Multiple Choice Questions:
1. A 5L vessel contains 2.8 g of N2 . When heated to 1800 K , 30% molecules are dissociated into atoms.
(A*) Total no. of moles in the container will be 0.13
(B*) Total no. of molecules in the container will be close to 0.421 × 1023.
(C) Total no. of moles in the container will be 0.098.
(D) All of these are correct.
Sol. (A) and (B) Explanation : 30% of molecule dissociated N2 2N
2 .8 70
Amount of N2 left = × = 0.1 × 0.7 = 0.07
28 100
(in moles)
30
No. of moles of N atoms formed = 2 × × 0.1 = 0.06
100
(A) Total no . of moles = 0.07 + 0.06 = 0.13
(B) Total number of molecules = 0.07 ×6.023 × 1023 = 4.2 × 1022 molecule = 0.421 × 1023
Q We have to calculate molecule of nitrogen not atoms.
2. Which of the following is / are heterocyclic compound (s)
(A) (B)
H2N OH
•(C) •(D)
N
H
3. Which of the following of compounds are position isomers
•(A) and •(B) and
(C) and (D) and
4. Consider the decay of P to A and B by two parallel first order reactions as shown in Fig. Given
Reaction H Rate constant Energy of activation
PA HA kA EA
PB HB kB EB
Which of the following is(are) true?
(A*) a = EB (B*) b = EA (C*) HA = b d (D) HB = c a
t87.5% = 3 × t50% = 3 × 20 = 60 min
2 2 400
t99% = × t99.9% = × 10 × t50% =
3 3 3
7. A reaction takes place in three steps. The rate constant of the three steps are K1, K2 and K3 respectively.
K1K 3
The overall rate constant K = K .
2
The energy of activation for the three steps are 40, 30 and 20 KJ respectively. Therefore :
(A) Overall energy of activation is 10 KJ
(B*) Overall energy of activation is 30 KJ
K1
(C*) The reaction mechanism is 2A A* + A ; A * product and overall order is one.
K2
K1
(D) The reaction mechanism is A K2 K3
B ; B C ; C product and overall order is one
K1K 3
Sol. K= K2
E E3
1
A1e RT A 3e RT
(Ea )overall
Ae = E
RT – 2
A 2e RT
(Ea )overall A1A 3 [E1E3 E2 ]
Ae RT
= A RT
2 e
(Ea)overall = E1 + E3 – E2 = 30 KJ/mole
2A A* + A [Fast]
K1 [ A *][ A ] K1
K2 = 2 or [A*] = K 2 [A]
[A]
K1K 3
rate = K3[A*] = K 2 [A]
Single Choice Questions:
1. For the follwing parallel chain reaction the overall half life of A is 12 hours If
rate of formation of C is 60% of a rate of decomposition of A then what will be half life of A while it is
converting into B ?
(A) 40 hours (B) 60 hours (C) 50 hours (D*) 30 hours
2. Inversion of sucrose (C12H22O11) is first-order reaction and is studied by measuring angle of rotation at
different instant of time
2 0.03 20
mole of solute (Na+ & Cl–) in other beaker = = 0.0012
1000
conc. of IInd beaker is higher then Ist beaker so water flowes from Ist beaker to IInd beaker till both beaker
achieved equal conc. let v volume of water flows from Ist to IInd beaker
0.001 0.0012
so
20 v 20 v
v = 1.8 ml
volume of Ist beaker = 20 – 1.8 = 18.2 ml
volume of IInd beaker = 20 + 1.8 = 21.8 ml.
6. x mole of KCI and y mole of BaCl2 are both dissolved in 1 kg of water. Given that x + y = 0.1 and Kf for water
is 1.85 K/molal, what is the observed range of Tf, if the ratio of x to y is varied ?
(A*) 0.370 to 0.505º (B) 0.1850 to 0.930 (C) 0.560 to 0.930 (D) 0.370 to 0.930
Sol. x + y = 0.1
x / y = 0.37
x x y 2y
Tf = × 1000 × 1.85
1000
0. 2 y
Tf = × 1000 × 1.85
1000
Tf = (0.2 + 0.0729927) × 1.85 = 0.505
7. Given P-x curve for a non-ideal liquid mixture (Fig.). Identify the correct T-x curve for the same mixture.
(A) (B*)
(C) (D)
H
H H
(i) (j) (k) H
H
H
[18] Annulene
Ans. Aromatic – a, c, g, h, i, j, k ; Antiaromatic – b, d, e ; Nonaromatic – f
4. How many of the given molecules have all carbon atoms in one plane :
Ans. 7 [1, 2, 3, 4, 6, 7 and 9. have all carbon atoms in one plane.]
