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UNIT 2
SOLUTIONS

ANAND PATRACHAR SCHOOL

BRANCHES:ROHINI,LAXMI NAGAR,RAJA GARDEN,HAUZKHAS
CONTACTS NO.9999132085,8860650600,9212025026

Points to Remember

1. The component that is having more number of moles is known as solvent. Solvent
determines the physical state of the solution. Water is an universal solvent.

2. Mole fraction (X) is a unitless quantity.

3. Molality (m) and mole fraction are temperature independent quantities whereas
molarity decreases with increase in temperature.

4. As the temperature increases Henry’s law constant, KH increases so the lower is

the solubility of the gas in the liquid.

5. 11.7% w/w Helium is added to air used by scuba divers due to its low solubility
in the blood.

6. Raoult’s law becomes a special case of Henry’s law in which KH becomes equal
to PA0, i.e., vapour pressure of pure solvent.

7. Azeotropes having the same composition in liquid and vapour phase and boil at a
constant temperature and therefore can’t be distilled.

8. Azeotropes arise due to very large deviation from Raoult’s law. Maximum
boiling azeotropes form when solutions exhibit negative deviation from Raoult’s
law whereas minimum boiling azeotropes form when solutions exhibit positive
deviation from Raoult’s law.

9. Relative lowering in vapour pressure is a colligative property but lowering in

vapour pressure is not.

10. Van’t Hoff factor (i) is the ratio of the observed value of the colligative property
in solution to the theoretically calculated value of the colligative property.

(a) A non-volatile solute undergoes dissociation, then i > 1.

(b) A non-volatile solute undergoes association, then i < 1.

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Some Important Formulae

1. Mole fraction (X)

If the number of moles of A and B are nA and nB respectively, the mole fractions
of A and B will be
nA nB
XA  and X B 
nn n n
A B A B

XA + XB = 1
Moles of solute 1
2. Molarity (M) = Volume of solution in litres mol L

Moles of solute
3. Molality (m) = mol kg1
Mass of solvent in kilograms

4. Parts per million (ppm)

 Number of parts of the compound 106
Total number of parts of all components of the solution

5. Raoult’s law for a solution of volatile solute in volatile solvent :

pA= p 0AX A
0
pB= p X B B

Where pA and pB are partial vapour pressures of component ‘A’ and component
‘B’ respectively in solution. p 0 and p 0 are vapour pressures of pure components
A B
‘A’ and ‘B’ respectively.
6. Raoult’s law for a solution of non-volatile solute and volatile solvent :

p A0  p n W B M
 
i nB  i W  M
A A
p 0 iX B (for dilute solutions)
A A A B
pA 0  pA
Where X is mole fraction of solute, i is van’t Hoff factor and is relative
B 0
lowering of vapour pressure. pA
7. Elevation in boiling point (Tb) :
Tb = i.Kb m
Where Tb= T –b T 0
b

Kb = molal boiling point elevation constant

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 Solutions | 21
m = molality of solution
Tb = Boiling point of solution
Tb0 = Boiling point of solvent
8. Depression in freezing point (Tf ) :
Tf = i.Kf m
Where Tf = Tf 0 – T f
Kf = molal freezing point depression constant
m = molality of solution
Tf 0 = Freezing point of solvent
Tf = Freezing point of solution
9. Osmotic pressure () of a solution :
V = i nRT or  = i CRT
where  = osmotic pressure in bar or atm
V = volume in litres
i = van’t Hoff factor
C = molar concentration in moles per litres
n = number of moles of solute
T = Temperature on Kelvin scale
R = 0.083 L bar mol–1 K–1
R = 0.0821 L atm mol–1 K–1
10. Van’t Hoff factor (i)

Number of particles in solution after association or dissociation


Number of particles actually dissolved in solution

Observed colligative property

i
Theoretically calculated colligative property

Normal molar mass

i
Abnormal molar mass

i > 1 For dissociation of solute

i < 1 For association of solute
i = 1 For ideal solution undergoing no association or dissociation

