SECTION - I : STRAIGHT OBJECTIVE TYPE

4.1 What is order with respect to A, B, C respectively

[A] [B] [C] rate (MFsec.)
0.2 0.1 0.02 8.08 x 10-3
0.1 0.2 0.02 2.01 x 104
0.1 1.8 0.18 6.03 x 10-3
0.2 0.1 0.08 6.464 x 10-2

(A) –1, 1, 3/2 (B) –1, 1, ½ (C) 1, 3F2,–1 (D) 1,–1,. 3F2

4.2 N20 5 ---* 2NO 2 + 0 2

When N205 decompose, its t12 does not change with its changing pressure during the
reaction, so which one is the correct representation for "pressure of 2NO2" vs lime°
during the reaction when initial N205 is equals to Po.

4.3 In a hypothetical reaction

A(aq) 2B(aq) + C(aq) (1st order decomposition)
'A' is optically active (dextro-rototory) while 'B' and 'C' are optically inactive but 'B' takes part
in a titration reaction (fast reaction) with H202. Hence the progress of reaction can be
monitored by measuring rotation of plane of plane polarised light or by measuring
volume of H202 consumed in titration.
In an experiment the optical rotation was found to be 0 = 30° at t = 20 min and 8 =15° at t=
50 min. from start of the reaction. If the progress would have been monitored by titration
method, volume of H202 consumed at t = 30 min. (from start) is 30 ml then volume of H202
consumed at t = 90 min will be:
(A) 60 ml (B) 45 ml (C) 52.5 ml (D) 90 ml
44 The elementary reaction A + B  products has k = 2 x 10-5 M-1 S-1 at a
temperature of 27°C. Several experimental runs are carried out using stoichiometric
proportion. The reaction has a temperature coefficient value of 2.0. At what temperature
should the reaction be carried out if inspite of halving the concentrations,
n 6
the rate of reaction is desired to be 50% higher than a previous run. (Given =
n 2
2.585).
(A) 47 °C (B) 53 °C (C) 57 °C (D) 37 °C

4.5 At a certain temperature, the first order rate constant k1 is found to be smaller than
the second order rate constant k2. If the energy of activation E1 of the first order reaction
is greater than energy of activation E2 of the second order reaction, then with increase in
temperature.
(A) k1 will increase faster than k2, but always will remain less than k2.
(B) k2 will increase faster than k1
(C) k1 will increase faster than k2 and becomes equal to k2.
(D) k1 will increase faster k2 and becomes greater than k2.

4.6 For the system A2(g) + B2(g) 2AB(g), AH = – 80 KJ/ mole

If the activation energy for the forward step is 100 kcal /mole. What is the ratio of
temperature at which the forward and backward reaction shows the same %
change of rate constant per degree rise of temperature ? (1 cal = 4.2 J)
.(A) 0.72 (B) 0.84 (C) 0.42 (D) 1

47.
All reactions are of Ist order
At time t = ti (ti > 0)
[B ]
  . Therefore at
[C ]
time t = t2 (where t2 > ti)
[C]
 β which of the following is correct.
[D]
(A) a > 13 (B) a = 13 (C) a13 =0.4 (D) a + 8 = 0.4

4.8 In the formation of HBr from H2 & Br2 , following mechanism is observed.
(A) Br 2 2 Br • Equilibrium step

(B) H 2 + Br   HBr + H• Slow step
(C) H• + Br2   HBr + Br• Fast step
Calculate the rate of reaction, it concentration of hydrogen is twice that of bromine and
the rate constant is equal to one rutherford. If conc. of bromine is 1 M.
(A) 2 x 106 dps (B) 10 X 109 dps (C) 20.2 X 1010 dps (D) 4 x 102 dps
4.9 For a two step reaction
K1
K3
A R+B R + C  Products
K2
(where, R is a reactive intermediate whose concentration in maintained at some low
steady state throughout the reaction). If the concentration of C is very high then the
order of reaction will be.
1
(A) 1 (B) 2 (C) 0 (D)
2
4.10 A graph between log t112 and log a (abscissa) a being the initial concentration of
A in the reaction For reaction A  4 Product, is the rate law is

