Liquid Solution

Liquid Solution
Hints for Subjective Problems

LEVEL – I
5. Get the value of ‘i’ in terms of .
6. Get value of total number of ions.
7. Calculate value of ‘i’ interms of  and then calculate K.
13. Wt. remains constant. With the help of total weight and density get the final volume.
14. Relate normality and weight of acid and get theoretical molecular weight. Apparent
molecular weight, calculate from given values.
LEVEL – I
8. With the help of ‘i’ get total number of ions.
12. Get the value of solvent which is required to maintain temperature = – 9.3°C.
13. Calculate empirical formula weight from the given values and molecular weight from
freezing point depression.
LEVEL – III
5. Get the solubility from lowering of vapour pressure and calculate value of Ksp.
6. Calculate value of ‘i’ and thus total number of ionisable species.
9. pT value gives [T+] and then value of ‘i’. Get value of N0 and then calculate Nt.
10. Get the weight of NH3 with the help of weight of H2O whose density is 1 g/ml.
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RSM79-P6-CH-LS(H&S)-2
Subjective Problems
LEVEL – I
1. wt. of sugar syrup (solution) = 214.2 gm

wt. of sugar (C12H22O6) = 34.2 gm
wt. of solvent = 214.2 – 34.2
W = 180 gm
mol. wt of sugar (C12H22O11) = 342 gm
w 1000
i) Molal concentration = 
m W (in gm)
34.2 1000
=  = 0.555 mol kg–1 = 0.555 m
342 180
ii) Mole fraction of sugar in the syrup
mole of sugar
=
mole of sugar  mol .of H2 O
1
10 0.1 0.1
= =  = 0.0099
1 180 0.1  10 10.1

10 18
2. In solution xA = 0.30 and hence xB = 0.70

In the vapour phase, xA, vap = 0.60 and xB, vap =0.40
Using Dalton’s law of partial pressures and Raoult’s law, we have
xA, vap = 0.60 = PA/P = PA /(PA + PB) = 0.30 P°A/ (0.30 P°A + 0.70 P°B)
xB, vap = 0.40 = PB/ P = PB /(PA + PB) = 0.70 P°B / (0.30 P°A + 0.70 P°B)
x A, vap 0.60 0.30PA0
 
xB, vap 0.40 0.70PB0
PA0 0.60  0.70 7
= =  3.5
PB0
0.40  0.30 2
P10  P1 w 2M1
3. 
P10 w1M2
In the present case,
w1 = 1.58 g ml–1  100 ml = 158 g, w2 = 0.5 g, M1 = 154 g mol–1
Substituting the various values, we have
143.0torr  141.9 torr 0.5g  154g mol 1

143.0 torr 158g  M2
M2 = 63.3 g mol–1
4.  = c2RT = (n2/V)RT
 n2 =
V 7.65 atm 1.00 dm3  
RT
=

0.0821 dm3 atm K 1 mol 1 310K  
= 0.301 mol
n2 = mass of the solute/molar mass of the solute = w2/M2

w2 = n2M2 = (0.301 mol) (180 g mol–1) = 54.18 g
5. Let the apparent molecular weight = mo

n w 1
Osmotic pressure =  = RT =   RT
v mo v
3  103 1
or, 0.3092  10 = 5
  3  8.314  298
mo 10
 mo = 240.2  10–3 kg
Since,
number of particles after dissociation normal mol . w t.

number of particles before dissociation observed mol. w t.
 Hg(CN)2 Hg ++
+ 2CN –
1–  2
 Number of particles after dissociation
= (1–) +  + 2 = 1+2
1  2 252.61 103
i.e., =
1 240.2  10 3
  = 0.02457 or 2.4567 %
11.7
6. nNaCl = = 0.2
58.5
9 .5
nMgCl 2 = = 0.1
95
8 .4
nNaHCO 3 = = 0.1
84
iNaCl = 1+  = 1+ 0.9 = 1.9
iMgCl 2 = 1 + 2 = 1+ 0.7  2 = 2.4
iNaHCO 3 = 1+ 2 = 1+ 0.5  2 = 2.0
Weight of solvent = 100 – (11.7 + 9.5 + 8.4) = 70.4 g
(iNaCl  nNaCl  iMgCl 2  nMgCl 2  iNaHCO 3  nNaHCO 3 )  K b  1000
Tb =
Weight of solvent
(1.9  0.2  2.4  0.1  2  0.1)  0.52  1000

= = 6.05°C
70.4
 Boiling point of solution = 100 + 5.94 = 106.05°C
7. Sucrose is a non–electrolyte,
Hence i = 1
Molecular weight of sucrose (C12H2O11) = m = 342 gm mol–1
Molality of the solution = 0.75 m
= 0.75 mol kg–1 solvent
= 0.75  342 gm Sucrose per kg solvent
= 256.5 gm Sucrose per kg solvent
hence, weight of 1 molal solution = 1000 + 256.5 = 1256.5 gm
256.5
Sucrose present in 1 kg solution =  1000 = 204.14 gm
1256.5
Weight of solvent (H2O) present in 1 kg solution = 1000– 204.14 = 795.86 gm

