Q (1) : 4.45 g of pure sulphuric acid is added to 82.20 g water. The density of the solution was found to be 1.

029 g/ml.
Calculate (a) weight percent (b) mole fraction (c) mole percent (d) molality (e) molarity and (f) normality of
sulphuric acid solution.

Sol.: Mass of H2SO4 = 4.450 g

Mass of water = 82.20 g
Mass of solution = 86.65 g
Density of solution = 1.029 g/ml
4.45
(a) Weight percent of H2SO4 in solution = 100 = 5.14
86.65

4.45
(b) Moles of H2SO4 = = 0.0454
98

82.20
Moles of H2O = = 5.566
18
Total no. of moles = 0.0454 + 4.566 = 4.6114
0.0454
Mole fraction of H2SO4 = = 0.0098
4.6114
Mole fraction of water = 1 – 0.0098 = 0.9902
(c) Mole percent
Moles of solute
Mole percent of solute =  100
Total moles in solution

= Mole fraction of solute  100 = 0.0098  100 = 0.98

Mole percent of solvent = Mole fraction of solvent  100
= 0.9902  100 = 99.02
(d) Molality
Moles of solute
Molality = Mass of solvent in g  1000

0.0454
=  1000 = 0.552.
82.2
(e) Molarity
Moles of solute
Molarity =
Volume of solution in litres

Mass of solution in g 86.65

Volume of Solution = Density of solution = 1.029  1000 litre

0.0454  1000  1.029

Molarity = = 0.539
86.65
(f) Normality
No. of equivalents of solute dissolved
Normality =
No. of litres of solution made

4.45
Equivalent of H2SO4 =
49

86.65
Volume of solution = 1.029  1000
 4.45  1000  1.029
Normality = 49  86.65 = 1.078

Q (2) : Certain liquid X boils at 33.5º C at 1 atm. At what temperature will it boil at 750 mm. Latent heat of vaporization
is 88.4 cal/g, R = 1.987 cal. and Mol. wt. of X is 74.

Sol.: We Known

P
2  Hv  T  T 
2 1
log P  2.302 R  T T 
1  1 2 
P1 = 760 mm
P2 = 750 mm
Hv = 88.4  74
T1 = 33.5 + 273 = 306.5
T2 =?

750 88.4  74  T2  306.5 

log 760  2.303  1.987  306.5  T 
 2 

T2 = 305.9 k
= (305.9 – 273)º C = 32.9ºC

Q (3) : Solutions of two volatile liquids A and B obey Raoult’s law. At certain temperature T, it is found that when the
total pressure above a given solution is 400 mm Hg the mole fraction of A in the vapour phase is 0.45 and in the
liquid it is 0.65. Find out the vapour pressure of two pure liquids at temp. T.

Sol.: Total Pressure = 400 mm

xA = 0.65 YA = 0.45 PºA = ?
xB = 0.35 YB = 0.55 PºB = ?
We know P = PºA xA + PºB.xB
400 = PºA. 0.65 + PºB. 0.35
Also we know
PA Pº A .x A
YA = 
P P

0.65 P º A
0.45 =
400

400 0.45
PºA = = 277 mm
0.65
Now,
400 = 277  0.65 + PºB  0.35
400  180
PºB = = 630 mm
0.35

Q (4) : At 30ºC A and B have vapour pressures of 119.6 and 36.7 mm respectively. What are the partial pressures of
each of these components and the total pressure over a solution consisting of equal weights of these two components
at 30ºC. What is the composition of the vapour in equilibrium with the solution at this temperature. Comment on
the results. [mol. wt. of A = 78 and mol. wt. of
B = 92].

Sol.: Say the amount taken is 92 g for each liquid.

 92
Moles of A = = 1.18
78

92
Moles of B = =1
92

1.18
xA = = 0.541
2.18

1
xB = = 0.459
2.18
PA = 0.541  119.5 = 64.7 mm
PB = 0.459  36.7 = 16.8 mm
Total pressure = 64.8 + 16.8 = 81.5
Composition of vapour
64.7
xA in vapour phase = = 0.793
81.5
xB in vapour phase = 1 – 0.793 = 0.207.
This indicates that the vapour is always richer in the more volatile liquid.

