SOLUTIONS

Concentration of solutions.
A solution is a homogenous mixture of two of more substances.The solution and its
solvent will always be in the same physical state.Concentration is the amount of solute
in a solution.There are different ways of expressing concentration or strength of a
solution.Considering a binary solution of solvent ‘A’ and solute ‘B’ and using the
following conventions wA- weight of solvent, wB -weight of solute, MA -mol mass of
solvent, MB mol mass of solute, nA-no of moles of solvent and nB -no of moles of
solute,the different ways of expressing concentration or strength of a solution are

1)Strength (g/L)- Here the weight of solute is expressed in grams present per litre of
solution.

Strength= weight of solute in grams

Volume of solution in litres

Strength= wB(g)

V(L)

Strength= wB(g)×1000 g/l

V(ml)

Strength= Molarity×Molecular mass.

Strength=Normality× Equivalent weight.

2)Expressing in terms of %
a) %(w/w) or % by mass- Here the weight of solute is expressed in grams present per
100g of solution.
b) %(w/v) -Here the weight of solute is expressed in grams present per 100ml of
solution.
c) %(v/v) -Here the volume of solute is expressed in ml present per 100ml of solution.

3)Molarity(M)- is the no of moles of solute present in one litre of the solution.Its unit is M
or mol/L.

Molarity(M)= no of moles of solute

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 Volume of solution in litres
Molarity(M)= nB

V(L)

Molarity(M)= wB(g)×1000

MB×V(ml)

To convert % by mass(w/w) to Molarity(M), we use the relation

Molarity(M)= % × 10 × d (d=density of the solution).

MB
Molarity equation or dilution equation is M1V1=M2V2 or M1V1 +M2V2=M3V3 (V3=V1+V2)

4) Molality(m)- is the no of moles of solute present in one Kg of the solvent.Its unit is ‘m’
or mol/Kg.

Molality(m)= no of moles of solute

Weight of solvent in Kg

Molality(m)= nB

wA(Kg)
Molality(m)= wB(g)×1000

MB× wA(g)

Molality(m) is preffered over Molarity(M) as ‘m’,being a mass term, its value does not
change with temperature.(For an aqueous solution generally 1‘M’ is more concentrated
than 1‘m’.)

5) mass fraction of a component= Weight of component

Total weight of compound

6) mole fraction of a component (χ )is the ratio of no of moles of that component to the
total no of moles.

mole fraction of a component (χ )= no of moles of that component

Total no of moles

Sum of mole fraction of all components is always equal to one or unity.

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7)ppm in terms of mass= Weight of solute ×106

Weight of solution

SOLUBILITY
Solubility is defined as the maximum amount of solute that can be dissolved in a given
quantity of solvent at a particular temperature. It depends upon the nature of solute, the
nature of solvent, temperature and pressure.

Solubility of solid in Liquid

When a solid is dissolved in a liquid to form a solution, initially the rate of dissolution will
be high and more solute goes into solution. After some time the reverse process i.e.
crystallization starts. The process will go on till an equilibrium is established when (the
rate of dissolution = rate of crystallization) and the solution is said to be saturated.
Solubility is defined as the maximum amount of solute that can be dissolved in a given
quantity of solvent at a particular temperature.
Dissolution of solid in liquid may be endothermic or exothermic. If it is endothermic,
increase in temp will increase solubility according to Le-chatelier’s principle. For
dissolution processes which are exothermic lowering of temperature will increase
solubility. Pressure has no effect on the solubility of solid in liquid.
Dissolution of Gas in Liquid.
The solubility of a gas in liquid increases with the increase of pressure.
Henry’s law states that solubility of a gas in solution is directly proportional to the
pressure applied over the gas.
Dalton found that solubility of gas in a liquid is a function of partial pressure of the gas. If
we use mole fraction of gas in solution as a measure of solubility then, mole fraction of
gas in solution is proportional to partial pressure of gas over the solution.
The commonly used form of Henry’s law states that partial pressure of gas in vapour
phase (p) is proportional to mole fraction of gas in solution (χ).i.e. a plot of p against χ
will be linear.
P=KH χ (KH = Henry’s constant).

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Different gases have different values of KH at the same temperature which shows that
KH is dependent on the nature of the gas. Higher the value of KH at a given pressure
lower would be the solubility of gas in liquid. The value of KH in general is found to
increase with increase of temperature thereby suggesting that the solubility of a gas in
liquid decreases with increase in temperature. (reason why aquatic species are more
comfortable in cold water than warm water).
Effect of temperature
Gases when dissolved in liquids lose their kinetic energy and thus the solution of gas in
liquid is an exothermic process, hence increase of temperature decreases the solubility
of a gas in liquid according to the Le-chatelier’s principle.
Application of Henry’s law
To increase the solubility of CO2 in soft drinks, soda water etc, the bottles are sealed
under high pressure.

