JH PC Chemical Kinetics DPP 22 To 34

PHYSICAL CHEMISTRY
TARGET DAILY PRACTICE PROBLEMS
JEE (ADVANCED) : 2014 DPP

COURSE NAME : UMANG (UP) DATE : 27.05.2013 to 01.06.2013 DPP NO. 22 & 23
* Marked Questions are having more than one correct option.

DPP NO. # 22
1. The rate of change in concentration of C in the reaction 2A + B  2C + 3D was reported as 1.0 mol litre–1
sec–1 . Calculate the reaction rate
(A) 0.05 mole litre–1 sec–1 (B) 0.01 mol litre–1 sec–1
(C) 0.5 mol litre–1 sec–1 (D) None of these
2. For a chemical reaction 2X + Y  Z, the rate of appearance of Z is 0.05 mol L–1 per min. The rate of
disappearance of X will be :
(A) 0.05 mol L–1 per hour (B) 0.05 mol L–1 per min
(C) 0.1 mol L min
–1 –1 (D) 0.25 mol L–1 per min
3. For the reaction : N2(g) + 3H2(g) 2NH3(g)

The rate of formation of ammonia = 0.002 Kgh–1
The rate of disappearance of hydrogen will be
(A) .001 (B) 0.003 (C) 0.002 (D) 0.004
7. The instantaneous rate of disappearance of the MnO4– ion in the following reaction is 4.56 × 10–3 Ms–1.
2MnO4– + 10 I– + 16H+  2Mn2+ + 5I2 + 8H2O. The rate of appearance of I2 is :
(A) 1.14 × 10–3 Ms–1 (B) 5.7 × 10–3 Ms–1 (C) 4.56 × 10–4 Ms–1 (D) 1.14 × 10–2 Ms–1
5. In the following reaction : x A  yB
 d[A ]   d[B] 
log   = log   + 0.48 where –ve sign indicates rate of disappearance of the reactant. Thus, x : y
 dt   dt 
is –
(A) 1 : 2 (B) 2 : 1 (C) 3 : 1 (D) 3 : 10
dC dn dP
6. Which is correct relation in between , and where C, n, P, represents concentration, mole
dt dt dt
and pressure terms for gaseous phase reactant A(g)  product.
dC 1 dn 1 dP dC dn dP
(A) – =– =– (B) = =–
dt V dt RT dt dt dt dt
dC RT dn dP
(C) = =– (D) All
dt V dt dt
7. The oxidation of iodide ion by arsenic acid, H3AsO4, is described by the balance equation :
3I– (aq) + H3AsO4 (aq) + 2H+ (aq) I3– (aq) + H3AsO3 (aq) + H2O (l)
(a) If – [I–] / t = 4.8 × 10–4 M/s, what is the value of [I3–] /t during the same time interval ?
(b) What is the average rate of consumption of H+ during that time interval ?
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8. For the chemical reaction A  products, the rate of disappearance of A is given by –
dC A
– rA = – = k 1 CA/(1 + k2CA).
dt
At low CA the reaction is of the first-order with rate constant –
(A) k1/k 2 (B) k 1 (C) k1/k2 (D) k1/(k1 + k 2)
9. The rate constant of a second order reaction is 10–2 lit mole–1 sec–1. The rate constant when expressed as
c.c. molecule–1 min–1 is –
(A) 9.96 × 10–22 (B) 9.96 × 10–23 (C) 9.96 × 10–21 (D) 9.96 × 1024
dp A
10. For a gas reaction at T(K) the rate is given by – = k’ p 2A atm/hr. If the rate equation is expressed as :
dt
1 dn A
– rA = – = kC 2A , mol/(litre–hr), the rate constant k is given by– where R = ideal gas law constant, cal/
V dt
g mol. K
(A) k = k’ (B) k = k’ RT (C) k = k’/RT (D) k = k’ (RT)2
DPP NO. # 23
1. Under a given set of experimental conditions, with increase in the concentration of the reactants the rate of
a chemical reaction-
(A) Decreases (B) Increases
(C) Remains unaltered (D) First decreases and then increases.
2. The rate constant of a reaction is equal to rate of reaction-

(A) When concentrations of reactants do not change with time
(B) When concentrations of all reactants and products are equal
(C) At time, t = 0
(D) When concentrations of all reactants are unity
3. If the concentration of the reactants in the reaction 2A + B  C + D is increased by three folds, the rate of
the reaction will be increased by-
(A) 27 times (B) 9 times (C) 64 times (D) 01 times
4. The specific reaction rate of a first order reaction depends on the :

(A) Concentrations of reactants (B) Concentrations of products
(C) Time of reaction (D) Temperature of reactions
5. (1) 0.5 gm Ca + 5 cc of 4N HCl product

(2) 0.5 gm Ca + 10 cc of 2N HCl product
The rate of (1) and (2) reactions are V1 and V2 respectively, then which is true
(A) V1 > V2 (B) V2 > V1 (C) V1 = V2 (D) None of these
6. RCl + NaOH(aq) ROH + NaCl

For the above reaction the experimental rate equation is : v = k1 [RCl]
The rate
(a) Becomes twice by doubling the conc. of NaOH
(b) Becomes half by reducing the conc. of RCl by one half
(c) Increases by raising the temperature
(d) Is not affected by temperature
The correct answer is
(A) b, c (B) a, d (C) a, b (D) d, b