Since depression in freezing point
w 1000
Tf = Kf  i   , Where W = weight of solvent
m W
w = weight of the solute
256.5 1000
or, 4 = 1.86  1  
342 W
 W = 348.75 gm
i.e., weight of solvent required to maintain this solution at – 4°C is
W = 348.75
Hence rest weight of H2O will convert into ice.
Hence amount of ice formed = 795.86 – 348.75
= 447.11 gm
8. From question
Tf = 0.21°C
Molality of solution = 0.109 m
The reaction is
HCOOH (aq) H+(aq) + HCOO– (aq)
Initially moles C 0 0
Moles after dissociation (1–) C C C
(1  )  C    C    C
i= = 1 + , where  = degree of dissociation
1 C
As we know,
Tf = Kf  i  Cm
0.21 = 1.86  (1+)  0.109 ( in very dilute solution molarity and molality can be
taken as same)
0.21
 1+ = = 1.0358
1.86  0.109
or,  = 0.0358 = 0.036
 [HCOOH] = (1–)  C = (1–0.036)  C = 0.964 C
[H+] =   C = 0.036  C, [HCOO–] = 0.036 C
[H ][HCOO ] 0.036  C  0.036  C
Ka = = = 1.34  10–3 C mol lit–1
[HCOOH] 0.964  C
= 1.34  10–3  0.109
Ka = 1.46  10–4
9. P = PA + PB …(i)
Where PA & PB are partial pressures of A and B respectively
P = PA0  X A  PB0  XB
 400 = PA0  0.65  PB0  0.35
Given, XA = 0.65,  XB = 1 – 0.65 = 0.35
mole fraction of A in vapour, YA = 0.45
PA0  0.65
0.45 = YA =
400
0.45  400
 PA 
0
= 276.9 mm Hg
0.65
Similarly,
P0  X P0  0.35
YB = B B  B
400 400
PB0  0.35
or, 1 – 0.45 =
400
0.55  400
 PB0  = 628.6 mm Hg
0.35
10. Density of acetic acid in 2.0 M acetic acid solution = 1.20 Kgm/ml of the solution
Mass of solution = volumedensity = (1.00 dm-3) (1.02 kg/dm3) = 1020 gm
 Mass of solvent (water) = 1020 – 120 = 900 g
n (acetic acid) = 120 g/60 g mol–1 = 2.0 mol
n (water) = 900 g/18 g mol–1 = 50.0 mol
 x (acetic acid) = 2.0 /(50.0 + 2.0) = 0.038
1.25 1.25
11. X E= = 0.5 and XM = = 0.5
1.25  1.25 1.25  1.25
Pt = PE + PM
= PE0  XE  PM0  XM = 44.5  0.5 + 88.7  0.5
= 22.25 + 44.35 = 66.6
PE = 22.25
PM = 44.35
From Dalton’s law of partial pressure
P 22.25
XE  E  = 0.33
Pt 66.6
P 44.35
XM  M  = 0.67
Pt 66.6
12.  Solution are isotonic

sugar = NaCl
Assuming NaCl to be dissociated completely
i for NaCl = 1 + 
=1
i = 2
i for sugar = 1 [as it is non-electrolyte]
1 9  1000 2.923 1000  5  T
  s  T = 2 
m  50 58.5 100
 m = 180.123 gm
13. Mass of ethanol = v  d

W = 20  0.7893 gm
= 15.786 gm
Mass of water = v  d
= 40  0.9971 gm
= 39.884 gm
Total volume = 60 ml
Total mass = 15.786 + 39.884 = 55.67 gm
Let the volume of solution = x ml
mass 55.67
X= =
density 0.9571
= 58.165 ml
Change in volume = 60 – 58.165
= 1.835 ml
1.835
% change in volume =  100
60
= 3.05%
w 1000
Molality, m = 
m W (in gm)
15.786 1000
=  = 8.604 m
46 39.884
N
14. 15.1 ml   alkali is required by 0.2 gm monobasic acid
 10 
0.2  1000
1000 ml (N) alkali is required by gm monobasic acid
1.51
= 132.45 gm monobasic acid
Equivalent wt. of monobasic acid, E = 132.45 = mol. wt.
T = K  i  Cm
w 1000
T = K  i  
m W
1 1000
or, 0.168 = 1.86  i  
132 .45 100
0.168  132 .45
i=
18.6
i = 1.196
For monobasic acid, HA H+ + A–
1–  
(1  )    
i= =1+
1
1 +  = 1.196
 = 0.196
15. Assuming mA & mB be mol. wt of A and B respectively