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VERY SHORT ANSWER TYPE QUESTIONS (1 Mark)
Q. 1. What is Van’t Hoff factor ?
Ans. It is the ratio of normal molecular mass to observed molecular mass. It is denoted
as i.
i = normal molecular mass/observed molecular mass
= no. of particles after association or dissociation/no. of particles before
dissociation or association
Q. 2. What is the Van’t Hoff factor in K4[Fe(CN)6] and BaCl2 ?
Ans. 5 and 3
Q. 3. Why the molecular mass becomes abnormal ?
Ans. Due to association or dissociation of solute in given solvent.
Q. 4. Define molarity. How it is related with normality ?
Ans. N = M  Basicity or acidity
Q. 5. How molarity is related with mass percentage and density of solution ?
Mass%  d  10
Ans. M  Here d is density of the solution in gmL–1
MB
Q. 6. What role does the molecular interaction play in the solution of alcohol and
water ?
Ans. Positive deviation from ideal behaviour.
Q. 7. What is van’t Hoff factor ? How is it related with :
(a) degree of dissociation (b) degree of association
Ans. (a)  = i – 1/n – 1 (b)  = i – 1/1/n – 1
Q. 8. Why NaCl is used to clear snow from roads ?
Ans. It lowers freezing point of water.
Q. 9. Why the boiling point of solution is higher than pure liquid ?
Ans. Due to lowering in vapour pressure.
Out of 1 M and 1 m aqueous solution which is more concentrated ?
Ans. 1 M as density of water is 1 gm/ml.
Henry law constant for two gases are 21.5 and 49.5 atm, which gas is more
soluble ?
Ans. KH is inversely proportional to solubility.

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 Solutions | 23

Define azeotrope. Give an example of maximum boiling azeotrope.

Calculate the volume of 75% of H2SO4 by weight (d = 1.8 gm/ml) required to prepare
1 L of 0.2 M solution.
Mass %  d 10
Hint : M1 =
98
M1V1 = M2V2
= 14.5 ml
Why water cannot be completely separated from aqueous solution of ethyl
alcohol ?
Ans. Due to formation of azeotrope at (95.4%).
What is the molarity of pure water ?
Ans. 55.5
Calculate the moles of PO4–3 present in 4L of 10–5 MCa3(PO4)2.
Ans. 8  10–5
Why anhydrous salts like NaCl or CaCl2 are used to clear snow from roads on
hills ?
Hint : They depress freezing point of water.
What is the effect on boiling and freezing point of a solution on addition of NaCl
?
Hint : Boiling point increases and freezing point decreases.
Out of M and m, which is better concentration term and why ?
Hint : m, it is independent of temperature change.
Why osmotic pressure is considered as colligative property ?
Hint : It depends upon number of moles of solute present in solution.
Liquid A and B on mixing produce a warm solution. Which type of deviation
does this solution show ?
Hint : – ve deviations
Give an example of a compound in which hydrogen bonding results in the
formation of a dimer.
Hint : Carboxylic acids or other example

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What role does the molecular interaction play in solution containing chloroform
and acetone ?
Hint : H-bonding formed, results in negative deviation from Raoult’s law.
SHORT ANSWER TYPE QUESTIONS (2 Marks)
Q. 1. Molecular weight of a solute X is greater than that of solute Y. Their equal weights
are dissolved separately in the equal quantity of same solvent. Which solution
will show greater relative lowering of vapour pressure and why ?
Q. 2. Out of the following three solutions, which has the highest freezing point and why ?
(a) 0.1 M urea (b) 0.1M BaCl2 (c) 0.1M Na2SO4
Q. 3. Which of the following solutions have highest boiling point and why ?
(a) 1M glucose (b) 1M KCl (c) 1M aluminium nitrate
Q. 4. Equal moles of liquid P and Q are mixed. What is the ratio of their moles in the
vapour phase ? Given that PP0 = 2  P Q0.
Q. 5. On mixing liquid X and Y, volume of the resulting solution decreases. What type
of deviation from Raoult’s law is shown by the resulting solution ? What change
in temperature would you observe after mixing liquids X and Y ?
Q. 6. Explain the significance of Henry’s constant (KH). At the same temperature,
hydrogen is more soluble in water than helium. Which of them will have higher
value of KH and why ?
Q. 7. How many grams of KCl should be added to 1 kg of water to lower its freezing
point to – 8.0ºC ? (Kf = 1.86 K kg/mol)
Ans. Since KCl dissociate in water completely, i = 2.
Tf = i Kf  m
Tf
m
iK f
8
m
2 1.86
= 2.15 mol/kg
Grams of KCl = 2.15  74. = 160.2 g/kg
Q.8. With the help of diagram, show the elevation in boiling point colligative properties ?
Q. 9. What do you mean by colligative properties ? Which colligative property is used
to determine molar mass of polymer and why ?
Define reverse osmosis. Write its one use.
Ans. Desalination of water.