7. The rate law for the reaction : Ester + H+ Acid + Alcohol is
v = k [ester] [H3O+]0
What would be the new rate if
(a) Conc. of ester is doubled (b) Conc. of H+ is doubled
(A) (a) v (b) 2v (B) (a) 2v (b) v (C) (a) 2v (b) 2v (D) None of these
8. The rate of the simple reaction 2NO+O2 2NO2, when the volume of the reaction vessel is doubled –
(A) Will grow eight times of its initial rate (B) Reduce to one-eighth of its initial rate
(C) Will grow four times of its initial rate (D) Reduce to one-fourth of its initial rate
9. The rate expression for the reaction A(g) + B (g)  C(g) is rate = kC 2A CB1/2. What changes in the initial
concentration of A and B will cause the rate of reaction increase by a factor of eight -
(A) CA × 2; CB × 2 (B) CA × 2; CB × 4 (C) CA × 1; CB × 4 (D) CA × 4; CB × 1
10. What is the order of a chemical reaction A + 2B K C, if the rate of formation of ‘C’ increases by a factor of
2.82 on doubling the concentration of ‘A’ and increases by a factor of 9 on tripling the concentration of ‘B’–
(A) 7/2 (B) 7/4 (C) 5/2 (D) 5/4
ANSWER KEY
DPP NO. # 22
1. (C) 2. (C) 3. (B) 7. (D) 5. (C) 6. (A)
7. (a) 1.6 × 10–4 M/s ; (b) 3.2 × 10–4 M/s 8. (B) 9. (A) 10. (B)
DPP NO. # 23
1. (B) 2. (D) 3. (A) 4. (D) 5. (A) 6. (A) 7. (B)
8. (B) 9. (B) 10. (A)

PHYSICAL CHEMISTRY

COURSE NAME : UMANG (UP) DATE : 10.06.2013 to 15.06.2013 DPP NO. 24 to 26

DPP NO. # 24
1. What should be (a) the rate of disappearance of B and (b) the rate of formation of C, if the rate of disappearance
–2
of A for the reaction A + B  2C is 10 mole/litre/second at a particular temperature ?
2. A gaseous reaction : 2A(g) + B(g)  2C(g),
Show a decrease in pressure from 120 mm to 100 mm in 10 minutes. The rate of appearance of C is
(A) 2 mm/min (B) 4 mm/min (C) 10 mm/min (D) 12 mm/min.
dx
3. The term – in the rate expression refers to the
dt
(A) concentration of the reactants (B) increase in concentration of the reactants
(C) instantaneous rate of the reaction (D) average rate of the reaction
4. Which of the following expression can be used to describe the instantaneous rate of the reaction ?
2A + B  A2B
2A + B  A2B
1 d[A] d[A] 1 d[A 2B] 1 d[A] d[B]
(A) – (B) – (C) (D) – .
2 dt dt 2 dt 2 dt dt
5. Which of the following will react at the highest rate ?

(A) 1 mol of A and 1 mol of B in a 1 L vessel (B) 2 mol of A and 2 mol of B in a 2 L vessel
(C) 3 mol of A and 3 mol of B in a 3 vessel (D) All would react at the same rate
6. For the reaction : 4NH3(g) + 5O2(g)  4NO(g) + 6H2O(g)

d[NO] –3 –1 –1
Given : = 3.6 × 10 mol l s
dt
Calculate : (i) rate of disappearance of ammonia (ii) rate of formation of water
d[A] –2 –1
7. In the reaction, A + 2B  6C + 2D, if the initial rate – at t = 0 is 2.6 × 10 m sec , what will be the
dt
d[B]
value of – at t = 0 ?
dt
–2 –1 –2 –1 –2 –1 –2 –1
(A) 8.5 × 10 m sec (B) 2.5 × 10 m sec (C) 5.2 × 10 m sec (D) 7.5 × 10 m sec
8. The dimensions of rate constant of a second order reaction involves :

(A) time and concentration (B) neither time nor concentration
(C) time only (D) concentration only
9. The rate constant of a reaction has same units as the rate of reaction. The reaction is of
(A) zero order (B) first order (C) second order (D) none of these
th
10. The rate constant of n order has units
1–n 1–n –1 1–n 1–n 2 2 –1 1–n n–1 –1
(A) litre mol sec (B) mol litre sec (C) mol1n litren sec (D) mol litre sec
11. On which of the following factors, the rate constant does not depend ?
(A) Temperature (B) Concentration (C) Presence of catalyst (D) Nature of reactants

DPP NO. # 25
1. In a first order reaction, the initial conc. of the reactant was M/10. After 8 minutes 20 seconds the conc.
becomes M/100. What is the rate constant ?
(A) 5 × 10–3 second–1 (B) 2.303 × 10–5 second–1
(C) 2.303 × 10 second
–4 –1
(D) 4.606 × 10–3 second–1
2. Substance A reacts according to a first order rate law with
k = 5.0 × 10–5 s–1. If the initial conc. of A is 1.0 M, the initial rate is
(A) 1 × 10–5 Ms–1 (B) 5.0 × 10–5 Ms–1 (C) 1 × 10–4 Ms–1 (D) 5.0 × 10–4 Ms–1
3. In a certain reaction 10% of the reactant decomposes in one hour, 20% in two hours, 30% in three hours and
so on. Dimension of the velocity constant (rate constant) are-
(A) Hour –1 (B) Mol litre–1hour –1 (C) Litre mol–1 sec–1 (D) Mol sec–1
4. If a graph is plotted between log (a – x) and t, the slope of the straight line is equal to – 0.03. The specific
reaction rate will be :
(A) 6.9 × 10–2 (B) 6.9 (C) 0.69 (D) 6.9 × 10–4

H
5. The hydrolysis of ethyl acetate is a reaction of - CH3COOEt + H2O  CH3COOH + EtOH
(A) First order (B) Third order (C) Second order (D) Zero order
6. The unit of rate constant for a zero order reaction is-