(I) V = (nA + nB) RT …(1)
V = 0.5 liter
 10 20 
pr,   0.5 =     RT …(2)
 m A mB 
On dividing equation (2) by equation (3)
10 20 6.67 30
  
m A mB mA mB
1 1
or, (10  6.67)   (30  20) 
mA mB
3.33 10
or, 
mA mB
m 3.33
 A  = 0.3
mB 10
LEVEL – II
1. In benzene i = 1
Tf = i  Kf  m
 1.28° = 1  5.12  m …(i)
In water
1.4° = i  1.86 m …(2)
 Dividing equation (1) by (2)
2.75
0.91 =
i
2.75
i= =3
0.91
Each molecule dissociates into 3 ions
2. NaCl  Na+ + Cl–

1–  
i=1–++=1+
11
  S  T = (1 + )  0.1  S  T
60
11
1+= = 1.83
6
 = 0.83 or 83%
3. CH3COOH CH3COO– + H+
1 0 0
(1 – )  
i=1–++=1+
i = 1 + 0.03 = 1.03
Tf = 1.03  0.02  1.86
= 0.038°
 F.P. = – 0.038°C
 = CST (assuming m = M)
= 1.03  0.02  0.0821  298
  = 0.504 atm
4. Glycol because of it’s lower molecular weight contains more moles than glycerol in a
given mass. It means glycol solution will have higher molality and thus lower freezing
point to a greater extent than glycerol.
5. Tf = i  m Kf (assuming i = 1)

36  1000
0.93 =
M  1200
 M = 60
Let the molecular formula is (CH2O)n
Empirical formula weight = 12 + 2 + 16 = 30
 n  30 = 60
n=2
i.e. molecular formula is C2H4O2
6. Ph3COH when dissolved in conc. H2SO4 dissociates completely follows

Ph3COHH2SO4  Ph3C+ + H2O + HSO4–
Ph3C+ is highly resonance stabilized cation. CH3OH, however, does not dissociate in
the same way because resulting CH3+ is highly unstable.
7. Due to ionization of KCl

KCl  K+ + Cl–
Initial moles 1 0 0
Moles after dissociation 1–  
i=
1      
= 1+ 
1
From question, degree of ionization =  = 0.86
i = 1+ 0.86 = 1.86
For Osmotic pressure of glucose,
For 4% glucose solution,
Weight of glucose = 4 gm
Volume of solution = V = 1L = 1dm3
Molecular weight of glucose C6H12O6= m = 180
1
 glucose =n
 RT, where glucose = osmotic pressure of glucose
v
w 1 40 1
=  RT=   RT
m v 180 1
1
Similarly , KCl = i  n   RT
v
1 w 1 w1 1
= 1.86  n  RT= 1.86  1   RT = 1.86   RT
v m1 v 74.5 1
As both solutions are isotonic
KCl = glucose
w1 40
1.86   RT =  RT
74.5 180
40 74.5
 W1 =  = 8.9 gm
180 1.86
8. From question, molality of solution = Cm = 0.1

Depression in freezing point = Tf = 0.558°C
Kf (H2O) = 1.86 kg mol–1 K–1
As we know that
Tf = Kf  i  Cm , Where i = Vont Hoff’s factor
0.558 = 1.86  0.1  i
0.558
i= =3
0.186
or, i  3 indicates that complex ionize to form three ions since co ordination number
is 6 hence x = 5
i.e., CoCl3.5NH3  [Co(NH3)5Cl]++ + 2Cl–
 
1 Cation 2 anions
So, the complex is [Co(NH3)5Cl]Cl2
9. K2SO4  2K+ + SO42–

1 0 0
1– 2 
i = 1 –  + 2 +  = 1 + 2
Tf = i  Kf  m
0.0268 = (1 + 2)  0.005  1.86
 1 + 2 = 2.88
2 = 1.88
 = 0.94 or 94%
10. Tf (KCN solution) = 0.704°C

molality of KCN solution = 0.1892
For KCN, i = 1 + , where  = degree of dissociation
Tf = Kf  i  molality
0.704 = 1.86  i  0.1892
0.704
i= =2
1.86  0.1892
or , 1 +  = 2
  = 1, indicates 100% ionization of KCN.
Now, Tf (of the complex) = 0.530°C
molality of Hg(CN)2 = 0.095 mol kg–1 = 0.095 m
Kn [Hg(CN)n+2] nK+ + [Hg(CN)n+2]–
1 0 0 ….. initially moles
1– n  ….. moles after dissociation
here i = (1–) + n +  = 1+n
=1
 i = 1+ n
0.503 = 1.86  I  0.095
0.503
i=  3
1.86  0.095
1+ n = 3 or, n = 2
Hence, the complex is K2[Hg(CN)4]
11. We have,
p0  21.85 30  18
 For I case (1)
21.85 90  m
Now weight of solvent = 90 + 18
= 108 g
p0  22.15 30  18
 For II case (2)
22.15 108  m
 By equation (1) Pm0 – 21.85 m = 21.85  6 = 131.1
By equation (2) Pm0 – 22.15 m = 22.15  5 = 110.75
––––––––––––––––––––––––––––––––––––––––––
0.30 m = 20.35
m = 67.83
On substituting in equation (1)
P0  21.85 30  18