– d[A] – d[A] – d[A] – d[A]

. (A) =K (B) =K[A] (C) =K[A]2 (D) =K[A]3
dt dt dt dt

4.11 The reaction A (g) + B (g) C (g) + D (g) is elementry 2nd order reaction. When
started with equimolar amounts of A and B, at equilibrium, it is found that the
concentration of A is twice that of C. Specific rate for forward reaction is 2 x 10-3 mol –-1
Lsec-1. The specific rate constant for backward reaction is :
(A) 5.0 x 10-4 M-1 see (B) 8 x 10-3 M-1 sec-1
(C) 1.5 x 1021A-4 sec-1 (D) none of these.

4.12 For the reaction R – X + OH- ROH + X- The Rate is given of

Rate = 5.0x 10-5[R – X [OH-] + 0.20x 10-5[R – X] what percentage R – X Reaction by
SN2 mechanism when [OH-–] = 1.0x 10-2 M
(A) 96.1 % (B) 3.9 % (C) 80 % (D) 20%

4.13 For a 1st order reaction (gaseous) (cont. V, T)

a A 
 4 (b 1) B + 1 C (with b > a) the pressure of the system
b 
rose by 50  –1 % in a time of 10 min. The half life of the reaction is therefore.
a 
(A) 10 min (B) 20 min (C) 30 min (D) 40 min.
4.14 For a certain reaction the variation of the rate constant with temperature is given by
the equation
(ln3)t
In Ft = In For + (t  0°C)
10
The value of tile temperature coefficient of the reaction is
(A) 0.1 (B) 1.0 (C) 10 (D) 3

4.15 The high temperature (  1200K) decomposition of CH3COOH) occurs as follows

as per simultaneous 1St order reactions.
k1
CH3COOH   CH4 + CO2
k2
CH3COOH   CH2C0 + H20
What would be the % of CH4 by mole in the product mixture (excluding CH3COOH)?
50k1 100k1
(A) (B)
k1+k 2  k1+k 2 
200k1
(C) (D) it depends on time
k1+k 2 

4.16 A reaction takes place in three steps ; the rate constants are Br k2 and k3.The
kk
overall rate constant K  1 3 . If energies of activation are 40 , 30 and 20 kJ, the
k2
overall energy of activation is (assumming 'A' to be constant for all )
(A) 10 (B) 15 (C) 30 (0) 60

417 The inversion of cane sugar proceeds with half life of 600 minute at pH = 5 for any
concentration of sugar, However at pH = 6, the half life changes to 60 minute, The
rate law expression for sugar inversion can be written as
(A) r = k [sugar]2 [H+]° (B) r = k [sugar]' [Hl°
2 + 1
(C) r = k [sugar] [H ] (D) r = k[sugar]°[H+]-1

4.18 Some graph are sketch for the reaction A  B (assuming different orders).Where
' α' represent the degree of dissociation.
.

The order of reaction is respectively.

. (A) 0, 1, 2 (B) 1, 0, 2 (C) 2, 0, 1 (D) 1, 2, 0
4.19 Compounds A and B react with a common reagent with first order kinetics in both
cases. If 99% of A must react before 1% of B has reacted. What is the minimum
ratio for their respective rate constants?
(A) 916 (B) 229 (C) 500 (D) 458

4.20 The activity per ml of a solution of radioactive substance is x. How much water be
added to 200 ml of this solution so that the acitivity falls to x/20 per ml after 4 half-
lives ?
(A) 100 ml (B) 150 ml (C) 80 ml (D) 50 ml.