(A) Litre sec–1 (B) Lit mole–1 sec–1 (C) Mol lit–1 sec–1 (D) Mol sec–1
7. A zero order reaction is one whose rate is independent of-

(A) The temperature of the reaction (B) The concentration of the reactants
(C) Proasence of catalyst (D) None of these
8. In the following reaction, rate constant is 1.2 × 10–2 M s–1 A  B. Concentration of B after 10 and 20 min.,
if we start with 10 M of A is :
(A) 7.2 M, 10 M (B) 2.8 M, 7.2 M
(C) 7.2 M, 0 M (D) Can not determine
9. For the following data for the zero order reaction A  products. Calculate the value of k.
Time (min.) [A]
0.0 0.10 M
1.0 0.09 M
2.0 0.08 M
(A) K = 0.02 M min–1 (B) K = 0.01 M min–1
(C) K = 0.03 M min –1 (D) K = 0.04 M min–1
10. A drop of solution (volume 0.10 ml) contains 6 × 10–6 mole of H+, if the rate constant of disappearance of H+
is 1 × 107 mole litre–1 sec–1. How long would it take for H+ in drop to disappear?
(A) 3 × 10–9 sec (B) 1.2 × 10–9 sec (C) 6 × 10–9 sec (D) 7.2 × 10–9 sec
DPP NO. # 26
1. A certain substance A is mixed with an equimolar quantity of substance B. At the end of an hour A is 75%
reacted. Calculate the time when A is 10% unreacted. (Given: order of reaction is zero)
(A) 1.8 hr (B) 1 hr (C)1.5 hr (D) 1.2 hr
2. A first order reaction is 75% completed in 72 min.. How long time will it take for 50% and 87.5% completion:
(A) 36 min., 108 min. (B) 18 min., 54 min. (C) 54 min., 108 min. (D) 18 min., 108 min.
3. The time required for 99.9% of the reaction to take place in a first order reaction is :
(A) 15 t1/2 (B) 5 t1/2 (C) 20 t1/2 (D) 10 t1/2
4. A first order reaction has a rate constant is 1.5 × 10–3 sec–1. How long will 5.0 g of this reactant take to
reduce to 1.25 g.
(A) 124.362 sec (B) 224.362 sec (C) 924.362 sec (D) 724.362 sec

5. A drug is known to be ineffective after it has decomposed 30%. The original concentration of a sample was
500 units/ml. When analyzed 20 months later, the concentration was found to be 420 units/ml. Assuming
that decomposition is of I order, what will be the expiry time of the drug?
(A) 41 (B) 14 (C) 20.5 (D) 82
6. A viral preparation was inactivated in a chemical bath. The inactivation process was found to be first order in
virus concentration. At the beginning of the experiment 2.0 % of the virus was found to be inactivated per
minute . Evaluate k for inactivation process.
(A) 2.3 × 104s1 (B) 6.3 × 104s1 (C) 5.3 × 104s1 (D) 3.3 × 104s1
7. If a reaction A Products, the concentrations of reactant A are C0, aC0, a2C0, a3C0, ............. after time
interval 0, t, 2t, 3t, ............. where a is a constant. Given 0 < a < 1. Hence the relation in k, a and t.
2.303 1 2.303 1 2.303 1 2.303 1
(A) k = log (B) k = log (C) k = log (D) k = log
2t a t a t 2a 3t a
8. The reaction SO2Cl2(g)  SO2(g) + Cl2(g) is a first order gas reaction with k =2.2 × 10–5 sec–1 at 320°C.
What % of SO2Cl2 is decomposed on heating this gas for 90 min.
(A) 11.2% (B) 33.6% (C) 22.4% (D) 44.8%
9. Two substances A (t1/2= 5 mins) and B (t1/2 = 15 mins) follow first order kinetics are taken in such a way that
initially [A]= 4[B]. Calculate the time after which the concentration of both the substance will be equal.
(A) 30 min (B) 5 min (C) 15 min (D) 45 min
10. For a first order reaction, nA  B whose concentration vs time curve is as shown in the figure. If half life
for the reaction is 24 minutes. Find out the value of n.
(A) 1 (B) 2 (C) 3 (D) 4
ANSWER KEY
DPP NO. # 24
1. (a) Rate of disappearance of A = Rate of disappearance of B
–2
= 10 mole/litre/second Ans.
1
(b) Rate of disappearance of A = × Rate of formation of C
2
Rate of formation of C = 2 × Rate of disappearance of A
–3 d[H2 O]
2. (B) 3. (C) 4. (A) 5. (D) 6. 5.4 × 10 = 7. (C)
dt
8. (A) 9. (A) 10. (D) 11. (B)
DPP NO. # 25
1. (D) 2. (B) 3. (B) 4. (A) 5. (A) 6. (C) 7. (B)
8. (A) 9. (B) 10. (C)
DPP NO. # 26
1. (D) 2. (A) 3. (D) 4. (C) 5. (A) 6. (D) 7. (B)
8. (A) 9. (C) 10. (C)

PHYSICAL CHEMISTRY

DPP NO. # 27
1/2 1/2 –1
1. The rate equation of a reaction is K[A] [B] [C] . What should be the order of the reaction ?
2. A first order reaction gets 90% completed in 40 minute. Find out the half-life period of the reaction.
3. Initial concentrations of both the reactants of a second order reaction are equal and 60% of the reaction gets
completed in 3000 seconds. How much time will be taken in 20% completion of the reaction ?
4. A second order reaction requires 70 minutes to change the concentration of reactants from 0.08 M to 0.01 M.
How much time will it require to become 0.04 M.
5. For a reaction, A  B, it has been found that the order of the reaction is zero with respect to A. Which of the
following expression correctly describes the reaction ?
2.303 [A] 0.693 1

(A) k = log 0 (B) [A]0 – [A] = kt (C) t1/2 = (D) t1/2  [A]
t [A] k 0
6. Which of the following graphs is for a second order reaction ?