Q (5): Calculate the freezing point of an aqueous solution of non-electrolyte having an osmotic pressure of 2.0 atmosphere
at 300 K. [Given Kf = 1.86 K kg mole–1 and S = 0.0821 litre atm K–1mol–1]

Sol.: We know
 = CST
Given
 = 2.0 atm
T = 300 K
S = 0.0821 litre atm K–1 mol–1
C=?
2.0 = C  0.0821  300
2.0
C= = 0.0812 mol litre–1
0.0821  300
Since solution is very dilute molality may be taken as equal to molarity
Tf = Kf  m
Tf = 1.86  0.0812
= 0.151
F.P. = –0.151ºC
Q (6) : If in a reaction A  Products, the concentration of the reaction A is C0, C0, 2C0, 3C0 .... after time values 0,
t, 2t, 3t, .... where  is a constant 0 <  < 1. Show that the reaction is of first order . How is the rate constant
k related to a and t ?
Solution : We know for first order reaction
2.303 a
k= log
t ax
Here a = C0
(a – x) = C0, 2C0, 3C0 etc. at times t, 2t, 3t etc.
Now, substituting these values in the rate equation

2.303 C0 2.303
k1 = log C  = log–1 .... (1)
t 0 t
 2.303 C0 2.303
k2 = log (C   ) = log –2
2t 0 2t
2.303 2.303
=  2log –1 = log –1 .... (2)
2t t
Similarly
2.303 C0 2.303
k3 = log (C   ) = log –3
3t 0 t
2.303 2.303
 3 log –1 = log –1 .... (3)
3t t
Since the value of rate constant, k(k1, k2, k3) are constant. Hence, the reaction is of first order.
The rate constant k is related to  and t as
2.303
k= log –1
t

Q (7) : Calculate the half life of the following first order reaction
C2H4O(g) CH4(g) + CO2(g)
Given the initial pressure of C2H4O(g) is 84 mm and the total pressure at the end of 16 min is 110 mm.
Solution : C2H4O(g) CH4(g) + CO2(g)
Initial conc. a 0 0
Conc. after 16 min. a–x x x
a  84 mm. Total no. of moles after 16 min = a – x + x + x = a + x
 a + x  110 mm
x  26
(a – x) 58
2.303 84 2.303
or 16 = log =  0.1608
t 58 k
2.303  0.1608
k= = 0.0231 min–1
16
0.693
Half life period t1/2 = = 30 min.
0.0231min 1

Q (8) : For a reaction 2A Product, it is found that the rate of reaction becomes 2.25 when the concentration
of A is increased 1.5 times, calculate the order of reaction.
Solution : Rate, r = k [A]n .... (1)
When concentration is increased 1.5 times, the rate of reaction become 2.25.
 2.25 r = k [1.5A]n .... (2)
2.25r k[1.5 A]n
Divide (2) by (1) = k[ A]n
r
n
2.25 = (1.5)
(1.5)2 = (1.5)n
n=2
Q (9) : The following data are for the reaction A + B  products :
Conc. A Conc. B Initial rate
(M) (M) (mol L–1 s–1)
0.1 0.1 4.0  10–4
0.2 0.2 1.6  10–3
0.5 0.1 1.0  10–2
0.5 0.5 1.0  10–2
(a) What is the order with respect to A and B for the reaction ?
(b) Calculate the rate constant
 (c) Determine the reaction rate when the concentration of A and B are 0.2 M and 0.35 M,
respectively.
Solution : R = K[A]m [B]n
4.0  10–4 = K (0.1)m (0.1)n ... (i)
–3 m n
1.6  10 = K (0.2) (0.2) ... (ii)
1.0  10–2 = K (0.5)m (0.1)n ... (iii)
–2 m n
1.0  10 = K (0.5) (0.5) ... (iv)
(a) Divide equation (iii) by (iv)
1.0  10  2 K (0.5) m (0.1) n
= K (0.5) m (0.5) n
1.0  10  2
n
1
1 = 5
 
 n=0
Thus the order of reaction with respect to B is zero.
Divide eq. (i) by (iii)

4.0  10  4 K (0.1) m (0.1) n

=
1.0 10  2 K (0.5) m (0.1) n
m
1
4  10–2 =  5 
 
(0.2)m = (0.2)2
m=2
Thus the order of reaction with respect to A is two
(b) Substituting the values of m and n in .....(ii)
–3 –1 –1 2
1.6  10 mol l s = 0.04 M K
1.6 10 3 mol l 1 s 1
K= 0.04 M 2
= 4.0  10–2 mol–1 s–1