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Why does an azeotropic mixture distills without any change in composition ?
Hint : It has same composition of components in liquid and vapour phase.
Under what condition Van’t Hoff factor is :
(a) equal to 1 ? (b) less than 1 ? (c) more than 1 ?
If the density of some lake water is 1.25 gm/ml and contains 92 gm of Na+ ions per
kg of water, calculate the molality of Na+ ion in the lake.
92
Ans. n   4
23
4
m   4m
1
An aqueous solution of 2% non-volatile exerts a pressure of 1.004 Bar at the normal
boiling point of the solvent. What is the molar mass of the solute ?
P0  P w m
Hint : A0 A
 mB w A
P
A B A

1.013  1.004 2 18


1.013 mB  98

mB = 41.35 gm/mol
Why is it advised to add ethylene glycol to water in a car radiator in hill station ?
Hint : Anti-freeze.
Calculate the molarity of pure water (d = 1 g mL–1).
Ans. Desity of water = 1 g mL–1
Mass of 1000 ml of water = V  d
= 1000 mL  1 gm–1
= 1000 g
1000
Moles of water = = 55.55 mol
18
Now, mole of H2O present in 1000 mL or 1 L of water.
So, molarity = 55.55M
Define Henry’s law. Give their two application.
The dissolution of ammonium chloride in water is endothermic process. What is
the effect of temperature on its solubility ?

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Ans. Since dissolution of NH4Cl in water is endothermic process, its solubility increases
with rise in temperature (i.e., Le-Chatelier process).
Two liquids A and B boil at 145ºC and 190ºC respectively. Which of them has
higher vapour pressure at 80ºC ?
Ans. Lower the boiling point more volatile is the respective compound. Therefore,
liquid A will have higher vapour pressure at 80ºC.
Why is liquid ammonia bottle first cooled in ice before opening it ?
Ans. At room temperature, the vapour pressure of liquid ammonia is very high. On
cooling vapour pressure decreases, therefore the liquid ammonia will not splash
out.
Which colligative property is preferred for the molar mass determination of
macromolecules ?
Ans. Osmotic pressure measurement is preferred for molar mass determination because :
(a) even in dilute solution the osmotic pressure values are appreciably high and
can be measured accurately.
(b) osmotic pressure can be measured at room temperature.
Define osmotic pressure determined from the measurement of osmotic pressure
of a solution.
Ans. Osmotic pressure : The excess pressure applied to solution side to stop the
process of osmosis is known as osmotic pressure.
C
T
  CT
 = CRT
nB
 RT
V

nB
 RT
MB V

nB RT
MB 
V

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 Solutions | 27

SHORT ANSWER-II TYPE QUESTIONS (3 Marks)

Q. 1. Determine the amount of CaCl2 dissolved in 2.5L at 27ºC such that its osmotic
pressure is 0.75 atm at 27ºC. (i for CaCl2 = 2.47)

Ans. For CaCl2, i = 2.47

 = iCRT

nB
i  RT
V

2.47  nB  0.082  300

0.75 
2.5

 0.75  2.5
n B
2.47  0.082  300

nB = 0.0308 mol

Amount = 0.0308 mol × 111g mol–1

= 3.418g

Q. 2. Determine the osmotic pressure of a solution prepared by dissolving 25 mg of

K2SO4 in 2 litre of water at 25ºC assuming that it is completely dissociated.

Ans. If K2SO4 is completely dissociated,

K2SO4  2K+ + SO42

i=3

Mol mass of K2SO 4= 2  39 + 32 + 4  16 = 174 g mol–1

 = iCRT

WB  RT
i
MB  V

3 25 103  0.082  298


174  2.0

= 5.27  10-3 atm

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Q. 3. If the solubility product of CuS is 6  10-16, calculate the maximum molarity

of CuS in aqueous solution.
Ans. Kspof CuS = 6  10-16
If S is the solubility, then
CuS  Cu2+ + S2-
[Cu2+] = S, [S2-] = S
Ksp = [Cu2+][S2-]
= S  S = S2