Rate
Rate
Rate
Rate
(A) (B) [ (C) (D)
2 2 2
[A]
2
[A] [A] [A]
7. For a first order reaction, t0.75 is 1386 seconds. Therefore, the specific rate constant is
–1 –1 –3 –1 –2 –1 –4 –1
(A) 10 s (B) 10 s (C) 10 s (D) 10 s
0.693
8. t1/2 of first order reactions is given by , t3/4 would be equal to
k
0.693 0.346 1.386 0.924

(A) (B) (C) (D)
k k k k
10. The t1/2 of a first order reaction is found to be 2 minutes. The percentage of the reactant left after
360 seconds is :
(A) 12.5 (B) 25 (C) 15 (D) 7.5

11. Which of the following is correct graph for the reaction ?
H2
Ni
log a
log a
log a
(A) (B) a (C) (D)
log t0.5 log t0.5 t0.5 log t0.5
12. Following is the graph between log T1/2 and log a(a–initial concentration) for a given reaction at 27ºC. Hence order
is
log T1/2
45º
log a
(A) 9 (B) 1 (C) 2 (D) 3
DPP NO. # 28
1. Which curve represents zero order reaction ?
(A) (A) (B) (A) (C) (A) (D) (A)
t t t t
2. The half life period t1/2 is independent of initial concentration of reactant when the order of reaction is
(A) Negative (B) 0 (C) 1 (D) Fractional
3. In the decomposition of N2O5, the plot between the reciprocal of concentration of the reactant and the time
was found to be linear as shown in figure. Determine the order of reaction.
1
Conc.
Time

4. For a reaction A + 2B  C + D, the following data were obtained
Expt. Initial concentration Initial Rate of formation of D
(miles litre–1) (moles litre–1 min–1)
[A] [B]
1. 0.1 0.1 6.0 × 10–3
2. 0.3 0.2 7.2 × 10–2
3. 0.3 0.4 2.88 × 10–1
4. 0.4 0.1 2.4 × 10–2
The correct rate law expression will be :
(A) Rate = k [A] [B] (B) Rate = k [A] [B]2 (C) Rate = k [A]2 [B]2 (D) Rate = k [A]2 [B]
5. For the reaction, 2A + B  Products, the following initial rates were obtained at various initial concentrations:
[A] [B] Rate (mol –1 sec–1)
0.1 M 0.2 M 0.46
0.2 M 0.2 M 1.84
0.2 M 0.1 M 0.92
The rate law for the reaction is :
(A) Rate = k [A]2 [B]0 (B) Rate = k [A] [B] (C) Rate = k [A]2 [B] (D) Rate = k [A] [B]2
6. Form the data given below for the reaction : A + B  Products

[A] [B] Rate
0.35 M 1.28 M 0.032 Ms–1
0.35 M 0.64 M 0.008 Ms–1
0.70 M 0.64 M 0.016 Ms–1
the expression for rate law is :
(A) rate = k [A]0 [B] (B) rate = k [A] [B] (C) rate = k [A]2 [B] (D) rate = k [A] [B]2
7. The following kinetic data are provided for a reaction between A and B :
Concentration Concentration Rate of reaction
of A/(M) of B/(M) (M min–1)
0.50 0.02 1.15 × 10–4
0.50 0.04 2.30 × 10–4
0.01 1.00 2.30 × 10–6
0.02 1.00 0.92 × 10–5
Then value of the rate constant for the above reaction is equal to :
(A) 1.15 × 10–4 dm3/mol min (B) 2.30 × 10–4 dm6/mol2 min
(C) 2.30 × 10–2 dm6/mol2 min (D) 1.15 × 10–2 dm3/mol min
8. The following data pertain to reaction between A and B ;

S.No. [A] [B] Rate
mol. l–1 mol. l–1 mol. l–1. t–1
I 1 × 10 –2
2 × 10–2
2 × 10–4
II 2 × 10–2 2 × 10–2 4 × 10–4
III 2 × 10–2 4 × 10–2 8 × 10–4
Which of the following inference(s) can be drawn from the above data
[a] Rate constant of the reaction is 10–4 [b] Rate law of the reaction is k [A] [B]
[c] Rate of reaction increases four times on doubling the concentration of both the reactants
Select the correct answer
Codes :
(A) a, b and c (B) a and b (C) b and c (D) c alone

9. Following data are obtained for the reaction A + B  product
[A] [B] Rate
(mole l–1) (mole l–1) (mole l–1 s–1)
4 × 10–2 4 × 10–2 2 × 10–2
4 × 10 –2
8 × 10 –2
4 × 10–2
2 × 10–2 8 × 10–2 2 × 10–2
The reaction confirms the rate law
d[B] d[B] d[B] d[A]

(A) – = k [A] (B) – = k [A] [B]2 (C) – = k [A] [B] (D) – = k [B]
dt dt dt dt
10. When the rate is determined by the change in concentration of two different reactants, then the kinetic
equation may be expressed as
2.303 (a  x)b 2.303 (a  x)

(A) k2 = log (B) k2 = log
(a  b)t (b  x)a (a  b)t (a  x)
2.303 (a  x) 1 x
(C) k2 = log (D) k2 = ×
(a  b) (b  x) t (a  x)
11. In the reaction A + B  C + D, the concentration of A and B are equal and the rate of the reaction is –
Rate = k[A] [B]. The integrated rate equation for this reaction is :
x xa 1 x 1 x
(A) k = t (a – x) (B) k = (C) k = . (D) k = .
(a – x) t a(a – x) t a(x – a)
Answer Key
DPP NO. # 27
1 1 1/2 0.693
1. n= + – 1 (zero) 2. T = = 10.3 minutes 3. t = 500 second
2 2 5.757  10 2
4. t = 10 minutes 5. (B) 6. (C) 7. (A) 8. (C) 10. (A)
11. (A) 12. (C)

