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SOLVED NUMERICALS-2

19- A solution is prepared by dissolving 1.27 g of an electrolyte whose molecular


mass is 310 in 50 g of water. The freezing point was found to be 0. 762 oC.
How many moles of solute particles are formed from each mole of solute.
Given kf of water = 1.86K kg mol-1 .
Tf = i Kf m
Or i = Tf
Kf m

eq.(1)

Molality of solution =Number of moles of solute


Kilogram of solvent
= 1.27 g x mol x 1000 Kg-1
310 g x 50
= 0.819 mol Kg-1 or 0.819 m

Substituting the value of m in eq.(1)


i = 0.762 K x m
1.86 K x 0.819m

=5

Thus 5moles of solute are formed for each mole of solute


Ans = 5 moles / mole of solute
20- In a mountainous location, the boiling point of pure water is 95 oC. How many
grams of NaCl must be added to 2 kg of water so that the boiling point of
100oC is realized?
Tb = i Kb m
Tb = Tsolution Tsolvent
Tb = 100 C 95 C
= 5 C or 5 K
For NaCl i= 2
Tb = m
i Kb

or m = 5 K x m
2 x 0.52 K

= 4.807m
1

1000 g of water contains 4.807 moles of NaCl


2000 g of water contains moles of NaCl = 4.807 mol x 2000 g
1000 g
= 9.614 mol
or mass of NaCl added = 9.614 mol x 58.5 g mol -1 = 562.419g
Ans = 562.42 g
21- 3.33 kg of ethylene glycol is mixed with1.0 L of water is used as an
antifreeze in car radiators up to what temperature the solution shall not
freeze?
( density of water = 1.0 gm/ml

Kf for water

= 1.86 K/)

Tf = i Kf m
= 1.86 K x Kg x mol x 3.33 x 10 3 g x 10 3
mol x 62 g x 10 3 x Kg
= 99.9 K or 99.9C
= Tf ( solvent ) Tf ( solution )

Tf
or 99.9C

0C

Tf ( solution )

or Tf ( solution ) = 99.9C
Ans =- 99.9oC.
22- When a certain amount of solute is added to 100g of water, the vapour
pressure reduces to one half of that of pure water ( 23.76 mm of Hg). Find
the amount of solute added.
As per Raoults Law
PA

PA

XB

23.7 cm 11.8 cm
23.7 cm

XB

or 0.5

PA

XB

XB = nB moles of solute
nA moles of solvent
1.5

[ for dilute solution ]

nB
100/18
0.5 x 5.55 = nB
2.77 mol = nB
Ans = 2.77 mol.

23- Two elements X & Y form compounds having molecular formulae XY2 and
XY4 respectively . When dissolved in 20g of benzene, 1.0 g of XY2 lowers
the freezing by 2.3oC where as 1.0g of XY4 lowers the freezing point by
1.3oC . Calculate the molar masses of X & Y .Given kf benzene = 5.1 k/m
Let the molar mass of compound XY2 = M1
the molar mass of compound XY4 = M2
1.0 g of XY2 lowers the freezing by 2.3oC
Tf = Kf m
or Tf = m
Kf

or

2.3 K X m
5.1 K

= m

or 0.451 m
Molality of solution =Number of moles of solute
Mass of solvent in Kilogram
0.451 mol Kg-1 = Number of moles of solute
0.02 Kg
0.451 mol Kg-1 x 0.02 Kg = Number of moles of solute
Number of moles of solute = Mass of solute in grams
Molar mass of solute
Molar mass of solute
( M1 )

= Mass of solute in grams


Number of moles of solute
M1 = 1 g
0.451 x 0.02 mol
M1 = 110.86 g mol-1
3

1.0g of XY4 lowers the freezing point by 1.3oC


Tf = Kf m
or Tf = m
Kf

or

1.3 K X m
5.1 K

= m

or 0.255 m
Molality of solution =Number of moles of solute
Mass of solvent in Kilogram
0.255 mol Kg-1 = Number of moles of solute
0.02 Kg
0.255 mol Kg-1 x 0.02 Kg = Number of moles of solute
Number of moles of solute = Mass of solute in grams
Molar mass of solute
Molar mass of solute
( M2 )