4.21 A hypothetical reaction :

A2 + B2   2AB Follows mechanism as given below :
KC
A2 A + A (fast) (Kc – is equilibrium constant)

K
A + B2  1
 AB + B…………..(slow) (k1- rate constant)
K2
A+B AB (fast) (k2 ,k3 - are rate constant)
K3
The order of overall reaction is :
(A) 2.5 (B) 1 (C) 3/2 (D) Zero

4.22 For the decomposition of H202(aq) it was found that VO2 (t =15 min.) was 100 mL
(at 0°C and 1 atm) while VO2 (maximum) was 200 mL (at 0°C and 2 atm). If the
(cM)
same reaction had been followed by the titration method and if VKMnO 4
(t = 0) had
(cM)
been 40 mL, what would VKMnO 4
(t = 15 min) have been ?
(A) 30 mL (B) 25 mL (C) 20 mL (D) 15 mL

4.23 The high temperature (z, 1200K) decomposition of CH3COOH(g) occurs as follows
as per simultaneous 1St order reactions.
k1
CH3COOH   CH4 + CO2
k2
CH3COOH   CH2CO + H20
What would be the % of CH4 by mole in the product mixture (excluding CH3COOH)?
50k1 100k1
(A) (B)
(k1  k2 ) (k1  k2 )
200k1
(C) (D) it depends on time
(k1  k2 )
K1 K2
4.24 For the system A B, A C which was started with only
K–1 K–2
A the equilibrium concentration [A]eq is correctly related to [B]eq and [C]eq. as:
 k –1[B]eq +k –2 [C]eq k –1[B]eq – k –2 [C]eq
(A) (B)
 k1+k 2  k1 – k 2 
k –1[B]eq +k –2 [C]eq k –1[B]eq – k –2 [C]eq
(C) (D)
 k1 – k 2   k1+ k 2 
4.25 A certain reaction A -3 B follows the given concentration (Molarity)-time graph. Which of the
following statement is true?

(A) The reaction is second order with respect to A

(B) The rate for this reaction at 40 second will be approximately 3.5 × 10–3 Ms–1
(C) The rate for this reaction at 80 second will be 1.75 x 10-3 M s–1
(D) The [B] will be 0.25 Matt = 60 second

4.26 The activation energies of two reactions are Ea and Ea’ with Ea > Ea’ If temperature of
the reacting systems is increased from T1 to T2, predict which of the following
alternatives

k1 k 2 k k k k k k
.(A) = (B) 1  2 (C) 1  2 (D) 1  2 2
k1 k 2 k1 k 2 k1 k 2 k1 k2
4.27 A simple mechanism for enzyme-catalyzed reaction is given by the following of
equations

E + S ES
(enzyme) (reactant) (intermediate-1)
ES EP
(intermediate-1) (intermediate -2)
EP E + P
(intermediate-2) (enzyme) (product)

This is known as the Michaleis-mechanism. The potential energy diagram is

shown in the figure. Which of the following sets of identifications is correct ?
(Assume that the temperature and pressure are constant).
(1) (2) (3) (4)
(A) E+P EP ES E+S
(B) ES Activated complex EP Activated complex
(C) EP Activated complex ES Activated complex
 (D) E + S ES EP E+S

SECTION - II: MULTIPLE CORRECT ANSWER TYPE

-1 -1
K1(time ) K 2 (time )
4.28 For the consectutive reaction A   B   C following curves were
obtained depending upon the relative values of k1 & K2

Now which of the following is the correct match?

(A) figure 1 — (k1 < k2) (B) figure 2 — (k1 < k2)
(C) figure 2 — (k1 » k2) (D) figure 1— (k1 » k2)

429 Which is correct graph:

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

4.30 For a certain reaction A   products, the t1/2 as a function of [A]0 is given as
below :
Which of the following is true :
1
(A) The order is (B) t112 would be 100 10 min for [A]0 = 1M
2
(C) The order is 1 (D) t112 would be 100 min for [A]0 = 1 M

4.31 Decomposition of 3 A(g)   2 B(g) + 2C(g) follows first order kinetics.

Initially only A is present in the container. Pressure developed after 20 min. and
infinite time are 3.5 and 4 atm respectively. Which of the following is true.
(A) t50 = 20 min (B) tams = 40 min (C) t99% = 64/3 min (D) t8, 5% = 60 min