DPP NO. # 28
1. (C) 2. (C)
3. The reaction is of second order, because for II order,
1 x 1 x 1
K= . or t= . or time (t) vs. graph is linear
t a(a – x) K a(a – x) conc.
4. (B) 5. (C) 6. (D) 7. (C) 8. (C) 9. (C) 10. (A)
11. (C)

PHYSICAL CHEMISTRY


DPP NO. # 29
1. Prove with the help of the following data that hydrolysis of H2O2 is a first order reaction. Initial
concentration in the reaction 25.0.
Time, t 10 20 30
(in minutes)
V 20.0 15.7 12.5
2. When the initial concentration of a reactant was doubled, its half life become half, What should be the order
of the reaction ?
3. The decomposition of H2O2 can be followed by titration with KMnO4 and is found to be a first order reaction.
The rate constant is 4.5×10-2 minute–1. In an experiment, the initial titre value was 25 ml. The titre value will
be 5 ml after a lapse of-
loge 5
(A) 4.5×10-2 × 5 minutes (B) minutes
4.5  10 2
loge 5 / 4
(C) (D) None of the above
4.5  10 2
4. Azo isopropane decomposes according to the equation :

(CH3)2CHN = NCH(CH3)2 (g) 
250– 290º
 N2(g) + C6H14(g)
It is found to be a first order reaction. If initial pressure is P0 and pressure of the mixture at time t is (Pt) then
rate constant (k) would be :
2.303 P0 2.303 P – Pt
(A) k = log (B) k = log 0
t 2P0 – Pt t P0
2.303 P0 2.303 2P0

(C) k = log (D) k = log
t P0 – Pt t 2P0 – Pt
5. In the Wilhelmey equation of a first order reaction Ct = C0e–kt if the initial concentration C0 is increased m times
then
(A) The value of k will increase m times (B) The value of k will decrease m times
(C) The value of k will remains unchanged (D) None of these
6. The data for the dissociation of ammonium nitrate are as under –

Volume of N2 in cm3 6.25 9.0 11.42 13.65 35.05
Time in min. 10 15 20 25 
The reaction is of
(A) Zero order (B) First order (C) Second order (D) Third order

7. In a second order reaction 20% of a substance is dissociated in 40 minutes. The time taken by the 80% of
its dissociation is
(A) 160 minutes (B) 640 minutes (C) 200 minute (D) 320 minute
8. Inversion of a sugar follows first order rate equation which can be followed by noting the change in rotation of
the plane of polarization of light in the polarimeter. If r, rt and r0 are the rotations at t = , t = t and t = 0, then,
first order reaction can be written as
1 rt – r 1 r0 – r 1 r – r0 1 r – rt
(A) k = t log r – r (B) k = t ln r – r (C) k = t ln r – r (D) k = t ln r – r
0  t   t  0
9. The half-life period for a reaction at initial concentration of 0.5 and 1.0 moles litre–1 are 200 sec and 100 sec
respectively. The order of the reaction is
(A) 0 (B) 1 (C) 2 (D) 3
10. The decomposition of N2O5 is a first order reaction represented by : N2O5  N2O4 + 1/2 O2
After 15 minutes the volume of O2 produced is 9 ml and at the end of the reaction 35 ml. The rate constant is
equal to
1 35 1 44 1 44 1 35
(A) ln (B) ln (C) ln (D) ln
15 44 15 26 15 35 15 26
11. A(g)  B(g) + C(g)

d [A]
– = k [A]
dt
At the start pressure is 100 mm and after 10 min , pressure is 120 mm. hence , rate constant (min–1) is :
2.303 120 2.303 100 2.303 100 2.303 100
(A) log (B) log (C) log (D) log
10 100 10 20 10 80 10 120
12. Show that for a first order reaction , R  P the concentration of product can be represented as
a function of time by , [P] = at + bt2 + ct3 + ------ and express a , b and c in terms of [R]0 and K.
DPP NO. # 30
1. For a homogeneous gaseous reaction , A  B + C + D, the initial pressure was P0 while pressure
after time t was P. Derive an expression for rate constant K in terms of P0, P and t. assume I order
reaction.
2. Acetone on heating gives CO and other hydrocarbons at 600°C. The reaction obeys I order kinetics
w.r.t. acetone concentration. The half life period is 81 sec. Calculate the time in which acetone taken in
a container at 600 ºC reduces its pressure from 0.5 atm to 0.4 atm.
3. Dimethyl ether gaseous phase decomposition is :

CH3OCH3  CH4 + H2 + CO at 750 K having rate constant 6.72 × 10–3 min–1. Calculate the time in
which initial pressure of 400 mm in closed container becomes 750 mm.
4. The decomposition of Cl2O7 at 400 K in gaseous phase to Cl2 and O2 is of I order reaction. After 55 sec
at 400 K, the pressure of reaction mixture increase from 0.62 to 1.88 atm. Calculate the rate constant
of reaction. Also calculate the pressure of reaction mixture after 100 second.
5. In the vapour phase decomposition of ethylene oxide, C2H4O  CH4 + CO at 414.5ºC, the initial
pressure and the pressure after 5 minute were 116.51 mm and 122.56 mm of Hg respectively. If the
reaction follows I order kinetics, what must be the pressure after 12 minutes?
6. Calculate the partial pressures of reactants and products , when azomethane decomposes at an initial
pressure of 200 mm for 30 minute according to (CH3)2 N2  C2H6 + N2. The rete constant is
2.5 ×10–4 sec –1.