= Mass of solute in grams


Number of moles of solute
M2 = 1 g
0.255 x 0.02 mol
M2 = 196.078 g mol-1
Ans. = M1 = 110.86 g mol-1, M2 = 196.078 g mol 1

24- The osmotic pressure of a dilute solution of KNO 3 in water is 0.47 atm at
298 K.What would be the vapour pressure of the solution, freezing point
and boiling point?The vapour pressure of water is 0.31 atm.
Assume molarity to be equal to molality.
Kb & kf for water = 0.52 K kg mol 1 & 1.86 K kg mol 1 respectively
= iCRT
Or = C
iRT

or

0.47 atm
= C
2 x 0.082atm L K-1 x mol-1 x 298 K
4

0.0096 mol L-1 = C


Since M = m 0.0096 mol of KNO3 are present in 1000 g of water
Thus , nB moles of solute KNO3 = 0.0096
nA moles of water

= 1000 g
18 g mol-1

= 55.56 mol

1) As per Raoults Law


PA

PA

PA

XB

XB nB moles of solute [ for dilute solution ]


nA moles of solvent
0.47atm x
0.47atm

0.0096
55.56

2) Tf = i Kf m
= 2 x 1.86 K x 0.0096 m
m
= 0.0357 K
Tf

or

0.0357C

= Tf ( solvent ) Tf ( solution )

Or 0.0357 C

0C

or Tf ( solution ) = 0.0357C

Tf ( solution )
or

272.982 K

3) Tb = i Kb m
= 2 x 0.52 K x 0.0096 m
m
= 0.00998 K
Tb
Or 0. 00998 C

or Tb ( solution ) =

or

0. 00998C

= Tb (solution ) Tb (( solvent )
=

100C

100C

Tb ( solution )

+ 0. 00998 C
5

or Tb ( solution)

100. 00998 C

Ans = 0.0313 atm., 272.982 K, 373.005 K


25 A 0.0140g sample of an ionic compound with formula [ Cr(NH 3)5Cl3] was
dissolved in water to give 25 ml of solution at 298 k. The osmotic pressure
was determined to be 119 mm Hg. How many ions are obtained when the
compound is dissolved in water? Suggest the formula of the complex.
= iCRT
or = i
CRT

but C = nB
V

V = i
nBRT

or

119atm x 25 L x 243.5 mol-1x mol x K


= i
760 x 1000 x 0.0140 x 0.0820atmxLx298K
2.79

=i 3

There are 3 ions in solutions.


[ Cr (NH3)5 Cl]Cl2 [ Cr (NH3)5 Cl]2+ + 2Cl
Ans 3, [ Cr NH3)5Cl]Cl2.
26-The freezing point of a 0.08 m solution of NaHSO 4 is 0.372 C. Calculate the
dissociation constant for the reaction:
HSO4 H+ + SO42

Kf for water = 1.86Km1

NaHSO4 dissociates as :
NaHSO4 Na+ + HSO4
Since the concentration of NaHSO4 is 0.08 m
[Na+] = [HSO4 ] = 0.08m
Now , HSO4 also dissociates as : HSO4 H+ + SO42If is the degree of dissociation, then after dissociation at equilibrium
[ HSO4] = 0.08 (1 ) , [H+] = 0.08 , [ SO42-] =0.08

Total concentration of all ions [Na++ HSO4+H+ + SO42-]


= 0.08 +0.08 (1 ) + 0.08 + 0.08
= 0.16 +0.08
Vant Hoff Factor i = 0.16 +0.08 = 2 +
0.08
Now ,
Tf = i Kf m
0.372 = i x 1.86 x 0.08
=

i x 0.1488

0.372 = i
0.1488
Thus, 2 + = 2.5

= 2.5
= 0.5

or

Dissociation constant for the reaction is


K = [H+] [ SO42-]
[HSO4]
[H+] = 0.08x 0.5 = 0.04

[ SO42-] = 0.08x 0.5 = 0.04

[HSO4] =0.08(1- 0.5 ) = 0.04


K = (0.04) x (0.04)
(0.04)