4.32 The reaction 2N0 + Br2   2N0Br follows the mechanism :

Fast
(1) N0 + Br 2 N0Br 2
Slow
(2) N0Br2 + N0   2N0Br
Which of the following islare true regarding this :
(A) The order of the reaction with respect to N0 is two
(B) The molecularly of the steps (1) and (2) are two each.
(C) The molecularly of the overall reaction is three.
(D) The overall order of the reaction is three.
4.33 In the following gaseous phase first order reaction
A(g)   2B(g) + C(g)
initial pressure was found to be 400 mm of Hg and it changed to 1000 mm of Hg
after 20 min. Then :
(A) Half life for A is 10 min
(B) Rate constant is 0.0693 min-1
(C)
Partial pressure of C at 30 min is 350 mm of Hg
(D) Total pressure after 30 min is 1150 mm of Hg
4.34 The polarimeter readings in an experiment to measure the rate of inversion of cane
suger (1st order reaction) were as follows
time (min) : 0 30 co
angle (degree) : 30 20 -15
Identify the true statement (s) log 2 = 0.3, log 3 = 0.48, log 7 = 0.84 , loge 10 = 2.3
(A) The half life of the reaction is 75 min
(B) The solution is optically inactive at 120 min.
(C) The equimolar mixture of the products is dextrorotatory
(D) The angle would be 7.5° at half time

4.35 Identify the true statement(s)

(A) A catalyst is chemically unchanged at the end of a reaction
(B) A catalyst may appear in the kinetic rate equation of the reaction
(C) A catalyst will not affect the composition of an equilibrium mixture
(D) A catalyst cannot cause a non-spontaneous (  G > 0) reaction to proceed

4.36 The half – period T for the decomposition of ammonia on tungsten wire, was
measured for different initial pressure P of ammonia at 25°C. Then
P (mm Hg) 11 21 48 73 120
T (sec) 48 92 210 320 525
(A) Zero order reaction
(B) First order reaction
(C) rate constant for reaction is 0.114 seconds
(D) rate constant for reaction is 1.14 seconds.

4.37 The substance undergoes first order decomposition. The decomposition follows two
parallel first orde reactions as :

.
K1
K1 = 10–2 Sec–1 and K2 = 4 × 10–2 Sec–1

K2

If the corresponding activation energies of parallel reaction are 100 and 120 kJ mol-1
then the net activation energy of A is / are :
(A) 120 KJ mol-1 (B) 116 KJ mol-1 (C) 100 KJ mot' (D) 150 KJ mot'

4.38 A certain reaction obeys the rate equation (in the integrated form) [Co -") - Co' - = (n -
1) kt where C, is the initial concentration and C is the concentration after time, t.
(A) the unit of k for n = 1 is sec-1 (B) the unit of k for n = 2 is litre mo1-1 sec1
(C) the unit of k for n = 3 is mol litre sec1 (D) the unit of k for n = 3 is litre mol-2 sec1

.
4.39 The ozone layer in the earth's upper atmosphere is important in shielding the earth
from very harmful ultraviolet radiation. The ozone, 03, decomposes according to the
 equation 203(g) -› 302(g). The mechanism of the reaction is thought to proceed through
an initial fast, reversible step and then a slow second step.
Step 1: Fast, reversible 03(g) 02(g) +0(g)
Step 2 : Slow 03 (g) + 0(g)  202(g)
The which of the following is correct ?
(A) Step 2 is rate determining step
d
(B) the rate expression for step 2 is -- [O3 ] = k[03][0]
dt
(C) For Step 1 , molecularity is 1
(D) For Step 2 , molecularity is 2