21.85 90  67.83
p0 = 23.78 m
WB  1000
12. T = Kf  (1)
mB  WA
mB = molecular weight of solute (ethylene glycol)
= 62
50
9.3 = 1.86   1000
62  WA
WA = 161.29 gm
Remaining water will separate out as ice
Weight of ice separated = 200 – 161.29 = 38.71 gm
13. Let A  C2H4Br2

mA = 24 + 4 + 160
= 188
B  C3H6Br2 mB = 36 + 6 + 160
= 202
W 10
nA  A  = 0.053
mA 188
W 80
nB = B  = 0.396
mB 202
nB 0.396
XB   = 0.881
nA  nB 0.396  0.053
Similarly, XB = 1 – XA =0.118
0 0
Given PA =173 mm, PB = 127 mm Hg
a) We know
P = PA + PB
= PA0 XA  PBo XB
= 173  0.118 + 127  0.881
= 20.414 + 111.888 = 132.301

Here PA = Partial pressure of C2H4Br2 = 20.414 mm
PB = Partial pressure of C3H6Br2 = 111.888 ml
b) Mole fraction of ethylene dibromide in the vapour (i.e.)

Partial pressure of A
YA =
Total Pr essure
20.414
= = 0.154
132 .301
c) Since, in vapour nA : nB = 50 : 50
YA = 0.5, YB = 0.5
We know that,
P  PA0 XA  PB0 XB
PA P
 YA B  YB
P p
PA0 X A P0 X
 YA B B = YB
P p
173  X A 127  XB
 0.5 (i) = 0.5 (ii)
P P
Dividing equation (i) by equation (ii), we get
173 X A X
 1 or A = 0.734
127 XB XB
We know, XA + XB = 1
0.734 XB + XB = 1
1
XB = = 0.58
1.734
14. Case 1: Given  mB (Cane sugar) = 342

WB = 342 gm
WA = 1000 gm
Kf = 1.,86
Tf = Kf Xm
WB
= Kf   1000
mB  X A
342
= 1.86   1000 = 1.86
342  1000
Case II: Given  W B = 11.7 gm NaCl, W A = 200 gm H2O

mB = 58.5 NaCl
t = i  Kf  m
11.7
2  1.86 = i  1.86   1000
58.5  200
i=2
Value of ‘i’ factor indicates that NaCl fully dissociates into 2 ions.
15. Given
T = 209 – 161 = 48°
w = 0.09 g
K f = 37.5° mol–1 kg
1000  Kf  W
0T =
m W
1000  37.5  0.09
48 =
m  0.55
w = 0.55 g
 m = 127.84
%
Now % value Value/lowest value
At. w t.
93.75 7.8125
C = 93.75  7.8125 = 1.25
12 6.25
6.25 6.25
H = 6.25 = 6.25 =1
1 6.25
C : H : : 1.25 : 1 or 5 : 4
(or) 5:4
 Empirical formula is C5H4 and
empirical formula weight = 64
127 .84
 Molecular formula is (C5H4)n and n = 2
64
 Molecular formula of solute is (C5H4)2 = C10H8
LEVEL – III
1. Wt. of carbon is 1.434g of CO2

12
=  1.434 = 0.391g
44
2
Wt. of hydrogen in 0.783 g H2O =  0.783 = 0.087g
18
Wt. of oxygen in compound = 1 – (0.391 + 0.087) = 0.522g
C H O
0.391 0.087 0.522
0.391 0.087 0.522
Relative no. of –––––– –––––– ––––––
atoms 12 1 16
= 0.0326 0.087 0.0326
or 1 2.667 1
or 3 8 3
Empirical formula = C3H8O3
Molecular formula = (C3H8O3)n
Tf = i  Kf+  m
1 1000
0.0894 = 1  1.86 
molecular w eight
 Molecular weight = 832.215 gm
Empirical formula wt = 12  3 + 8 + 3  16 = 92
832 .215
n= =9
92
 Molecular formula = (C3H8O3)9 or C27H72O27
2. Elevation in B.P. = 101.24 – 100

= 1.24°C
Since solute is non volatile
Since the elevation in boiling point is
Tb = Kb  i  molality
w 1000
= Kb  1 
m W
288 1000
1.24 = 0.512  
m 90
 m = 1321.2 gm mol–1 Kb = 0.512
m = mol.wt. of solute
molar mass of CxH2xOx = 12x + 1  2x + 16x = 30x
 30x = 1321.2
 x = 44
Hence the molecular formula is
= C44H88O44
3. Let acetic acid = A