7. Rate constant of a first order reaction A  B is 6.93 ×10–2 minute. If initial concentration of reactant
is 1 M . Then calculate :
(i) Initial rate (ii) Rate after 600 seconds
(iii) Rate after 75 % of the reaction is completed (iv) Rate after 30 minutes.
8. In a first order reaction concentration of reactant decreases from 10 M to 2.5 M in 500 seconds.
Calcualte :
(i) t1/2 of the reaction
(ii) rate of reaction when concentration is 5 M.
9. Rate constant of a first order reaction is 10–3 sec. Calculate time in seconds when concentration is
changing from :
(i) 2 M to 0.25 M (ii) 16 M to 1 M
(iii) 6.4 M to 1.6 M (iv) 4 M to 0.125 M
10. The decomposition of N 2 O 5 in chloroform was followed by measuring the volume of O 2 gas
evolved; 2N2O5 2N2O4 + O2 (g). The maximum volume of O 2 gas obtainable was 100cm 3 . In
500 minutes, 90cm 3 of O 2 were evolved. Calculate the first order rate constant of the reaction.
11. The specific rate constant of the decomposition of N2O5 is 0.008 min–1. The volume of O2 collected after
20 minute is 16 mL. Find the volume that would be collected at the end of reaction. NO2 formed is
dissolved in CCl4.
12. The acid catalysed hydrolysis of an organic compound A at 30ºC has half life of 100 minute when
carried out in a buffer solution of pH = 5 and 10 minute when carried out at pH = 4. Both the times the
half life are independent of the initial concentration of A. If the rate of reaction is given by : rate = k[A]m
[H+]n, what are the values of m and n?
13. In the inversion of cane sugar in presence of an acid, the following polarimeter readings are obtained
Time in minute 0 30 90 230 
Rotation in degree +46.75 +41.0 +30.75 +12.75 –18.75
Calculate rate constant.
ANSWER KEY
DPP NO. # 29
2. n=2 3. (B) 4. (A) 5. (C) 6. (B) 7. (B) 8. (C)

9. (C) 10. (D) 11. (C)
DPP NO. # 30
2.303 2P0
1. K= log10 2. 26 sec 3. 85.64 4. 1.58 ×10–2, 233 atm
t 3P0  P
'
5. 130.41 6. P('CH3 ) 2 N 2 = 127.55 mm , PC2H6 = 72.45 mm
7. (i) 6.93 × 10–2 M/min. (ii) 3.465 ×10–2 M/min (iii) 1.7325 × 10–2 M/min. (iv) 8.67 × 10–3
8. (i) 250 seconds(ii) 0.01386 M sec –1
9. (i) 2079 sec (ii) 2772 sec, (iii) 1386 sec. (iv) 3465 sec.
11. 108.23 ml 12. k = 3.27 × 10 min–1
–3
13. k = 3.12 × 10–3 min–1

PHYSICAL CHEMISTRY


DPP NO. # 31
–5 –1
1. Value of rate constant for a first order reaction at 500 K is 1.60 × 10 second , whereas at 600 K, it is
–3 –1
6.36 × 10 second . Find out the activation energy of the reaction.
2. An exothermic reaction, X  Y, has an activation energy 30 kJ mol–1. If energy change (E) during the
reaction is – 20kJ, then the activation energy for the reverse reaction is :
(A) –30kJ (B) 20 kJ (C) 50 kJ (D) 10 kJ
3. An endothermic reaction, A  B, has an activation energy as x kJ mol–1 of A. If energy change of the reaction
is y kJ, the activation energy of reverse reaction is
(A) – x (B) x – y (C) x + y (D) y – x
4. Which of the following relations is correct ?

Ea/RT Ea Ea Ea
(A) k = A e (B) ln k – ln A = (C) ln A – ln k = (D) ln A – ln k = –
RT RT RT
5. Which of the following expression give the effect of temperature on the rate constant ?
(A) ln A = RT ln Ea – ln k (B) ln k = ln A – Ea/RT
(C) k = AEa/RT (D) None of these
1
6. The plot of log k vs helps to calculate
T
(A) Energy of activation (B) Rate constant of the reaction
(C) Order of the reaction (D) Energy of activations as well as the frequency factor
7. For A + B  C + D; H = 20 kJ mol–1 ; the activation energy of the forward reaction is 85 kJ/mol. Calculate
activation energy of the reverse reaction.
8. Find the activation energy [kJ/mol] for the reaction, A(g) + B(g)  C(g) + D(g). From the plot given below :
100
C+D
80
60
+B
40 A
20
0
Reaction course
(A) 20 (B) 60 (C) 40 (D) 80
9. The rate constant of a reaction is 1.5 × 10-3 at 25oC and 2.1×10-2 at 60oC. The activation energy is :
35 2.1 10 2 298  333 21
(A) R log e (B) R log e
333 1.5  10  2 35 1 .5
298  333 298  333 2.1
(C) R log e 2.1 (D) R loge
35 35 1.5
10. At 290K the rate constant of a reaction is 3.2 × 10–3. Its value at 310 K will be :
(A) 1.28 × 10–2 (B) 3.2 × 10–4 (C) 9.6 × 10–4 (D) 6.4 × 10–3

DPP NO. # 32
1. The rate of a certain reaction increase by 2.3 times when the temperature is raised from 300 K to 310K. If K
is the rate constant at 300K then the rate constant at 310 K will be
(A) K (B) 3K2 (C) 2K (D) 2.3K
2. According to Arrehenius equation, rate constant of a chemical reaction is equal to-
(A) Ae E a / RT (B) Ae Ea / RT (C) A 

