(C*) increase to eight times of its initial value (D) increase to four times of its initial value.
Sol. Rate1 = k [NO]2 [O2]
When volume is reduced to 1/2, concentration become two times,

Rate1 k [NO]2 [O2 ] Rate1 1

Rate2 = k [2NO]2 [2O2] Rate 2 = 2 or Rate =
k [ 2NO] [2O2 ] 2 8

 Rate2 = 8 Rate1.
3. Consider an endothermic reaction X  Y with the activation energies Eb and Ef for the backward and
forward reaction, respectively. In general [AIEEE- 2005]
(A*) Eb < Ef (B) H = U (C) H < U (D) H > U
Sol. For endothermic reaction, H = ve H = E – Eb, it means Eb < E.

4. A reaction was found to be second order with respect to the concentration of carbon monoxide. If the
concentration of carbon monoxide is doubled, with everything else kept the same, the rate of reaction will be
[AIEEE- 2006]
(A) remain unchanged (B) tripled
(C*) increased by a factor of 4 (D) doubled
Sol. Given rate = k [CO]2
Thus, according to the rate law expression doubling the concentration of CO increases the rate by a factor of
4.

5. The following mechanism has been proposed for the reaction of NO with Br2 to form NOBr.
NO (g) + Br2 (g) NOBr2 (g) ; NOBr2 (g) + NO (g)  2NOBr (g) (slow step)
If the second step is the rate determining step, the order of the reaction with respect to NO(g) is
[AIEEE- 2007, 3/120]
(A) 1 (B) 0 (C) 3 (D*) 2
Sol. NO(g) + Br2(g) NOBr2(g)
NOBr2 (g) + NO (g)  2NOBr (g) [rate determining step]
Rate of the reaction (r) = k [NOBr2] [NO]
where [NOBr2] = Kc [NO] [Br2]
r = k. KC. [NO] [Br2] [NO]
r = k' [NO]2 [Br2].
The order of the reaction with respect to NO(g) = 2.

RESONANCE AIEEE_Chemical Kinetics - 1

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6. The energies of activation for forward and reverse reactions for A2 + B2 2AB are 180 kJ mol–1 and 200
–1
kJ mol respectively. The presence of a catalyst lowers the activation energy of both (forward and reverse)
reactions by 100 kJ mol–1. The enthalpy change of the reaction (A2 + B2 2AB) in the presence of catalyst
will be (in kJ mol–1). [AIEEE- 2007, 3/120]
(A) 280 (B*) 20 (C) 300 (D) 120
Sol. HR = E – Eb = 180 – 200 = – 20 kJ mol–1
The correct answer for this question should be –20kJ mol–1. But no option given is correct. Hence we can
ignore sign and select option
HR = E – Eb = 180 – 200 = – 20 kJ mol–1

7. A radioactive element gets spilled over the floor of a room. Its half-life period is 30days. If the initial activity is
ten times the permissible value, after how many days will it be safe to enter the room :
[AIEEE- 2007, 3/120]
(A) 10 days (B*) 100 days (C) 1000 days (D) 300 days
Sol. Let A be the activity for safe working.
Given Ao = 10 A Ao × No and A× N
2.303 No 2.303 Ao
t= log = log
 N  A

2.303
0.693 10 A 2.303  30 2.303  30
= log = log 10 = = 99.69 days  100 days.
30 A 0.693 0.693

1
8. For a reaction A  2B, rate of disappearance of 'A' related to the rate of appearance of 'B' by the
2
expression. [AIEEE- 2008, 3/105]
d [ A ] 1 d [B] d [ A ] d [B] d[A] d [B] d [ A ] 1 d [B]
(A*)   (B)   (C)  4 (D)  
dt 4 dt dt dt dt dt dt 2 dt

1
Sol. A  2B
2
1 d( A ) 1 d(B)
 =
1/ 2 dt 2 dt

d( A ) 1 d(B)
 
dt 4 dt
9. The half life period of a first order chemical reaction is 6.93 minutes. Time required for the completion of 99%
of the chemical reaction will be (log 2 = 0.301) : [AIEEE - 2009, 8/144]
(A) 23.03 minutes (B*) 46.06 minutes (C) 460.6 minutes (D) 230.3 minutes
Sol. In first order reaction for X% complation
2 .303  100 
k= log  100 – x% 
t  

0.693 2 .303  100 

t1/ 2 = log  100 – 99 
t  

0.693 2 .303  2
= =
6.93 t
So, t = 46.06 min.

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10. Consider the reaction [AIEEE - 2010, 4/144]
Cl2 (aq) + H2S(aq)  S(s) + 2H+ (aq) + 2Cl– (aq)
The rate equation for this reaction is
rate = k [Cl2][H2S]
Which of these mechanisms is/are consistent with this rate equation?
A. Cl2 + H2S  H+ + Cl– + Cl+ + HS– (slow)
Cl+ + HS–  H+ + Cl– + S (fast)
B. H2S  H+ + HS– (fast equilibrium)
Cl2 + HS–  2Cl– + H+ + S (slow)
(1) B only (2) Both A and B (3) Neither A nor B (4*) A only

Sol. Mechanism (1) rate = K [Cl2] [H2S]

Mechanism (2) rate = K1 [Cl2] [HS–]

[H ][HS  ]
Keq =
[H2S]

K eq [H2 S]
[HS–] =
[H  ]

[Cl2 ][H2S ]
= K1Keq
[H  ]
 Mechanism (1) is consistent with this rate equation.