Benzene = B
Assume,  part of A forms dimer
2A A2
1 0 initially moles
1– /2 moles after dimer is formed
i=
1      2 = 1 – /2
1
Mol. fraction of A = xA = 0.02
Mol. fraction of B = xB = 0.98
x 1000
Molarity of A in B = A 
m XB
0.02 1000
=  = 0.262 mol kg–1
78 0.98
Since, Tf = Kf  i  molality
278.4–277.4 = 5  i  0.262
or, 1 = 5  i  0.262
i = = 0.763
1– /2 = 0.763
  = 0.47
Hence the molality of A after dimer is formed = (1–)  initial molality
= (1 – 0.48)  initial molality
= 0.52  0.262
Molality of A2 after dimer is formed


=  molality
2
0.48
=  0.262 = 0.24  0.26
2
= 0.06288
The equilibrium constant
Keq =
A 2 
A 2
0.06288
= = 3.39 kg mol–1
(0.13624 )2
4. We know that,
Tf = i  kf  m (i)
Where i = Vant Hoff factor
T = 0.06
Kf = 1.86
m = molality
Molality may be taken as molarity because solution is dilute and solvent is water.
=3  10–2
Substituting the values in equation (i), we get,
0.06 = i  1.86  3  10–2
0.06
i=
1.86  3  10  2
i = 1.07526
Let acid is MH
MH M– + H+
Tequilibrium C (1 – ) C C
C  C
Ka = = C2
C(1   )
Total mole after dissociation C(1  )  C  C
i = =1+
initial mole C
=i–1
 = 1.07526 – 1
 = 0.07526
Ka = C2 = 3  10–2  (0.07526)2
Ka = 1.6992  10–4
pKa = –logKa
= –log (1.6992  10-4) = + 3.769
5. Let the solubility of X2Y3 be s moles /lit

X2Y3 2X3+ + 3Y2–
2S 3S
Ksp = (2S)2 (3S)3 = 108S5
P0  P n S
 i  5 [W = 1000 gm, MH2 O = 18 m]
P N 55.56
31.9  31.8 55
or 
31.8 55.56
 S = 0.035 moles/lt
Ksp 5.67  10–6
6. T = K  i  Cm
w 1000
= K  (1 + )  
m W (in gm)
0.7 1000
0.406 = 1.86  (1 + )  
58.5 100
0.4  58.5  100
1 +  =
1.86  0.7  1000
assuming dilute solution
100 gm H2O 100 ml H2O = 0.1 L solution
n
 = i  1  RT
V
w 1
= (1 + )  1   RT
m1 v
0.406  58.5  100 0.7 1
=    0.082  298
1000  1.86  0.7 58.5 0.1
 = 5.34 Atm
7. Let the complex be [Pt(NH3)4Clx]Cl4-x

Now, the complex ionises as:-
[Pt(NH3)4Clx]Cl4-x [Pt(NH3)4Clx]+(4-x) + (4-x)Cl–
Initial moles 1 0 0
Moles after dissociation mole 1- (4-x)
(1  )    ( 4  x )
i=
1
(1  )  ( 4  x )
i= , where  = degree of dissociation
1
for 100% dissociation  = 1
i = 1 + (4 – ) 1
=5–x
T = K  i  molality
or, 0.0054 = 1.86  (5 – )  0.001
x = 02.152 (x is a whole no.)
2
Hence the complex is[Pt (NH3)4Cl2]Cl2
8. Mol. wt. of NH4Cl = 14 + 3 + 35.5 = 53.5

20
Moles of NH4Cl = = 0.19
53.5
NH4Cl  NH 4 + Cl 
Initially moles 0.19 0 0
After dissociation, moles 0.19 (1–0.75) 0.19  .75 0.19  0.19  0.75
0.05 0.14 0.14
Now, NH 4 + H2O NH4OH + H+

0.14 – 0.14 h 0.14 h 0.14 h
(Let h = degree of hydrlysis)
Total moles =0.05 + 0.14 + (0.14 – 0.14 h) + 0.14 h + 0.14 h
= 0.33 + 0.14 h
As we know, T = K  Cm
0.637 = 186  (0.33 +0.14 h)
h = 0.089
9. TF T+ + F–
Initially concentration C 0 0
Concentration at equilibrium C – C C
[T+] = c
–PT = log (T+)
–1.5 = log [T+]
[T+-] = 0.316
C = 0.0316
(c  c)  c  c
Here i =  1 
c
As we know,
T = K  i  c
= K  ( 1 + )  c
T = K ( c + c)
or, 0.372 = 1.86  (c + c)
or, c + c = 0.2
or, c + 0.0316 = 0.2
c = 0.1684 mole/lit
(c) 2 (0.0316 ) 2
Ka =  = 7.299  10–3
c  c 0.1368
 1000 ml of freshly prepared solution contains 0.1684 moles
0.1684  600
600 ml of freshly prepared contents moles
1000
= 0.101 mole
total time
No. of half-lives n =
half  life
24.8
 =2
12.4
N
Since, 0  2 n where N0 = initially amount = 0.101/mole
N
N
 0  22 = 4 N = rest amount
N
1 1
N =  N0 =  0.101 mole
4 4
Moles decayaed, dN = N0 – N
1
= 1.101 –  0.101
4
 1
= 0.101 1  
 4 
3
= 0.101 
4
= 0.758 mole atoms
= 0.0758  6.023  1023 atoms
= 4.55  1022 atoms
No. of atoms decayed = No. of -particles emitted
= 4.55  1022 -particles
10. Let the volume of NH3 solution = V ml