4.0 x 10 -2

Ans. 4.0 x 10 -2

27.1.22g of benzoic acid (C6H5COOH) is added in 100 g of acetone and 100g of


benzene .The boiling point of the solution in acetone increases by 0.17C
while that in benzene increases by 0.13C .Calculate the molar mass of
of benzoic acid in both the cases and justify your result. [K b
Kg mol -1 and Kb
Tb = Kb m

or

( benzene )

( acetone )

= 1.7 K

= 2.6 K Kg mol -1 ]

Tb = Kb x WB x 1000
GMMB x WA
7

Or GMMB = Kb x WB x 1000
Tb x WA
In the first case Kb

( acetone )

= 1.7 K Kg mol -1 WB = 1.22 g WA= 100g

Tb = 0.17
GMMB = 1.7 K Kg mol -1 x 1.22 g x 1000 Kg-1
0.17K x 100
In the first case Kb

( benzene )

= 122 g mol -1

= 2.6 K Kg mol -1 WB = 1.22 g WA= 100g

Tb = 0.13
GMMB = 2.6 K Kg mol -1 x 1.22 g x 1000 Kg-1
0.13K x 100

= 244 g mol -1

Actual molar mass of C6H5COOH = 122 g mol -1 which means that C6H5COOH
Exist as monomer in acetone and dimer in benzene.Dimeric nature is due to
intermolecular H bonding .
28.To 500 ml of water , 3 x 10 -3Kg of acetic acid is added.If 23% of acetic acid
is dissociated , what will be the depression in freezing point ?
Kf (water ) = 1.86 K Kg mol -1 and density of water is 0.997 g ml -1.
Volume of water = 500 mL

density of water = 0.997 g ml

-1

Mass of water = volume x density


or mass of water = 500 mL x 0.997 g ml -1 = 498.5 mL
Number of moles of solute = Mass of solute in grams
Molar mass of solute
moles of acetic acid

Molality of solution =

= 3 x 10 -3 x 103g
60 g mol -1

= 0.05 mol

Number of moles of solute


Mass of solvent in Kilogram
0.05 mol x 1000 Kg -1 = 0.10003m
498.5

Acetic acid dissociates in solution as :


8

CH3COOH CH3COO- + H +
Degree of dissociation = i -1
()
n-1
or (n-1)

= i -1

or (n-1) +1

= i

or 0.23 (2-1) +1

= i

Now ,

Tf =

or

i = 1.23

i Kf m

= 1.23 x 1.86 K m-1 x0.10003m = 0.229 K


Ans. Depression in freezing point = 0.229 K
29- Phenol associates in benzene to a certain extent to form a dimer. A
solution containing 20 x10 -3 kg of phenol in 1.0 kg of benzene has
freezing point depressed by 0.69 K. Calculate the fraction of phenol that
has dimerised. Given Kf ( benzene ) = 5.12 K Kg mol -1

=i1
11
n

= degree of association i = Vant Hoff factor (1)


n = no. particles associated

Tf = i Kf m
Or i = Tf
Kf m
Or i = Tf x GMMB x WA
Kf x WBx 1000
Or i = 0.69 K x 94 g mol-1 x 1000 Kg
5.12 K x Kg mol -1 x 20gx 1000
Or i = 0.633
Substituting the value of i in eq(1)

= 0.633 -1
0.5 - 1
Or = 0.366
0.5

= 0.732

Ans.0.73
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30-A solution containing 8.6 g per litre of urea was found to isotonic with a 5% of
an organic non-volatile solute (A).Calculate the molecular mass of the organic
non-volatile solute (A).
Isotonic solutions have the same osmotic pressure and hence have same
number of solute particles.
= CRT
1 = 2

C = nB
V
or

nB1RT
V1

= nB RT
V

or

nB2RT
V2

when V1 = V2
w1 =
M1

w2
M2

where w1 and w2 are the masses of the solutes per litre of the
solution.

w1 =

mass of urea per litre of solution = 8.6 g

w2 =

mass of (A) per litre of solution

= 5 g x1000 mL = 50g
100 mL

Molar mass of Urea = 60 g mol-1


w1 =
M1

w2
M2

M2

w2 x w1
M1

or

M2

= 60g mol-1 x 50g = 348.8 g mol-1


8.6 g

Ans.348.8 g mol-1

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