5. 1 g of a monobasic acid dissolved in 200 g of water lowers the freezing point by 0.186ºC. On the other hand
when 1 g of the same acid is dissolved in water so as to make the solution 200 mL, this solution requires
K kg
125 mL of 0.1 N NaOH for complete neutralization. Calculate % dissociation of acid ? (Kf = 1.86 )
mol
Ans. 60
1 125
Sol. Macid = 1000 × 0.1 Macid = 80 g mol–1
1
80
0.186 = (1 + ) × 1.86 × = 0.6 60 percent
0 .2
6. The rate constant for the II order neutralization of 2-nitropropane by aqueous alkali obeys the equation
3163
log10 K = + 12
T
T is temperature in Kelvin.
Time and concentration were in minute and mol litre–1 respectively. Calculate half life at 43.3°C and for an
initial concentration of 0.001 mol litre–1 for each of the reactant.
Ans. 10–19 minute
3163
Sol. log10K = + 12
T
at T = (273 + 43.3) = 316.3 K
3163
log10K = + 12
316.3
log10K = (10+12) = 22
K = 1022
Then half life period
1 1 1
t1 / 2 = K a = = 19 = 10–19
1022 .001 10
t1 / 2 = 10–19 min Ans. 10–19 minute.
1. Rate constant (k) = (log 64 – log 49) s–1. Value of t1 in seconds is :
(A) 2.15 s (B) 1.5 s (C) 2.3 s (D*) 1.15 s
2. Ratio of rate constant at t = 0 to t = t1 to t = tx is :
(A) 2 : 3 : 4 (B*) 1 : 1 : 1 (C) 1 : 3 : 5 (D) 1 : 3 : 5
Comprehension # 3
Study the following experiment and answer the questions at the end of it.
The following reactions was studied at 250C in benzene solution containing 0.10 M pyridine
CH3OH + (C6H5)3 CCl (C6H5)3 C . OCH3 + HCl
A B C
The following sets of data were observed :
Set Initial concentration time difference Final concentration [C]
[A] 0 [B] 0
I 0.10 M 0.05 M 25 min 0.0033 M
II 0.10 M 0.10 M 15 min 0.0039 M
III 0.20 M 0.10 M 7.5 min 0.0077 M
d [C ]
51. Rates in sets I , II and III are respectively (in M min–1) :
dt
I II III
(A*) 1.30 × 10–4 2.6 × 10–4 1.02 × 10–3
(B) 0.033 0.0039 0.0077
(C) 0.02 × 10–4 0.04 × 10–4 0.017
(D) None of above
52. Rate law of the above experiment is :
(A) r = k [A] [B] (B*) r = k [A]3 [B] (C) r = k [A] [B]2 (D) r = k [A]2 [B]0
53. Rate constant of the above experiment is :
(A) 1.3 × 10–1 (B) 2.6 × 10–2 (C*) 2.6 × 10–1 (D) 1.3 × 10–2
Sol.
dc c .0033
51. (I) Rate (nj) = = t = = 1.32 × 10–4
dt 25
dc c .0039
(II) Rate (nj) = = t = = 2.6 × 10–4
dt 15
c .0077
(III) Rate (nj) = t = = 1.02 × 10–3
15
52. (II) Rate of Rxn = Rate of formation of C.
Then we say by I data.
Suppose [Rate = k [A]a [B]b] ....(i)
1.32 × 10–4 = k [.10]a [.05]b ....(ii)
2.6 × 10–4 = k [.10]a [.10]b ....(iii)
1.02 × 10–3 = k [.20]a [.10]b ....(iv)
By equation (ii) and (iii) we find b = 1
By (iii) and (iv) we find a = 2.97 3.
Then Rate = k [A]2 [B]1
53. (III) Rate (nj) 1.32 × 10–4 = k [.10]2 [.05]
k = 2.6 × 10–1