Wt. of NH3 solution = V  0.9 gm
Wt. of NH3 = V  0.9 – 105 gm
Here wt. of water = 105 gm
There is 30% NH3 by mass of solution
30
wt. of NH3 =  V  0.9 gm
100
= 0.27 v gm …..(2)
From equation (I) and (2), we have
V  0.9 – 105 = 0.27 V
or, 0.63 V = 105
105
V = = 166.66 ml
0.63
= 44.9982 gm
44.9982
moles of NH3 = = 2.6469
17
PV = nRT
775
 V = 2.6469  0.0821  278
760
V = 59.24 litres
11. T = K  i  Cm
WA 1000
T = k  1  
m A W (in gm)
WA 1000
6 = 1.85  1  
62 40,000
 WA = 804.32 gm
12. P = 180 XB + 90
when XB = 0
P = P0T
 P0T = 90
when XB = 1
P = P0B
 P0B = 270
12 8
P = 270   90 
12  8 12  8
= 162 + 36 = 198 mm
P0 X 162
YB = B B  = 0.82
P 198
 YT= 0.18
On condensation
YB = XB (X = mole fraction in condensed liquid)
YT = XT
P = 0.82  270 + 0.18  90
= 237.6
0.82  270
 YB = = 0.93
237.6
13. Given
PA0  300 torr , .
X'A  0.25 , X 'B  1  0.25  0.75.
a) By the condensation of only one drop, we can assume that composition of the
vapour remains the same.
P0 X P0 X
X 'A  A A and X B'  B B
P P
X'A PA0 X A
or  0
XB' PB 1  X A 
Putting various known values we get
XA = 0.47 and XB = 0.53
b) P = PAo X A  PBo X B
= 0.47  300 + 0.53  800 = 565 torr
c) 760 = 300 XA + 800XB

XA = 0.08 and XB = 0.92
d) When only the last bubble of vapour remains, we can assume composition of
vapour is now the composition of the condensate.
Hence, P = 0.25  300 + 0.75  800
= 675 torr
e) Composition of the last bubble:
Po X 0.25  300
X"A  A A   0.11
P 675
XB"  0.89
14. Let the degree of dimer formation be . The reaction occurs as under:-
2A (A)2
Initially m 0
m
after dimer formation m- m
2
where m = molality = molarity (as also given)
Due to dimer formation,, the resultant
m
Molality will be = (m  m ) 
2
m
(m  m ) 
Vont Hoff’s factor, i = 2
m
 
m1  
i= 
2
m

i = 1
2
As we know the elevation in boiling point,
 Tb = Kb  i  Cm,
 
 Tb = Kb  1    m, here Cm = m
 2
2(K b m  Tb )
=
K bm
The equilibrium constant for dimer formations
 
m m
[A 2 ] 2
Keq =  = 2 2 2
[A] 2
m(1  ) 2
m (1   )

Keq = …(1)
2m(1   ) 2
Putting the value of  in equation (1)
2(K b m  Tb )
K bm
Keq =
 2(K b m  Tb ) 2 
2m1  
 K bm 
K eq (Kbm  Tb )
or, Kequ =
(2Tb  Kbm )2
15. a) The first vapour will be formed when the external pressure becomes equal to the
vapour pressure of the system.
P = XT PT0  PB0 XB
P  32.05   103 
1 1
2 2
= 67.52 mm Hg
b) Composition of the first trace of vapour formed

Po X 0.5  32.05
X'T  T T   0.24
P 67.52
XB'  1  0.240 = 0.76
c) The last trace of liquid will disappear when the composition of the vapour phase
has become XB'  0.5andX'T  0.5
The pressure at which this occurs can be calculated as

1 X'T XB' 0.5 0.5
 0  0  
P PT PB 32.05 103
P = 49.01 mm Hg
d) Composition of the last trace of the liquid will be.

P0 X
XB'  B B
P
32.05 XB
0.5 
49.01
XB = 0.76 and XT = 0.24
e) XT = 0.642, XB = 0.358 and X’B = 0.642 , X’T = 0.358, P = 57.46 mm Hg
Objective Problems
LEVEL - I
1. Both K4Fe(CN)6 and Al2(SO4)3 give 5 ions on ionisation