1 (D) A 2  e Ea
2
/ RT
Ea / RT 2
e
1
3. In Arrehenius equation if a graph is plotted between log k and , the slope of the curve will be :
T
Ea Ea Ea Ea
(A) – (B) – 2.303 R (C) (D) 2.303 R
R R
1 1
4. The slope of the line for the graph of log k versus for the reaction, N2O5  2NO2 + O2 is – 5000.
T 2
Calculate the energy of activation of the reaction - (kJ K–1 mol—1)
(A) 95.7 (B) 9.57 (C) 957 (D) None
5. For the decomposition of N2O5 (g), it is given that 2N2O5  4NO2(g) + O2(g) ; Activation energy Ea,
1
N2O5(g)  2NO2(g) + O (g) ; Activation energy Ea’ then :
2 2
(A) Ea = Ea’ (B) Ea > Ea’ (C) Ea < Ea’ (D) Ea = 2Ea’
6. For a reaction, the rate constant is expressed as, k = A.e–40000/T . The energy of the activation is :
(A) 40000 cal (B) 88000 cal (C) 80000 cal (D) 8000 cal
2500

7. A reaction rate constant is given by : k = 1.2 × 1014 e RT sec–1. It means
(A) Log k versus log T will give a straight line with a slope as 25000
(B) Log k versus log T will give a straight line with a slope as –25000
(C) Log k versus T will give a straight line with a slope as –25000
(D) Log k versus 1/T will give a straight line
8. An exothermic reaction A  B has an activation energy of 17 kJ per mole of A. The heat of the reaction is 40
kJ. Calculate the activation energy for the reverse reaction B  A :
(A) 60kJ (B) 57kJ (C) 75kJ (D) 90kJ
9. In a reaction, the threshold energy is equal to-

(A) Activation energy
(B) Activation energy - normal energy of reactants
(C) Activation energy + normal energy of reactants
(D) Normal energy of reactants
10. The temperature coefficient of most of the reactions lies between-

(A) 1 and 3 (B) 2 and 3 (C) 2 and 4 (D) 1 and 4
ANSWER KEY
DPP NO. # 31
5
1. Ea = 1.49 × 10 2. (C) 3. (B) 4. (C) 5. (B) 6. (D)
7. 65 kJ mol–1 8. (B) 9. (D) 10. (A)
DPP NO. # 32
1. (D) 2. (A) 3. (B) 4. (A) 5. (A) 6. (C) 7. (D)
8. (B) 9. (C) 10. (B)

TARGET CH EMISTRY
DAILY PRACTICE PROBLEMS

COURSE NAME : UMANG (UP) DATE : 08.07.2013 to 13.07.2013 DPP NO. 33 TO 34

DPP No. # 33
1. A reaction is represented by-
K1
A  K2
 B (slow) and A + B 
 C (fast) where K1 and K2 and the rate constants of the mechanistic
steps. The rate of production of C will be given by-
(A) K1[A] [B] (B) K1 [A] (C) K1 K2 [A] (D) K2 [A] [B]
2. The mechanism of the reaction :

k1 k2
2NO + O2  2NO2 is- NO + NO N2O2 (fast) ; N2O2 + O2  2NO2 (slow)
k–1
The rate constant of the reaction is
 k1 
(A) k2 (B) k2k1 (k–1) (C) k2k1 (D) k2  k 
 –1 
3. In the sequence of reaction :

k1 2 k k
A  B   C 
3
 D, k3 > k2 > k1 then the rate determining step of the reaction is :
(A) A  B (B) C  D (C) B  C (D) A  D
k1
Y
a d[x]
4. For a reaction (aX , is equal to :
x )
k2
dt
Z
(A) k1 (a – x) – k2 (a – x) (B) k2 (a – x) – k1 (a – x)
(B) k1 (a – x) + k2 (a – x) (D) –k1 (a – x) – k2 (a – x)
5. Dinitrogen pentaoxide decomposes as follows :
d N2O5  dNO2  d  O2 
N2O5  2NO2 + ½ O2. If   k ' N2O5  ;  k'' N2O5  ;  k ''' N2 O5  .
dt dt dt
Derive a relation in k’ , k” and k”’
k ' k " k "' k"

(A)   (B) (k’)2 = k” = k”’ (C) 2k’ = k” = 2k”’ (D) k’ = = 2k”’
2 3 4 2
6. The incorrect statement is-

(A) All the collisions between reactant molecules do not lead to a chemical change
(B) A zero order reaction proceeds at a constant rate independent of concentration or time
(C) Fast reactions have low activation energies
(D) In a first order reaction, the reaction ideally takes finite time to be completed

1 K 2 K d[B]
7. For a reaction A  B   C. If the reaction are of Ist order then is equal to :
dt
(A) – k2[B] (B) + k [A] (C) k1 [A] – k2 [B] (D) k1 [A] + k2 [B]
8. The reaction : 2A 2B + C occurs by the mechanism :

K1 K2
A B + X (slow) ....... (1) A+X B + C(fast) ....... (2)
Which of the following step is incorrect ?
(A) Molecularity of the reaction is one (B) The order of the reaction with respect to A is two
(C) The rate law is : v = k1 [A] (D) k2 > k1
9. The mechanism of the reaction : A + 2B + C D is

(step-1) (fast) equilibrium A + B X (step-2) (slow) X + C Y
(step-3) (fast) Y + B D
Which rate law is correct
(A) v = k[C] (B) v = k [A] [B]2 [C] (C) v = k [A] [B] [C] (D) v = k [D]
DPP No. # 34
1. The mechanism of the reaction : 2X + Y C + D