11. Given that for a reaction of order n, the integrated form of the rate equation is

1  1 1 
k=  n1  n 1  where C0 and C are the values of the reactant concentration at the start
t (n  1)  C C0 
and after time t. What is the relationship between t 3/4 and t 1/2 where t 3/4 is the time required for C to
become 1/4 C0?
(A*) t 3/4 = t 1/2 [2n1 + 1] (B) t 3/4 = t 1/2 [2n1  1]
(C) t 3/4 = t 1/2 [2 n+1  1] (D) t 3/4 = t 1/2 [2n+1 + 1]
12. The rate constant, the activation energy and the frequency factor of a chemical reaction at 25°C are
3.0 × 10–4 s–1 ,104.4 KJ mol –1 and 6.0 × 1014 s–1 respectively. The value of the rate constant as T  
is :
(A) 2.0 × 1018 s–1 (B*) 6.0 × 1014 s–1 (C) infinity (D) 3.6 × 1030 s–1

13. Consider the reaction 2A(g)  3B(g) + C(g). Starting with pure A initially, the total pressure doubled in
3 hrs. The order of the reaction might possibly be
(A*) zero (B) first
(C) second (D) unpredictable from this data
d [A ]
14. For the reaction A Products,  = k and at different time interval, [A] values are :
dt
Tim e 0 5 m in 10 m in 15 m in
[A] 20 m ole 18 m ole 16 m ole 14 m ole

At 20 minute, rate will be :

(A) 12 mol /min (B) 10 mol/min (C) 8 mol/min (D*) 0.4 mol/min

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15. What will be the order of reaction and rate constant for a chemical change having log t vs log concentration
of (A) curves as :

(A*) 0, 1/2 (B) 1, 1 (C) 2, 2 (D) 3, 1

16. Two substances A (t 1/2 = 5 min) and B (t 1/2 = 15 min) are taken in such a way that initially [A] = 4[B].
The time after which both the concentration will be equal is :
(A) 5 min (B*) 15 min (C) 20 min (D) concentration can never be equal
17. In the following first order reactions
K1 K2
(A)   Product, (B)   Product, the ratio k 1 /k2 if 90% of (A) has been reacted in time 't'
while 99% of(B) has been reacted in time 2t is :
(A*) 1 (B) 2 (C) 1/2 (D) None of these
18. For a reaction A  Products, the concentration of reactant are aC 0 , a2C0, a3C0 ........... after time
interval 0, t, 2t ........where 'a' is constant. Then :
(A) reaction is of 1st order and K = (1/1) ln a
(B) reaction is of 2nd order and K = (1/tC 0)(1–a)/a
(C*) reaction is of 1st order and K = (1/t) ln a
(D) reaction is of zero order and K = {(1 – a)C 0}/t.
19. In a certain reaction, 10% of the reactant decomposes in one hour, 20 % in two hours, 30% in three
hours and so on the dimensions of the rate constant is :
(A) hour–1 (B*) mole litre–1 sec–1 (C) litre mole–1 sec–1 (D) mole sec–1

20. For a reaction pA + qB  products, the rate law expression is r = k[A]1 [B]m , then :
(A) (p+1) < (1+ m) (B) (p + q) > (1 + m)
(C*) (p + q) may or may not be equal to (1+ m) (D) (p + q) = (1 + m)

21. In acidic medium the rate of reaction between (BrO 3)¯ and Br¯ ions is given by the expression.
– [d (BrO 3–) /dt] = K [BrO 3– ] [Br¯] [H+] 2 It means :
(A) Rate constant of overall reaction is 4 sec –1
(B) Rate of reaction is independent of the concentration of acid
(C) The changes in pH of the solution will not affect the rate
(D*) Doubling the concentration of H + ions will increase the reaction rate by 4 times.
22. For rate constant is numerically the same for three reactions of first, second and third order respectively.
Which of the following is correct :
(A) if [A] = 1 then r 1 = r2 = r3 (B) if [A] < 1 then r 1 > r2 > r3
(C) if [A] > 1 then r 3 > r2 > r1 (D*) All

23. Rate of formation of SO3 in the following reaction 2SO2 + O2  2SO3 is 100 g min–1. Hence rate of
disappearance of O2 is :
(A) 50 g min-1 (B) 40 g min–1 (C) 200 g min–1 (D*) 20 g min–1

d[ A ] d[B] d[C ]
24. xA + yB  zC. If  =  = 1.5 = then x,y and z are :
dt dt dt
(A) 1,1,1 (B) 3,2,3 (C*) 3,3,2 (D) 2,2,3

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25. A reaction follows the given concentration (M)–time graph. The rate for this reaction at 20 seconds will be:
0.5
0.4
0.3
0.2
0.1

0 20 40 60 80 100
Time/second
(A) 4 × 10–3 M s–1 (B) 8 × 10–2 M s–1 (C) 2 × 10–2 M s–1 (D*) 7.77 × 10–3 M s–1

RESONANCE AIEEE_Chemical Kinetics - 5