 (A)
2. KNO3 is 100% ionised while CH3COOH is weak electrolyte

 iKNO3  iCH3COOH  P1  P2
(C)
3. Reverse osmosis involves movement of solvent particles through semipermeable

membrane from concentrated solution to dilute solution under pressure.
(D)
TfA 2 1
4.   i.e. B should associate to show higher T
TfB 1 1/ 2
(C)
w
5. Osmotic pressure of solution is given by   RT
mv
mv 60  20.4  0.1
w = = 5g
RT 0.082  298
 (A)
6. Depression in freezing point  molality  n

For NaCl, Tf  2  2
For AlCl3, Tf  4  1.5
For Al2(SO4)3 Tf  5  1
For Urea Tf  3  1
Since, lowest depression is observed for solution containing urea, hence it will have
highest Freezing Point.
 (D)
7. The weak electrolyte partially dissociates as under

AxBy  xA+y -+ yB–x
Initially moles 1 0 0
After dissociation moles 1 –  x y
So, i = 1 + (x + y – 1) 
i 1
or,  =
x  y 1
 (B)
8. As we know, the depression in freezing point is

From question, molal concentration = Cm = 0.05m
For, non-electrolytes, i = 1
Kf = 1.86
Tf = 1.86  1  0.05
= 0.0930°C
hence, F.P. of solution = 0 – 0.093°C = –0.093°C
(C)
9. We know that the value of colligative property is directly proportional to no. of

particles of solute.
Since K4[Fe(CN)6] and Al2(SO4)3 both form 5 ions on dissociation. Hence osmotic
pressure of Al2(SO4)3 solution will be nearest to that of equimolar solution of
K4[Fe(CN)6]
(C)
1000 K f w
10. Tf =
mW
1000 K f w 1000  5  0.48
m =
Tf W 1.8  10.6
= 125.79
(C)
11. Elevation in b.p. is given by

Tb = i  Kb  molality
w
or Tb = i  1000 Kb 
mW
W
is same for all, hence
W
1
Tb 
M
Since sucrose has the highest molecular weight hence, lowest elevation will be
observed in this case so, 1% sucrose solution will have lowest b.p.
(D)
12.  = iCRT
i = 1, for glucose, urea & sucrose
  = CRT
w
= RT
M V
1

M
Since w and v are same for all at given temperature
Hence P2 > P1 > P3 (  Murea  Mglucose  Msucrose
(C)
13. Mass of solvent does not change with temperature.

 (D)
14. Tb = i  m  Kb  0.5 = I  0.51  i  m = 0.5/0.51

0.5 = i  m  Kf
0 .5
=  1.86 = 1.82
0.51
 F.P. = 0 – 182 = – 1.82°C
(B)
15. Mole fraction in vapour phase also depend upon volatility of A and B i.e. P0A and P0B
 (B)
16. Tb = I  Kb  m
i = 1, for an ideal solution
 (A)
17. Solute molecules are not small enough to pass through pores of semipermeable
membrane.
(B)
18. In ideal solution intermolecular forces among molecules of A and B are identical to
that among the molecules of A and to that among the molecules of B.
 H(mixing) = 0
V(mixing) = 0
S(mixing) = 0
(D)
19. Intermolecular forces among molecules of n-heptane and ethyl alcohols are weaker
than among hexane and among ethyl alcohol molecules  V.P. of solution is more
than V.P. of pure solvents.
(B)
20. F = 6 nrV
(C)
21. La(NO3)3 will furnish four ions and thus will develop more lowering in freezing point
where as glucose gives only one particle and thus lowering in freezing point is
minimum.
(D)
22. 5.8% (wt./vol.) NaCl has molarity

5.8  1000
= =1M
58.5  100
Thus it will show approximately 2 M in solution ( i = 2., strong electrolyte)
(C)
1000  K f  w
23. T =
m w
1000  1.86  20
 0.74 =
m  500
 m = 100
normal ,mol .w t.
Now, =1+
exp. mol . w t.
100
  1    = 0
100
(D)
24. More is the valency of effective ion, greater is its coagulating power. (Here cation)
(D)
25. Negatively charged sols require minimum amount of electrolyte having higher
valency of cation.
(A)
26. Soil particles possess the tendency to adsorb preferentially the common ion present
in solution.
(B)
27. On passing H2S through cold solution of an oxidant, colloidal sulphur is formed.
(B)
28. Gold no. is to be reported in mg.