4.40. Consider the following case of COMPETING 1ST ORDER REACTIONS

\.
After the start of the reaction at t = 0 with only A, the [C] is equal to the [D] at all times. The
time in which all three concentrations will be equal is given by
1 1 1 1
(A) t = n3 (B) t  n 3 (C) t  n 2 (D) t  n 2
2k1 2k2 3 k1 3k 2
.4.41 Rate of a chemical reaction 2A (g)   B (g) is defined as
1 dnB
'rB ' 
V dt
Where nB = number of moles of B formed and CB = concentration of B then which of the
following relation is correct.
dCB CB dv
(A) rB = + (If volume V is not constant)
dt v dt
dCB
(B) rB = (If volume V is constant)
dt

dCB CB dv
(C) rB =  (If volume V is not constant)
dt v dt
dCB CB dv
(D) rB = –  (If volume V is not constant)
dt v dt

SECTION - III : ASSERTION AND REASON TYPE

4.42 Statement-1 : If the activation energy of reaction is zero temperature will have no
effect on the rate constant.
Statement-2 : Lower the activation energy fasten is the reaction.
 (A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for
Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

4.43 Statement-1 : If the order of reaction is zero than degree of dissociation will be
independent upon initial concentration.
kt
Statement-2 : The degree of dissociation of Zero order reaction is given by  =
c0
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for
Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

4.44 Statement-1 : For a reaction A(g)  B(g)

—re =2.5 PA at 400K
—re =2.5 PA at 600K
activation energy is 4135 J/mol.
Statement-2 : Since for any reaction, values of rate constant at two different temp is
same therefore activation energy of the reaction is zero.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for
Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for
Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

4.45 Statement-1 : For A+ 2B   C (rate = K [A]1[B]°), the half life time of reaction
is only defined when conch of A and B are in stoichometric ratio
Statement-2 : For above given order half life of reaction is directly proportional to
conch of A and not to conch of B due to its zero order.
(A) Statement-1 is True, Statement-1 is True; Statement-1 is a correct explanation
for Statement-1.
(B) Statement-1 is True, Statement-1 is True; Statement-1 is NOT a correct
explanation for Statement-2.
(C) Statement-1 is True, Statement-1 is False.
(D) Statement-1 is False, Statement-1 is True.
 SECTION - IV: TRUE AND FALSE TYPE

d[A]
4.46 The rate of the reaction A  B having the rate law – = k [A] [B] when plotted
dt
against time will exhibita maximum at some time.

4.47 A catalyst in a chemical reaction increases the forward Ea and decreases the
backward Ea

4.48 A catalyst in a chemical reaction decreases both forward and backward Ea

4.49 For a first-order reaction, the time required to reduce successively the
concentration of reactant by a constant fraction is always same.

4.50 As a first order reaction proceeds at a constant temperature, the ode rewislis
constant

4.51 Generally the rate of reaction decreases with decrease in temperature.

4.52  B + C, must be r = k [A]2

The rate law of the elementary reacton; 2A 

4.53 Generally the rate of reaction depends upon the surface area of the solid reactants

4.54 Zero order reaction is uniform rate reaction but it can not be elementry reaction (single
step reaction)

4.55 Molecularly of a reaction may includes the number of product melecules taking part in the
reaction.

4.56 Larger the value of Ea , greater is the effect on the value of k for a given temperature
change.

4.57 At lower temperature, increase in temperature cause more change in the value of k than
at higher temperature.

4.58 If concentration of catalyst appear in rate law (rate = k [catalyst]1[reactant]1) then it may
becomes pseudo first order reaction during the reaction.

SECTION - V : COMPREHENSION TYPE

Comprehension # 1
Consider the inter conversion of nitrosotnacetoamine into nitrogen phorone and
water.
 The reaction is 1st order in each direction, with an equilibrium constant of 104, the activation
energy for the forward reaction is 11usactivation energy for the forward reaction is 57.45 kJ / mol.
Assuming arrehemus preexponetial factor of 1012 S–-1

4.59 What is the expected forward constant at 300K , it we initiate this reaction
starting with only reactant
(A) 102 (B) 106 (C) 106 (D)104

4.60 If the change in entropy of the reaction is 0.07 KJ. K-1 mol-1 at 1 atm pressure.
Calculate up to which temperature the reaction would not be spontaneous. (For
forward reaction)
(A) T < 285.7 K (B) T > 250 K (C) T < 340.2 K (D) T > 200 K