Solubility S = Ksp  6 106

= 2.45  108 M
Highest molarity = 2.45  108 M
Q. 4. Suggest the most important type of intermolecular attractive interaction in
the following pairs :
(a) n-hexane and n-octane (b) I2 and CCl4
(c) NaClO4 and water
Ans. (a) Vander Waals interaction
(b) Vander Waals interaction
(c) Ion-dipole interaction
Q. 5. The vapour pressure of water is 12.3 Kpa at 300K. Calculate vapour pressure
of 1 molal solution of a non-volatile solute in it.
1
Ans. Mole fraction of solute   0.0177
1000
 1
18
P0  P
A
 0.0177
0
P
12.3  PA
 0.0177
12.3
PA = 12.08 Kpa
Q. 6. 6.90M solution of KOH in water contains 30% by mass of KOH. Calculate
the density of the KOH solution. (Molar mass of KOH = 56 g mol-1)
Ans. Mass of KOH = 30 g
n 
M B
1000
V ml

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WB 30
 1000  1000
MB V ml 56  V

30 1000
6.90 
56 V
30 1000
V  81.43 mL
56  6.90
M
D
V
100
 =1.28 g mL1
81.43
Q. 7. An anti-freeze solution is prepared from 222.6 g of ethylene glycol C2H4(OH)2
and 200 g of water. Calculate the molality of the solution. If the density of this
solution be 1.072 g mL-1, what will be the molarity of the solution ?
Ans. MBof C H (OH) =2 62 g mol-1
2 4
nB
1000  WB 222.6 1000
Molality = 1000 
WA M B  WB 62  200
= 17.95m
Mass
Density =
Volume
Mass  422.6  394.22 ml
So, Volume =
Density 1.072
nB
M = 1000
V
222.6
= 1000 = 9.11M
394.22  62
Q. 8. What would be the molar mass of compound if 6.21 g of it is dissolved in 24.0
g of CHCl3 from a solution that has a boiling point of 68.04ºC. The boiling
point of pure chloroform is 61.7ºC and the boiling point elevation constant
Kb for chloroform is 3.63ºC/m.
Ans. Elevation in boiling point Tb= 68.04 – 61.7 = 6.31ºC
Mass of substance WB = 6.21 g
Mass of CHCl3 WA = 24.0 g
KB = 3.63 ºC/m

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Kb  WB 1000 3.63 6.211000
MB = 
Tb  WA 6.34  24

= 148.15 g mol-1
Q. 9. A solution of glycerol (C3H8O3) in water was prepared by dissolving some glycerol
in 500 g of water. This solution has a boiling point of 100.42ºC while pure water
boils at 100ºC. What mass of glycerol was dissolved to make the solution ? (Kb =
0.512 K kg mol-1)
Ans. 37.73 g
Q.10. 18 g of glucose (C H O ) (molar mass = 180 g mol-1) is dissolved in 1 kg of water
6 12 6
in a sauce pan. At what temperature will this solution boil ? (Kb for water = 0.52
K kg mol-1, boiling point of pure water = 373.1 K)
Ans. 373.202 K
LONG ANSWER TYPE QUESTIONS (5 Marks)
Q. 1. (a) Define Raoult’s law of binary solution containing non-volatile solute in
it.
(b) On dissolving 3.24 g of sulphur in 40 g of benzene, boiling point of
solution was higher than that of benzene by 0.81K (Kb = 2.53 K kg mol-
1
). What is molecular formula of sulphur ? (Atomic mass s = 32 g mol-1)
Ans. (a) At a given temperature, the vapour pressure of a solution containing non-
volatile solute is directly proportional to the mole fraction of the solvent.
K  W 1000 2.53  3.24 103

(b) MB = b b

Tb  WA 0.81 40
= 253 g mol–1
Let the molecular formula of sulphur = Sx
Atomic mass of sulphur = 32
Molecular mass = 32  x
32x = 253
x = 7.91  8
Molecular formula of sulphur = S8
Q. 2. (a) Outer shells of two eggs are removed. One of the egg is placed in pure
water and the other is placed in saturated solution of NaCl. What will be
observed and why ?
(b) A solution prepared by dissolving 8.95 mg of a gene fragment in
35.0 ml of water has an osmotic pressure of 0.335 ton at 25ºC.Assuming the
gene fragment is a non-electrolyse, determine the molar mass.