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Scuba divers must cope with high concentration of dissolved gases while breathing air
at high pressure under water. Increased pressure increases. the solubility of
atmospheric gases in blood. When the divers come towards the surface the pressure
gradually decreases leading to release of the gases and to the formation of bubbles of
N2 in the blood. This blocks capillaries and creates a medical condition called as bends .
To avoid bends, tanks used by scuba divers are filled with air diluted with helium.
At high altitudes partial pressure of 02 is less and this leads to low concentration of 02 in
the blood and tissues of people living at high altitudes and climbers. Low blood oxygen
causes climbers to become weak and unable to think clearly. These are symptoms of a
condition known as Anoxia.

Colligative properties
Are those properties which are dependant only on the amount of solute and not on the
nature of the solute. The important colligative properties exhibited by solutions are:-
1. Relative lowering of vapour pressure
2. Elevation in boiling point.

3. Depression in freezing point.

4. Osmotic pressure.

Vapour pressure of liquid-liquid solutions.

Vapour pressure is defined as the pressure exerted by the vapours of the liquid which
are in equilibrium with the liquid at that particular temperature.Vapour pressure depends
only on temperature and is directly proportional to it.

According to Raoult’s law for a solution of volatile liquids, the partial vapour pressure of
any component in a solution is directly proportional to its mole fraction. A graph of
vapour pressure against mole fraction will be linear.

RAOULT’S LAW

Consider a solution consisting of a solvent A and solute B. Let the partial vapour
pressure of solvent be equal to pA and that of the solute be equal to pB. Then according
to Dalton’s law total pressure p is equal to pA +pB

p= pA +pB.

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According to Raoult’s law, the partial vapour pressure of any component in a solution is
equal to the product of vapour pressure of pure component and mole fraction of that
component in the solution

Or

pA= p⁰A χA

pB= p⁰B χB

Solutions containing volatile solute.

For solutions containing volatile solute, both solvent and solute contribute to total vapour
pressure.

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p= pA +pB

p= p⁰A χA + p⁰B χB

p= p⁰A (1-χB) + p⁰B χB .

mole fraction in vapour phase= partial vapour pressure
Total vapour pressure
Solutions containing non-volatile solute.
Consider a pure solvent taken in a closed container. Let the vapour pressure of the pure
solvent be p⁰.A non-volatile solute is then added to the solvent to make a solution. Let
the vapor pressure of the solution be ‘p’.Comparing the two values we will find that the
vapour pressure of the solution ‘p’ is lower than that of the solvent ‘p’. This is because
when the solvent is changed to solution some of the solvent molecules on the surface
are replaced by solute particles, thus the surface area available for evaporation
decreases or the fraction of molecules available for evaporation decreases. The
difference between the two values (p⁰- p) is called as the lowering of vapour pressure

For solutions containing a non-volatile solute vapour pressure of solution has

contribution only from the solvent and not the solute. A graph of vapour pressure
against mole fraction of solvent will be linear .

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p= pA

p= p⁰A χA

p⁰-p = χB

p⁰

Alternate (2nd) definition of Raoult’s law-The relative lowering of vapour pressure of a

solution containing a non-volatile solute is equal to the mole fraction of the solute in the
solution.
Ideal solutions.
Ideal solutions are those liquid-liquid solutions which obey Raoult’s law at all
concentrations and temperatures. For an ideal solution ∆mixH and ∆mixV will be zero.
Though there are no perfectly ideal solutions, near ideal solutions can be obtained by
mixing liquids of similar structures and identical polarities. Example 1) Benzene and
toluene 2) cyclohexane and cycloheptane 3) n- hexane and n-heptane 4) bromoethane
and chloroethane etc.
Non Ideal solutions
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Non-ideal solutions are those liquid-liquid solutions which do not obey Raoult’s law at all
temperatures and concentrations. They are of two types
1) Solutions which show +ve deviation from Raoult’s.law
2) Solutions which show –ve deviation from Raoult’s law.