4. 61 Calculate Kp of the reaction at 300 K

(A) 2.4 x 104 atm-1 (B) 104atm (C) 24.6 x 104atm (D) 2.82x102 atm1

Comprehension # 2
.REACTIONS TENDING TO EQUILIBRIUM
Not all chemical reactions proceed to a stage at which the concentrations of the
reactants become vanishingly small. Here we consider the kinetics of such
reactions.
Let a reaction be represented in general terms by the scheme
K1
A B
K2
where k., and k_., represent the rate constants for the forwards and reverse
reactions, respectively. The equilibrium constant for this reaction may be written
as
K = [B] /[A] = K1/K–1 --(1)
where the subscript 00 refers to a time t, sufficiently long to establish equilibrium at
the given temperature. The initial concentration of species A is [A]O, and that of B
is [B]O . After a time t, let the concentration of species A be [A/t and that of B be
[Bat. The total rate of change of [At is given by
d[A]t/dt= - K1[A]t + k-1[B]t
 If, as is usual, [B]O is initially zero, it follows from a mass balance that at any time t,
[Bat = [A]0 - [A]t, whence
d[A]t/dt = –K1[A]t + k-1([A]O - [A]t)
or d[A]t/dt = – (K1 + k-1)

k1
4.62 For the reaction A C (having both 1ts order reactions),
K2
the concentration as a function of time are given for a certain experimental run
along with a tangent to the graph at the origin. The ratio of the magnitude of the
slopes of the graph of [A/ and [C/ at the origin would be :

3 4
(A) 1 (B) (C) (D) None of these.
4 3

4.63 At what time is the rate of change of concentration of A equal to rate of change
of concentration of C in magnitude ?
(A) t = 0 only (B) t  t equilibriumonly (C) t = 10 only (D) at all time

4.64 What is the Cc of the reaction 2C 2A?

2 3
(A) (B) (C) 1 (D) None of these
3 2

Comprehension # 3
PSEUDO - MOLECULAR REACTIONS
There are many reactions which obey a first order rate equation although it reality
they are bi- or ter-molecular. As an example of these may be taken the decomposition
of Carbonyl sulfide in water, namely,
COS + H20   002 + H2S
According to the law of mass action this reaction should be second order with the rate
dependent on the concentration of both the carbonyl sulfide and the water. Actually
however, the rate is found to be first order with respect to the carbonyl sulfide and
independent of the water Reactions exhibiting such behaviour are said to be pseudo-
molecular.
The pseudo-unimoecuar nature of this reaction is explainable by the fact that water is
present in such excess that its concentration remains practically constant during the
course of the reaction. Under these condition b x = b, and the rate equation
becomes
dx
 k2 (a  x )b
dt
On integration this leads to
2.303 a
k  bk 2  log10
t ax
 which is the equation for a first order reaction. It is evident, however, that the now
constant k is not independent of the concentration, as is the case with true first order
constants, but may vary with b if the latter is changed appreciably, When such is the
case, the true constant k2 can be obtained from k by dividing the latter by b.
pseudo-molecular reactions are encountered whenever one or more of the
reactants remain constants during the course of an experiment. This is the case
with reactions conducted in solvents which are themselves one of the reactants, as
in the decomposition of carbonyl sulfide in water, or in the esterification of acetic
anhydride in alcohol
(CH3C0)20 + 2C2H5OH   2CH3C00C2H5 + H20
Again, this is also true of reactions subject to catalysis, in which case the
concentration of the catalyst does not change. The decomposition of diacetone
alcohol to acetone in aqueous solution is catalysed by hydroxyl ions, with the
rate proportional to the concentration of the alcohol and that of the base. Since
the concentration of the base does not change within any one experiment,
however, the rate equation reduces to one of first order with respect to the
alcohol. But the rate constant k obtained for various concentrations of base are
not identical, as may be seen from table. To obtain from these the true second
order velocity constant, the k's must be divided by the hydroxyl ion
concentration. When this is done excellent k2 values result, as column 3
indicates.