K
may be written as : 2X X2 (fast), X2 + Y Z + P (slow)
The rate of the reaction would be equal to :
(A) k[X]2 [Y] (B) k[X]2 (C) k[Y] (D) k[X]2 [X2]
2. Mechanism of the reaction 2NO + Cl2 2NOCl may be written as

K
2NO [NO]2 ............. (fast)
k
(NO)2 + Cl2 2NOCl(slow)
Rate equation would be :
(A) kK[NO]2 [Cl2] (B) kK[NO]2 [Cl2] (C) kK[Cl2] (D) kK[NO] [Cl2]
3. The mechanism of the reaction : A + B C is as under :

K1
A D (slow), D+B C (fast)
Choose the set showing rate equation and order with respect to A and B :
(A) k1 [A], 1, 0 (B) k1 [A]2, 0, 1 (C) k1 [A] [B], 2, 0 (D) k1 [A]2, 2, 0
4. The mechanism of the reaction :

Nu– + R – X R – Nu + X– is :
Nu– + R – X [Transition state] (slow)
[Transition state] Nu – R + X– (fast)
The rate of reaction can be increased by
(A) Increasing the conc. of Nu– only (B) Increasing the conc. of R – X only
(C) Increasing the conc. of both Nu– and R – X (D) Decreasing the conc. of both Nu– and R – X
5. True statement is-

(A) Positive catalyst increases the rate of a reaction
(B) During the course of the reaction, specific reaction rate remains constant.
(C) Rate constant always increases with rise in temperature whether the reaction is endothermic or exo-
thermic
(D) All are correct

6. When ethyl acetate was hydrolysed in presence of 0.1 N HCl, the rate constant was found to be
5.40 ×10–5 sec–1, but when 0.1 N H2SO4 was used for hydrolysis, the rate constant was found to be
6.20 × 10–5 sec–1 Thus
(A) H2SO4 is stronger than HCl (B) H2SO4 is weaker than HCl
(C) H2SO4 and HCl both have the same strength (D) None of these
7. If the surface area of the reactant is increased then the order of reaction :
(A) Increases (B) Decreases
(C) Remains unaffected (D) Sometimes increases and sometimes decreases
8. A chemical reaction is catalysed by a catalyst X. Hence X [CPMT 1995]

(A) Increases activation energy of the reaction (B) Does not affect equilibrium constant of the reaction
(C) Decreases the rate constant of the reaction (D) Reduces enthalpy of the reaction
9. A catalyst only [AFMC 1995]

(A) Decreases activation energy (B) Increases activation energy
(C) Both of them (D) Comes to equilibrium
ANSWER KEY
DPP No. # 33
1. (B) 2. (D) 3. (A) 4. (D) 5. (D) 6. (D) 7. (C)
8. (B) 9. (C)
DPP No. # 34
1. (A) 2. (B) 3. (A) 4. (C) 5. (D) 6. (A) 7. (C)

8. (B) 9. (C)


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PHYSICAL CHEMISTRY

TARGET DAILY PRACTICE PROBLEMS

JEE (ADVANCED) : 2014 DPP

* Marked Questions are having more than one correct option.

3. For the reaction : N2(g) + 3H2(g) 2NH3(g)

5. In the following reaction : x A  yB

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2. The rate constant of a reaction is equal to rate of reaction-

4. The specific reaction rate of a first order reaction depends on the :

5. (1) 0.5 gm Ca + 5 cc of 4N HCl product

6. RCl + NaOH(aq) ROH + NaCl

ETOOS ACADEMY Pvt. Ltd

8. (B) 9. (B) 10. (A)

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JEE (ADVANCED) : 2014 DPP

* Marked Questions are having more than one correct option.

5. Which of the following will react at the highest rate ?

6. For the reaction : 4NH3(g) + 5O2(g)  4NO(g) + 6H2O(g)

8. The dimensions of rate constant of a second order reaction involves :

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6. The unit of rate constant for a zero order reaction is-

7. A zero order reaction is one whose rate is independent of-

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(A) 1 (B) 2 (C) 3 (D) 4

ETOOS ACADEMY Pvt. Ltd

JEE (ADVANCED) : 2014 DPP

* Marked Questions are having more than one correct option.

2.303 [A] 0.693 1

6. Which of the following graphs is for a second order reaction ?

(A) (B) [ (C) (D)

0.693 0.346 1.386 0.924

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log t0.5 log t0.5 t0.5 log t0.5

(A) 9 (B) 1 (C) 2 (D) 3

1. Which curve represents zero order reaction ?

(A) (A) (B) (A) (C) (A) (D) (A)

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6. Form the data given below for the reaction : A + B  Products

8. The following data pertain to reaction between A and B ;

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d[B] d[B] d[B] d[A]

2.303 (a  x)b 2.303 (a  x)

4. t = 10 minutes 5. (B) 6. (C) 7. (A) 8. (C) 10. (A)

11. (A) 12. (C)

3. The reaction is of second order, because for II order,

4. (B) 5. (C) 6. (D) 7. (C) 8. (C) 9. (C) 10. (A)

ETOOS ACADEMY Pvt. Ltd

JEE (ADVANCED) : 2014 DPP

* Marked Questions are having more than one correct option.

4. Azo isopropane decomposes according to the equation :

2.303 P0 2.303 2P0

6. The data for the dissociation of ammonium nitrate are as under –

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11. A(g)  B(g) + C(g)

3. Dimethyl ether gaseous phase decomposition is :

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2. n=2 3. (B) 4. (A) 5. (C) 6. (B) 7. (B) 8. (C)

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JEE (ADVANCED) : 2014 DPP