Solutions which show +ve deviation from Raoult’s law have higher vapour pressure than
expected by Raoult’s law. For such solutions ∆mixH and ∆mixV will be +ve.
Solutions which show –ve deviation from Raoult’s law have lower vapour pressure than
expected by Raoult’s law. For such solutions ∆mixH and ∆mixV will be –ve.
The deviation from ideal behavior can be explained in terms of the intermolecular forces
of attraction that exist inside a solution. In a solution there are 3 types of interactions. A-
A,B-B and A-B. If A-B interaction is weaker than A-A or B-B interactions molecules of A
or B will find it easier to escape than in pure state (vapour pressure increases) and the
solution will show +ve deviation from Raoult’s law.e.g.ethanol and water, ethanol and
acetone, carbon disulphide and acetone.
In the case of ethanol and acetone, ethanol molecules are hydrogen bonded. On adding
acetone its molecule gets in between the ethanol molecules and breaks some of the
hydrogen bonds between them. Due to weakening of interactions the solution shows
+ve deviation from Raoult’s law.

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In the case of ethanol and H2O, both are individually hydrogen bonded. However the
new hydrogen bonds formed are weaker than the already exisisting ones and hence the
solution will show +ve deviation from Raoult’s law.
In the mixing of CS2 and acetone, the dipolar interactions between solute and solvent
molecule are weaker than the interactions among solute and solute and solvent –
solvent molecules and the solution will show +ve deviation from Raoult’s law.
Solutions which show –ve deviation from Raoult’s law have A-B interactions stronger
than A-A and B-B interactions, hence molecules of A or B will find it difficult to escape
than in pure state (vapour pressure decreases) and the solution will show -ve deviation
from Raoult’s law e.g. Phenol and aniline, chloroform and acetone etc.
In the case of phenol and aniline, the inter-molecular hydrogen bonding between
phenolic proton and lone pair on nitrogen atom of aniline is stronger than the respective
intermolecular hydrogen bonding between similar molecules.
In the case of chloroform and acetone, the vapour pressure decreases because new
hydrogen bonds are formed between acetone and chloroform.
Solutions which show +ve and –ve deviation from Raoult’s law also differ in the type of
azeotropic mixtures that they form. When liquids are mixed at a particular concentration,
the composition becomes equal in the liquid and vapour phase. At this point an
azeotropic mixture is formed and the two liquids lose their identities in terms of boiling
points and behave like a new liquid with a new boiling point which is different from the
boiling point of the two liquids which constitute it. Thus the azeotropic mixture is also
called as constant boiling point mixture and cannot be separated by distillation. It is also
a constant composition mixture as the % of the two liquids remains the same
throughout. Solutions which show +ve deviation from Raoult’s law form lower boiling
point azeotropic mixture whereas that which show –ve deviation form higher boiling
point azeotropic mixture.
Eg. Lower boiling point azeotropic mixture:- 95% ethanol by volume
Higher boiling point azeotropic mixture :-HNO3 68% and water 32% by mass
(boiling point 393.5k)
Elevation in Boiling point
The boiling point of a substance is defined as that temperature when the atmospheric
pressure equals the vapour pressure.
The boiling point of a solution is always higher than the boiling point of the pure solvent.
This is because the vapour pressure of the pure solvent is always higher than that for
the solution. The difference in boiling point between that of the solution (T b) and pure
solvent (T⁰b) is called as elevation in boiling point represented by ∆Tb .

∆Tb = boiling point of solution - boiling point of solvent = (Tb-T⁰b).

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The elevation in boiling point (∆Tb) like lowering of vapour pressure is a colligative
property and for dilute solutions is found to be directly proportional to the molality of the
solution.
∆Tb α m (molality)
∆Tb = Kb × m
(Kb =molal elevation constant or boiling point elevation constant or ebullioscopic
constant. Its value is constant for a particular solvent).
∆Tb = Kb × wB(g)×1000

MB× wA(g)

MB = Kb × wB(g)×1000

∆Tb × wA(g)

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Kb = R ×Tb2 (lv=latent heat of vapourisation, Tb =b.p of pure solvent in K).

1000 lv

Kb = R× MA×Tb2 (∆vapH=enthalpy of vapourisation,MA=molar mass of solvent).

1000 ×∆vapH

Depression in Freezing point

The freezing point of a substance is defined as the temperature at which the vapour
pressure of a substance in its liquid phase equals the vapour pressure in the solid
phase.A solution will freeze when its vapour pressure equals the vapour pressure of the
pure solid solvent.
The freezing point of a pure solvent is always higher than the freezing point of the
solution. This is because the vapour pressure of the pure solvent is always higher than
that for the solution. The difference in freezing point between that of the pure solvent
(T⁰f) and solution (Tf) is called as in freezing point represented by ∆Tf .

∆Tf = freezing point of solvent - freezing point of solution = (Tf-T⁰f).

