Liquid Solution & Atomic Structure (Physical Chemistry)

PRACTICE PROBLEMS
1. 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) 0.37 ºC to 0.555 ºC (B) 0.185 ºC to 0.93 ºC
(C) 0.56 ºC to 0.93 ºC (D) 0.37 ºC to 0.93 ºC

2. When only a little quantity of HgCl2(s) is added to excess KI(aq) to obtain a clear solution,
which of the following is true for this solution? (no volume change on mixing).
The reaction is 4KI(aq.) + HgCl2(s) ⎯→ K2[HgI4] (aq.) + 2KCl (aq.)
(A) Its boiling and freezing points remain same
(B) Its boiling point is lowered
(C) Its vapour pressure become lower
(D) Its boiling point is raised

3. The vapour pressure of two miscible liquids (A) and (B) are 300 and 500 mm of Hg
respectively. In a flask, 10 moles of (A) are mixed with 12 moles of (B). However, as soon as
(B) is added, (A) starts polymerizing into a completely insoluble solid. The polymerization
follows first-order kinetics. After 100 minutes, 0.525 moles of a solute is dissolved which
arrests the polymerisation completely. The final vapour pressure of the solution is 400 mm of
Hg. The rate constant of the polymerisation reaction is (Assume negligible volume change on
mixing and polymerisation and ideal behaviour for the final solution:)

4. Tritium, T (an isotope of H ) combines with fluorine to form weak acid TF, which ionizes to
give T + . Tritium is radioactive and is a 𝛽-emitter. A freshly prepared aqueous solution of TF
has pT (equivalent of pH ) of 1.5 and freezes at −0.372∘ C. If 600ml of freshly prepared solution
were allowed to stand for 24.8 years. Calculate (i) ionization constant of TF. (ii) Number of 𝛽-
particles emitted.
(Given K f for water = 1.86 kg mol K −1 , t1/2 for tritium = 12.4 years)

5. Pressure over ideal binary liquid mixture containing 20 moles each of liquid A and B is
gradually decreased isothermally. If PA0 = 200 mm Hg PB0 = 100 mm Hg, find the pressure at
which half of the liquid is converted into vapour.

6. Angular wave function of Px orbital is : (Given : q is angle from z-axis)

1 1
 3 2  3 2
(A)   sin  sin  (B)   sin  cos 
 4   4 
1 1
 3 2  15  2
(C)   cos  (D)   sin  cos  cos 
 4   4 

7. Which statement is not true, regarding 2s orbital.

(A) Number of radial nodes is greater than zero
(B) Angular nodes is equal to zero
(C) ( ) = constant
(D) Probability density is zero at nucleus

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 Liquid Solution & Atomic Structure (Physical Chemistry)

Paragraph for Question 8 & 9

In a H-like species there are two energy levels A and B above the ground state having principal
quantum numbers of n1 and n2 respectively. A sample of this H-like species has all atoms/ions
in excited levels A or B only and none in any other energy level. Energy of level B is greater
than that of level A and a total of 15 different lines are emitted from this sample on returning
to ground state out of which 6 lines are emitted due to electronic transitions between the
levels n1 and n2 only. Also energy difference between levels n2 and n1, En2 − En1 = 4.53 eV.

8. How many lines will be emitted by this sample in Balmer series ?

(A) 6 (B) 5 (C) 4 (D) 3

9. The hydrogen like species for which data is given in above passage is -
(A) He+ (B) Li+2 (C) Be+3 (D) B+5

10. Match the Column :

rn,z = Radius of nth orbit of a single electron specie having atomic number 'z'.
vn,z = Velocity of electron in nth orbit of a single electron specie having atomic number 'z'
En,z = Magnitude of total energy of electron in nth orbit of a single electron specie having atomic
number 'z'
Kn,z = Magnitude of kinetic energy of electron in nth orbit of a single electron specie having
atomic number 'z'
Pn,z = Magnitude of potential energy of electron in nth orbit of a single electron specie having
atomic number 'z'
fn,z = Frequency of electron in nth orbit of a single electron specie having atomic number 'z'
Tn,z = Time period of electron in nth orbit of a single electron specie having atomic number 'z'
Column-I Column-II
f r2,3
(A) 1,2 (P)
f1,1 f1,3
r3,2 T1,1
(B) (Q)
K 3,1 T1,2