Table : Decomposition of diacetone alcohol in water at 25°C (Catalyst : NaOH)

4.65 Which of k or k2 is dependent on concentration ?

(A) only k (B) only k2 (C) both k and k2 (d) neither k nor k2

4.66 By what factor does the rate of reaction of diacetone alcohol in water solution
change if p0H is increased by 2 units other things remaining same ?
(A) increases 100 times (B) decreases 100 times
(C) increases 2 times (D) decreases 2 times

4.67 For the reaction A + B  C ; r = k [A] [B] with [A]0 = 0.001 M and [B]0 = 10 M, the
time in which the conc. of A becomes 0.005 M will be nearly
0.693 0.693 6.93 693
(A) (B) (C) (D)
10k k k k
Comprehension # 4

From the following data answer the questions :

Reaction : A + B  P

4.68 The order w. r.t A is

(A) 1 (B) 2 (C) 3 (D) -1.

4.69 The value of rate constant at 300 K is (M-2 sec-1)

(A) 2.667 n 108 (B) 2.667 x 105 (C) 2.667 x 105 D) 2.667 X 109

4.70 The energy of activation for reaction (KJ/mol) is

(A) 20.83 (B) 13.83 (C) 15.23 (D) 10.23

Comperhension # 5

The rate law expressed the relationship of the rate of a reaction to the rate
constant and the concentration of the reactants raised to some powers for the
general reaction
aA + bB   cC + dD
Rate law takes the form
r = k [A]X [B]y
where x and y are number that must be determined experimentally k is the rate
constant and [A] and [B] are concentration of A & B respectively.
4.71 Gaseous reaction A   B + C follows first order kinetics concentration of A
changes from 1M to 0.25M in 138.6 min. Find the rate of reaction when conc. of
A is 0.1 M.
(A) 10-2M min1 (B) 10-3 M min-1 (C) 10-4M min–1 (D) 10-5M min–1

4.72 The initial rate of zero order reaction of the gaseous equation A (g)   2B
-2 1
(g) is 10 M min if the initial conc. of A is 0.1 M what would be conc. of B after
60 sec.
(A) 0.09 M (B) 0.01 M (C) 0.02 M (D) 0.03 M
 4.73 The variation of concentration of 'A'
with time in two experiments starting
with two different initial concentration
of 'A' is given by the following
graph.The reaction is represented by
A (aq)   B(aq) what is rate of
reaction 1.5M (M/min) when conc. of A
in aqueous solution was 1.8 M.

(A) 0.072 M min -1 (B) 0.1296 M min–1

(C) 0.036 M min -1 (D) 1 M min-1

Comprehension # 6 K1 2B
k1 1
For a hypotherical elementary reaction A where 
k1 2
K2 2B
.Initially only 2 moles of A are present.

4.74 The total number of moles of A, B and C at the end of 50% reaction are:
(A) 2 (B) 3 (C) 5 (D) None

4.75 Number of moles of B are :

(A) 2 (B) 1 (C) 0.666 (D) 0.333

4.76 The sum of mole of (B) and (C) is :

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

SECTION - VI : MATRIX - MATCH TYPE

4.77 For A + B   C in column - II the graphs given can be from any of these
four types.
dA
(a)  Vs time (x axis) (b) t1/12 Vs initial conc. (x axis)
dt
 C  Ct 
(c)  0  Vs time (x axis) (d) Conc. Vs time (x axis)
 Ct 
Match the graphs in Column—I I for the given order of reactions in Column – I
 .Column – I Column – II

(A) 1st order

.(B) Zero order

.(C) Second order

. (D) Pseudo first order

4.78 Match the following :

Coloumn – I Coloumn – II
(A) A + B   C + D (p) Unit of rate constant possess concentration unit
r = k1[A] [B]
(B) A + B   C +D (q) Rate constant for the reaction of both the reactants are
r = k2 [A] [B]° equal
(C) A + B   C + D (r) Rate of consumption of at least one of the reactants is
r = k3 [A]° [B]° is equal to rate of production of at least one of the
products
(D) 2A + B r  2C +3D (s) If both reactants are taken in stoichiometric ratio, half
k3 [A]° [B]° life for both reactants are equal.