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The depression in freezing point (∆Tf) like lowering of vapour pressure is a colligative
property and for dilute solutions is found to be directly proportional to the molality of the
solution.
∆Tf α m (molality)
∆Tf = Kf × m
(Kf =molal depression constant or freezing point depression constant or Cryoscopic
constant. Its value is constant for a particular solvent).
∆Tf = Kf × wB(g)×1000

MB× wA(g)

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MB = Kf × wB(g)×1000

∆Tf × wA(g)

Kf = R ×Tf2 (lf=latent heat of fusion, Tf =f.p of pure solvent in K).

1000 lf

Kf = R× MA×Tf2 (∆fusH=enthalpy of vapourisation,MA=molar mass of solvent).

1000 ×∆fusH

OSMOTIC PRESSURE
Osmosis is the movement of solvent molecules from a region of its high concentration
(pure solvent) to its low concentration (to solution) across a semi-permeable membrane
(semi-permeable membrane (SPM) is one which allows only the solvent molecules and
not the solute molecules to pass through).
Osmotic pressure is the hydrostatic pressure exerted on the walls of the semi-
permeable membrane when osmosis takes place. Osmotic pressure is also defined as
the external pressure which is applied on the high concentration side of solution to just
prevent osmosis. If the pressure applied on the high concentration side of solution is
higher than the osmotic pressure, then reverse osmosis takes place i.e. the solvent
molecules will move from its lower concentration to its high concentration.

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 Osmotic pressure is a colligative property and for dilute solutions is found to be directly
proportional to the molarity of the solution at a given temperature.
παM
παT
π = MRT (R=universal gas constant)
M=n
V
Hence π = nRT
V
π = WBRT
MBV

Between two solutions the one which has higher osmotic pressure is called as
hypertonic solution and the one with lower osmotic pressure is called as hypotonic
solution. Solutions with the same osmotic pressure are called as isotonic solutions.e.g
0.9%(mass/volume (w/v)) NaCl solution is isotonic with the fluid inside the blood cell
and hence it is safe to inject this solution intravenously .On the other hand, if the cells
are placed in a solution containing more than 0.9%(/v) NaCl, water will flow out of the
cells and they would shrink. If ionic concentration is less than 0.9 %(w/v) then water will
flow into the cells and they would swell.
The main use of colligative properties is to determine the molecular masses of solutes.
Of all the methods, the best available one is that based on osmotic pressure
measurements .one of the major advantages of using osmotic pressure method is that
measurements can be carried out at room temperature and that molarity can be used
instead of molality. Moreover, the magnitude of osmotic pressure in general is large
even for very dilute solutions; hence the error in measurement is less. Osmotic pressure
method is particularly useful for biomolecules as they are generally not stable at higher
temperature and are not stable at higher temperatures and for polymers because they
have poor solubility.
Vant-Hoff”s factor (‘i’)
Vant-Hoff”s factor (‘i’) takes into consideration the association or dissociation of solutes
in solution. If the solute doesn’t undergo association or dissociation then the observed
value of colligative property will be equal to the calculated value of colligative property
i.e.‘I’=1.On the other hand if the solute dissociates the no. of particles in solution would
be higher than expected and the observed value of colligative property would be greater
than the calculated value of colligative property i.e.(‘I’>1). If the solute undergoes

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association the no. of particles would be lower than expected and observed value of
colligative property would be less than the calculated value of colligative property and
(‘I’<1).
Higher the number of particles (i.e. higher the value of ‘i’) greater would be the value of
colligative property.
‘i’= Observed value of colligative property.
Calculated value of colligative property.

‘i’= Calculated value of.molecular mass

Observed value of molecular mass
‘i’= Total no of moles of particles after association/dissociation
No of moles of particles before association/dissociation.
‘I’= Total no of moles at equilibrium.
Taking ‘I’ factor into consideration, the equations for colligative properties are modified
as:-