 1   P2,1   K 
(C)    (R) 2 2,3

 2   E3,1 

 E1,2



E  v 2,3
(D)  1,4  (S)
E  v1,1
 2,2 
 v − v 2,1 
(T) 4  2,5
 v − v 
 2,3 2,2 

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 Liquid Solution & Atomic Structure (Physical Chemistry)

11. Match the column:

Column-I Column-II

(A) 1s (P)

r
(B) 2s (Q)

r2

r
(C) 2p (R)

r2

r
(D) 3p (S)

r
(T)

12. The ratio of the wavelength of a proton & -particle will be 1 : 2 if their
(A) Velocity of proton to velocity of  particle is in the ratio 1 : 8
(B) Velocity of proton to velocity of  particle is in the ratio 8 : 1
(C) Kinetic energy of proton to Kinetic energy of  particle is in the ratio 64 : 1
(D) Kinetic energy of proton to Kinetic energy of  particle is in the ratio 16 : 1

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 Liquid Solution & Atomic Structure (Physical Chemistry)

Answer. Key
1. (A) 2. (B) 3. k  1.004  10−4 min−1
4. (i) K a = 7.3 × 10−3 (ii) 4.55 × 1022 5. (141.4)
6. (B) 7. (D) 8. (C) 9. (A)
10. (A) → (P,Q), (B) → (P,Q), (C) → (R,S), (D) → (T)
11. (A) → (S,P); (B) → (R,T); (C) → (S); (D) → (Q,R)
12. (BD)
Solution
1. (A)
x + y = 0.1
If y = 0 , x = 0.1 (0.1 mole KCl)
Tf = I × Kf m = 2 × 0.1 × 1.85 = 0.37
If x = 0 , y = 0.1 (0.1 mole KCl)
Tf = I × Kf m = 3 × 0.1 × 1.85 = 0.555
2. (B)
4 kJ(aq) + HgCl2 (s) ––→ K2[HgI4](aq) + 2KCl(s)
ni 5 1 (LR) 0 0
nf 1 0 1 2
no. of particles initial = 5 × 2 = 10
no. of particles finally = 1 × 2 + 1 × 3 + 2 × 2 = 9
no. of particles are decreasing
Tb  , Tb 
3. Initial moles of A = 10
Let the number of moles of A when polymerization is arrested be n.
Moles of B = 12
Moles of solute added = 0.525
Total moles = (n + 12 + 0.525)
= (n + 12.525)
n
xA =
( n + 12.525)
12
xB =
( n + 12.525)
P = PA .XA + PB. XB
n 12
or 400 = 300 × + 500 
( n + 12.525) ( n + 12.525)
Solving, we get
n = 9.9
For the first order polymerization,
2.303 A 2.303 
k= log. 0 or k = log.
t A t −x
2.303 10
= log.
100 9.9

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 Liquid Solution & Atomic Structure (Physical Chemistry)

Solving, we get
k  1.004  10−4 min−1
4. (i) K a = 7.3 × 10−3 (ii) 4.55 × 1022
5. (141.4)
Let nB be the mole of B present in 10 mol of the mixture that has been vaporized
n 10 − n B
 yB = B ; xB = ;
10 10
 10 − n B 
PB0  
PB0 ·x B nB  10 
yB =  =
P 10 P
n B PB0 PB0 n B n P0
= −  B − B 0 …..(1)
10 P 10P 10 P + PB
& P = PA0 + (PB0 − PA0 ) x B
P − PA0 10 − n B P − PA0
 xB = 0  = 0
PB − PA0 10 PB − PA0
nB P0 − P
 = 0B 0 .....(2)
10 PB − PA
From (1) and (2)
PB0 PB0 − P
=
PB + PB0 PB0 − PA0
P= PA0 ·PB0 = 200 100
= 141.4 mm Hg Ans.
6. (B)
7. (D)
8. (C)
9. (A)
En2  En1  n2  n1
( n2 − n1 )( n2 − n1 + 1) = 6 & n2 ( n2 − 1 )
= 15  n2 = 6 & n1 = 3.
2 2
No. of lines in Balmer series = 6 – 2 = 4
En2 – En1 – = 4.53 = E6 –E3
Z2 Z2
 −13.6  + 13.6  = 4.53
36 9
 Z=2
 species is He+ ion.

10. (A) → (P,Q), (B) → (P,Q), (C) → (R,S), (D) → (T)

11. (A) → (S,P); (B) → (R,T); (C) → (S); (D) → (Q,R)
12. (BD)

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