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 Solutions | 31
Ans. (a) In pure water the egg swells and in saturated solution of NaCl it will shrinks.
(b) Mass of gene fragment = 8.95 mg
= 8.95  10-3 g
Volume of water = 35.0 ml = 35  10-3 L
 = 0.335 ton = 0.335/760 atm
Temp = 25 + 273 = 298 K
WBRT
 
MB  V
0.335 8.95 103  0.0821 298

760 M B 35 103

MB= 141933 g mol-3

Q. 3. (a) Define van’t Hoff factor.
(b) Calculate the freezing point depression expected for 0.0711M aqueous
solution of Na2SO4. If this solution actually freezes at – 0.320ºC, what
would be the value of van’t Hoff factor ? (Kf = 1.86ºC mol-1)
Ans. (a) Van’t Hoff factor : It is the ratio of the normal molar mass to the observed
molar mass of the solute.
(b) Tf = Kf  M
Tf = 1.86  0.0711 = 0.132
Observed freezing point = 0 – (– 0.320) = 0.320ºC
Observed freezing point
i
Calculate freezing point
0.320
  2.42
0.132
Q. 4. (a) What is the value of i when solute is associated and dissociated ?
(b) Calculate the freezing point of an aqueous solution containing 10.50 g of
MgBr2 in 200 g of water. (Molar mass of MgBr2 = 184, Kf = 1.86 K kg
mol-1)
Ans. (a) i < 1 when solute is associated and
i > 1 when solute is dissociated.
ng 1000
(b) m 
WA  g 
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 32 | Chemistry-XII

WB 1000 10.50 1000
   0.2853M
M B  WA 184  200

MgBr2ionizes as MgBr 
2
Mg2+ + 2Br-
i=3
Tf = i  Kf  M
= 3  1.86  0.2855
= 1.59
Freezing point = 0 – 1.59ºC = – 1.59ºC
Q. 5. (a) What is the value of i for Al2(SO4)3 when it is completely dissociated ?
(b) Calculate the boiling point of a solution prepared by adding 15.00 g of
NaCl to 250 g of water. (Kb = 0.512 K kg mol-1 and molar mass of NaCl
= 58.44 g mol-1)
Ans. (a) Al2(SO 4) 3 2Al3+ + 3SO 2
4


i=5
iKb 1000  WB
Tb W M
(b) A B

NaCl  Na+ + Cl-

i =2
2  0.512 1000 15
Tb 
250  58.44
= 1.05
Boiling point of solution = 100 + 1.05
= 101.05ºC

VALUE BASED QUESTIONS (4 Marks)

Q. 1. Sauba divers when come towards the surface, pressure gradually decreases
resulting in release of dissolved gases leading to formation of bubbles of N2 gas in
the blood which block the capillaries and thus bends are created. To avoid bends
and toxic effect of high concentration of N2 gas, the air is diluted with helium.
After the above passage, answer the following :
(a) Why is the harmful condition of bends overcome by the use of helium ?
(b) Which law is used to calculate the concentration of gases in solution ?

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 Solutions | 33
(c) Mention the value associated with providing divers air diluted with helum.
(d) Which gas has less value of KH , O2 or He, and why ?
Q. 2. Ram takes an open pan to cook vegetables at a hill station while Shyam cooked
the same in a pressure cooker at the same place.
(a) Define normal boiling point of a liquid.
(b) Explain the reason who will cook vegetables faster.
(c) Mention the reason for delay in cooking.
(d) Which value is learnt by the student in the process of cooking food in pressure
cooker ?
Q. 3. Sneha’s grandmother lives in Manali. In winter, there is a lot of snow in front of
the house. She asked Sneha to clear the snow. Sneha added NaCl to snow to clear
it.
(a) Why Sneha does so ?
(b) Is the addition of Ca(NO3)2 a better choice than NaCl ? If yes, why ?
(c) What is the value in Sneha’s thinking ?
(d) Define molal freezing point, depression constant, Kf.
Q. 4. Ira Singh, a student of class XII Chemistry stated that normal saline solution
having 0.9% (mass/volume) NaCl is isotonic with the fluid inside the cell.
Therefore, it is safe to inject normal saline solution intravenously.
(a) Define isotonic solutions. What would happen if the concentration of saline
solution is (a) more, (b) less than 0.9% (mass/volume) NaCl ?
(b) What values are associated with the statement of Ira Singh ?

ANAND PATRACHAR SCHOOL-8860650600,9999132085 CHEMISTRY-XIIT