(c) R = K[A]2[B]0
= 4  10–2 mol–1 l s–1  0.04 M2  1 = 1.6  10–3 mol l–1 s–1

Q (10) : The decomposition of hydrogen peroxide in an aqueous solution is a first order reaction. It can be studied by
titrating quickly 10 ml. portions of reactions mixture at various times from the
t = 0 of reaction against a standard solution of KMnO4. Volume of KMnO4 solution used in each case is
proportional to the remaining concentration of H2O2.
From the following data calculte the rate constant of the reaction.
Time (seconds) 0 600 1200
KMnO4 solution used (ml) 22.8 13.8 8.2
Solution : Here, a = 22.8, a – x = Vol. of KMnO4 used at various times t.
At time 600 seconds :
2.303 22.8
K= log = 0.000837
600 13 .8
At time 1200 seconds :
2.303 22.8
K= log =0.000852
1200 8 .2
0.000837  0.000852
Average value of K = = 0.000844 or 8.44  10–4 sec–1
2
Q (11) : The gas phase decomposition of dimethyl ether follows first order kinetics
CH3 – O – CH3(g) CH4(g) + H2(g) + CO(g)
The reaction is carried out in a constant volume container at 500ºC and has a hlf life of 14.5 minutes. Initially
only dimethyl ether is persent at a pressure of 0.40 atmosphere. What is the total pressure of the system
after 12 minutes ? Assume ideal gas behaviour.
Solution : Given t1/2 = 14.5 min, initial pressure = 0.40 atm, t = 12 min
0.693
Now, K = = 4.78  10–2 min–1
14.5
2.303 0 .4
4.78  10–2 = 12 min log
0 .4  x
which gives x = 0.175 atm.
Since volume and temp. are constant, final pressure :
CH3 – O – CH3(g) CH4(g) + CO(g) + H2(g)
0.4
0.4 – 0.175 0.175 0.175 0.175
Hence total pressure = 0.4 – 0.175 + 3  0.175
= 0.749 atm
Comprehension-1
Conformation are structures obtained by rotation around  bonds without breaking and remaking the bonds. Ethane
has staggered and eclipsed conformations. Staggered conformation is more stable than eclipsed conformation.

12. The total number of possible conformation of ethane are

(a) 2 (b) 3 •(c) infinite (d) zero

13. Which conformation of cyclohexane is most stable?

•(a) Chair (b) Boat (c) Half-chair (d) Half boat

14. Which of the following is correct?

•(a) Conformations cannot be isolated due to less difference in their energy
(b) Conformations can be isolated
(c) Conformations are obtained by breaking and remaking the bonds
(d) Conformations are same as configurational isomers

Comprehension-2

Those compounds which rotate plane polarised light are optically active compounds. They must be chiral, i.e., should
not have any plane of symmetry. They should have chiral carbon atom. Meso compounds have internal plane of
symmetry.

15. Which of the following alkane shows optical isomerism?

(a) 2-methyl pentane (b) 3-methyl pentane
•(c) 2,3-dimethyl pentane (d) Both (b) and (c)

16. Which of the following are enantiomer?

•(a) d-glucose and l-glucose (b) D-glucose and L-glucose
(c) Racemic-tartaric acid (d) Meso-tartaric acid

17. Which of the following is meso compound?

 COOH COOH CHO
CHO
H OH H OH H OH
(a) HO H •(b) H OH (c) HO H (d) H OH
CH2OH
COOH COOH CHO
Q (18) Match the column :
Column I Column II
(Property) (Compound)

H Me
(A) Plane of symmetry (P) C C
Me H

Me Me

(B) Centre of symmetry (Q)

Me
H
(C) Meso Compound (R) C
Me

Ph COOH
OH
CO H
Ph
(D) Chiral atom is / are present (S) H
H H

Cl H
(T) H
C=C=C=C
Cl

[Ans. (A) P,S,T (B) P,T (C) S (D) Q,R,S]

Q (19) Match the following:

Column I Column II
(Wrong IUPAC name) (Reason)

(A) CH 3  CH 2  CH  CH 2  CH 3 (P) Numbering of selected carbon chain is wrong

|
CN
Pentane 3  cyanide

Br Cl
| |
(B) CH 2  C  CH  CH 3 (Q) Selection of carbon chain is wrong
2  chloro  3  bromo  3  butene
 OH

(C) (R) Selection of principal F.G. is wrong

Bicyclo [4,2,0] octan-2-ol

CH3
CH3
(D) (S) Alphabetic order is not considered for writting
3,5-dimethyl octa-1,3-diene
the name

(T) Suffix of functional group is wrong

[Ans. (A) Q,T (B) P, S (C) P (D) P]

Q (20) Match the column:
Column I Column II
Cl Br
Cl
(A) A pair of metamers (P) &
Br
(B) A pair of functional isomer (Q) Acetaldoxime & acetamide

OH CH2–OH

(C) A apir of position isomer (R) &

CH3

(D) A pair of chain isomer (S) CH3  CH 2  CH 2 & CH 3  CH  CH 3

| |
CN CN

Cl

(T) Cl C–O–C &

O O
Cl Cl

C–O–C
O O

[Ans. (A) T, (B) Q,R (C) P (D) S]