(C)
29. P = P0B xB + P0TxT

P = 119  0.5 + 37  0.5
P0 X 37  0.5
YT = T T = = 0.2037
P 119  0.5  37  0.5
 (C)
ΔP 0.1
30.  , P =
296 1000
0.1 
18
100
where = no. of moles water  P = 0.533 torr
18
 (A)
31. P = P0AxA+ P0BxB
1 4 1
= 0.359  + 0.453  = (0.359  1.812 ) = 0.434
5 5 5
P0  Ps n
32. 
P 0
n  N
20
0.25  Ps 120 0.167
 =
0.25 20 10 0.167  0.217

120 46
0.25  0.167
 0.25 – Ps =  Ps = 0.141
0.167  0.217
33. Mass of solvent does not change with temperature.
 (D)
0.736  Ps 5
34. 
0.736 152
5 50

152 112.5
On solving Ps = 0.677 atm
 (C)
P60 X6 408  0.3

35. Y6 =  …(1)
P P
P70  X7 141  0.7
Y7 =  …(2)
P P
Dividing equation (1) by (2)
Y6
= 1.24 & Y6 + Y7 = 1
Y7
 Y7 = 0.446 & Y6 = 0.554
 (B)
36. 0.35 = 0.507  XB + 0.184  Xt …(1)

XB + Xt = 1 ...(2)
On solving equation (1) and (2)
XB = 0.514
 (A)
PB0  XB
37. YB =
P
93.2  0.5
YB =
P
28.2  0.5
YT =
P
YB
  3.3 & YB + YT = 1
YT
On solving yB = 0.768
(A)
38. PT = P0T  XT
= 0.188  0.5
= 0.094
(D)
39. Intermolecular forces among molecules of n-heptane and ethyl alcohols are weaker
than among hexane and among ethyl alcohol molecules  V.P. of solution is more
than V.P. of pure solvents.
(B)
40. Vont’s Hoff factor (i) for K4[Fe(CN)6] is 5 (assuming complete ionization)
K4[Fe(CN6]  4K+ + [Fe(CN)6]-4
 
1 molecule 4 cations 1 anion
Similarly, i for Fe4[Fe(CN)6]3 is 7
As we know, colligative properties  i
iK 4 [Fe( CN) ] Colligativ e properties of K 4 [Fe(CN )6 ] 5
6
  = 0.71
iFe 4 [Fe( CN)6 ] 3 Colligativ e properties of Fe 4 [Fe(CN )6 ]3 7
(B)

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Hints for Subjective Problems

5. Get the value of ‘i’ in terms of .

6. Get value of total number of ions.

7. Calculate value of ‘i’ interms of  and then calculate K.

8. With the help of ‘i’ get total number of ions.

6. Calculate value of ‘i’ and thus total number of ionisable species.

1. wt. of sugar syrup (solution) = 214.2 gm

2. In solution xA = 0.30 and hence xB = 0.70

n2 = mass of the solute/molar mass of the solute = w2/M2

5. Let the apparent molecular weight = mo

(1.9  0.2  2.4  0.1  2  0.1)  0.52  1000

Weight of solvent (H2O) present in 1 kg solution = 1000– 204.14 = 795.86 gm

12.  Solution are isotonic

13. Mass of ethanol = v  d

15. Assuming mA & mB be mol. wt of A and B respectively

2. NaCl  Na+ + Cl–

5. Tf = i  m Kf (assuming i = 1)

6. Ph3COH when dissolved in conc. H2SO4 dissociates completely follows

7. Due to ionization of KCl

8. From question, molality of solution = Cm = 0.1

9. K2SO4  2K+ + SO42–

10. Tf (KCN solution) = 0.704°C

13. Let A  C2H4Br2

= 20.414 + 111.888 = 132.301

b) Mole fraction of ethylene dibromide in the vapour (i.e.)

14. Case 1: Given  mB (Cane sugar) = 342

Case II: Given  W B = 11.7 gm NaCl, W A = 200 gm H2O

1. Wt. of carbon is 1.434g of CO2

2. Elevation in B.P. = 101.24 – 100

3. Let acetic acid = A

Molality of A2 after dimer is formed

5. Let the solubility of X2Y3 be s moles /lit

7. Let the complex be [Pt(NH3)4Clx]Cl4-x

8. Mol. wt. of NH4Cl = 14 + 3 + 35.5 = 53.5

Now, NH 4 + H2O NH4OH + H+

10. Let the volume of NH3 solution = V ml

c) 760 = 300 XA + 800XB

b) Composition of the first trace of vapour formed

The pressure at which this occurs can be calculated as

d) Composition of the last trace of the liquid will be.

e) XT = 0.642, XB = 0.358 and X’B = 0.642 , X’T = 0.358, P = 57.46 mm Hg

1. Both K4Fe(CN)6 and Al2(SO4)3 give 5 ions on ionisation

2. KNO3 is 100% ionised while CH3COOH is weak electrolyte

3. Reverse osmosis involves movement of solvent particles through semipermeable

6. Depression in freezing point  molality  n

7. The weak electrolyte partially dissociates as under

8. As we know, the depression in freezing point is

9. We know that the value of colligative property is directly proportional to no. of

11. Elevation in b.p. is given by

13. Mass of solvent does not change with temperature.

14. Tb = i  m  Kb  0.5 = I  0.51  i  m = 0.5/0.51

22. 5.8% (wt./vol.) NaCl has molarity

28. Gold no. is to be reported in mg.

29. P = P0B xB + P0TxT

P60 X6 408  0.3

36. 0.35 = 0.507  XB + 0.184  Xt …(1)

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