479 Match the following:

Column – I Column – II
st
1 order
.(A)2N205 (g)   4NO2(g) + 02(g) (p) All the gaseous products are
paramagnetic in nature
 st
1 order
(B) 2H202 (aq)   2H20(aq)+02(g) (q) Hybridisation of reactant involves only

s & p orbitals
Zero order
.(C) 2NH3(g)  N2 (g) + 3H2(g) (r) As the reaction proceeds half life or
reactant changes with time
Zero order
(C) .2Cl207(g)  4C102 (g) + 302(g)(s) rate of production of, gases decreases
with increases in concentration of
products.

4.80 Match the following

Column I Column II
(A) If the activation energy is 65 kJ then how much time (p)5
faster a reaction proceed at 25°C than at 0°C
(B) Rate constant of a first - order reaction is 0.0693 min-1 . (q)11
-1 -1
If we start with 20 mol L , it is reduced to 2.5 mol L
in how many minutes
(C) Half - lives of first - order and zeroth order reactions are same. (r)30
Ratio of rates at the start of reaction is how many times of 0.693.
(D)The half-life periods are given , (s)1/4
[A]0 (M) 0.0677 0.136 0.272 (t)2
t1,2 (sec) 240 480 960 (u)1
order of the reaction is (v) 0

SECTION - VII : SUBJECTIVE ANSWER TYPE

SHORT SUBJECTIVE :
4.81 Reaction A   B carried inside a container concentration varies as At = a + bt. Rate
of reaction can be expressed in term of pressure at temp T = 300 K take b = 4, R=
1
atm mol–1k–1
12

4.82 If dt= k [H+]n and rate becomes 100 times when pH changes from 2 to 1. Find the
order of reaction.

1
4.83 The graph between log k and A [K is rate constant (sec-') and T the temperature.
T
 1 
(K)] is a straight line with OX = 5 and θ = tan-1   .Calculate the value of Ea is
 2.303 
cal.

4.84 For the reaction A  products, the following data is given for a particular run.
time (min.) : 0 5 15 35
1
(M–1 ) : 1 2 4 8
A
Determine the order of the reaction.
LONG SUBJECTIVE :

4.85 The rate constant of 1st order decomposition reaction of an organic compound (X)
into another organic compound Y and an inorganic compound (gas) (Z) may be given

1.25×10 4
Iog1ok (sec-1) = 12.37 –
T  inkelvin 
Find the activation energy and rate constant at 750 K and indicate your answer as
the product of Ea (in Joules moll and rate constant (in unit sec-1) and fill the answer as
a neares whole number.
Take R = 8.3 JK-1mo1-1, {antismog (-4.3) = 5 x 10-5}

4.86 Find out the percentage of the reactant molecules crossing over the energy barrier
at 325 K, given that  H325 = 0.12 kcal, Ea(b) + 0.02 kcal.

4.87 For the same first-order reaction, A   B + C, occurring in solution phase, now
let us assume that the reagent reacts with all the species A, B and C. The 'n' factor
of A, B and C with the regent is α,β and  respectively and that of the reagent with A,
B and C is a, b, and c.

. Calculate the expression of rate constant.

4.88 Decomposition of H202 (1st order)

1
 H2O(  ) +
H2O(aq)  O2(g)
2
Can be monitored by titration method by pressure measurement..If
Time (min) t=0 30 
Pressure (mm of Hg) 200 375 400
While when progress of same reaction was monitored by titration mnanit volume of
titrant consumed after 10 min was found to be 20 ml. Then complete the following Win.
Time (min) t=0 10 30
Pressure (mm of Hg) 200 (b) (c)
Volume of KMn04 (a) 20 (d)
consumed (m1)