p⁰-p = i × χB

p⁰

∆Tf = i× Kf × m
∆Tf = i× Kf × m
π = iMRT

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SOLUTIONS -EXCERSISES
1. Define the term solution. How many types of solutions are formed? Write briefly about
each type with an example. [NCERT]
2. Give an example of a solid solution in which the solute is a gas. [NCERT]
3. Define the following terms : (i) Mole fraction (ii) Molality (iii) Molarity (iv) Mass
percentage. [NCERT]
4. Calculate the mass percentage of benzene (C6H6) and carbon tetrachloride (CCl4) if
22 g of benzene is dissolved in 122 g of carbon tetrachloride. [NCERT]
5. A solution is obtained by mixing 300 g of 25% solution and 400 g of 40% solution by
mass. Calculate the mass percentage of the resulting solution. [NCERT]
6. Calculate the mass percentage of aspirin (C9H8O4) in acetonitrile (CH3CN) when 6.5
g of C9H8O4 is dissolved in 450 g of CH3CN. [NCERT]
7. Calculate the mole fraction of ethylene glycol (C2H6O2) in a solution containing 20%
of C2H6O2
by mass. [NCERT]
8. Calculate the mole fraction of benzene in solution containing 30% by mass in carbon
tetrachloride. [NCERT]
9. Calculate the mole fraction of a solute in 2.5m aqueous solution.
10. Calculate molality of 2.5 g of ethanoic acid (CH3COOH) in 75 g of benzene.
[NCERT]
11. Calculate the mass of urea (NH2CONH2) required in making 2.5 kg of 0.25 molal
aqueous solution. [NCERT]
12. Calculate the molality of a sulphuric acid solution in which the mole fraction of water
is 0.85.
13. Solubility of Ba (OH) 2.8H2O in water is 5.6g per 100g of water. What is the molality
of the hydroxide ions in the saturated solution of barium hydroxide?
14. Calculate molality of 1 litre solution of 93% sulphuric acid (w/v).density=1.84g/ml.
15. Calculate the number of moles of methanol in 5 litres of its 2m solution, if
density=0.981Kg/L.
16. If the density of some lake water is 1.25g mL–1 and contains 92 g of Na+ ions per kg
of water, calculate the molality of Na+ ions in the lake. [NCERT]
17. A sugar syrup of weight 214.2g contains 34.2g of sugar (C12H22O11).Calculate
molality and mole fraction of sugar in the syrup.
18. Density of 3M Na2S2O3 solution is 1.25g/cm3.calculate1)weight % of Na2S2O3 2)
mole fraction of Na2S2O3 3) molality of Na+ and S2O32- ions.
19. A sample of drinking water was found to be severely contaminated with chloroform
(CHCl3) supposed to be a carcinogen. The level of contamination was 15 ppm (by
mass): (i) express this in percent by mass (ii) determine the molality of chloroform in the
water sample. [NCERT]
20. Calculate the molarity of a solution containing 5 g of NaOH in 450 mLsolution.
[NCERT]
21. Calculate the amount of benzoic acid (C6H5COOH) required for preparing 250mL of
0.15 M solution in methanol. [NCERT]

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22.Calculate the molarity of each of the following solutions: (a) 30 g ofCo(NO 3)2.6H2O in
4.3L of solution (b) 30 mL of 0.5 M H2SO4 diluted to 500 mL. [NCERT]
23. Concentrated nitric acid used in laboratory work is 68% nitric acid by mass in
aqueous solution. What should be the molarity of such a sample of the acid if the
density of the solution is 1.504 g mL–1? [NCERT]
24. A 6.9 M solution of KOH in water contains 30% by mass of KOH. Calculate the
density of KOH solution.
25. Calculate the volume of 80% sulphuric acid (d=1.8g/cc) required to prepare one litre
of 20% sulphuric acid (d=1.25 g/cc).
26. Calculate (a) molality (b) molarity and (c) mole fraction of KI if the density of 20%
(mass/mass) aqueous KI is 1.202 g mL-1. [NCERT]
27.4g of NaOH is contained in one decilitre of solution .what is mole fraction, molality
and molarity of NaOH solution.
28. A solution of glucose in water is labelled as 10% w/w, what would be the molality
and mole fraction of each component in the solution? If the density of solution is 1.2 g
mL–1, then what shall be the molarity of the solution? [NCERT]
29. An antifreeze solution is prepared from 222.6 g of ethylene glycol (C 2H6O2) and 200
g of water. Calculate the molality of the solution. If the density of the solution is 1.072 g
mL–1, then what shall be the molarity of the solution? [NCERT]
30. Calculate the molarity and molality of 20% aqueous ethanol solution by volume.
31. Conc of a sulphuric acid solution is 18M.What is mole fraction and weight
percentage of the solution.
32. How many mL of 0.1 M HCl are required to react completely with 1 g mixture of
Na2CO3 and NaHCO3 containing equimolar amounts of both? [NCERT]
33. If the solubility product of CuS is 6 × 10–16, calculate the maximum molarity of CuS
in aqueous solution. [NCERT]
34. Nalorphene (C19H21NO3), similar to morphine, is used to combat withdrawal
symptoms in narcotic users. Dose of nalorphene generally given is 1.5 mg. Calculate
the mass of 1.5x10–3 m aqueous solution required for the above dose. [NCERT]
34. Based on solute-solvent interactions, arrange the following in order of increasing
solubility in n-octane and explain. Cyclohexane, KCl, CH3OH, CH3CN. [NCERT]
35.Amongst the following compounds, identify which are insoluble, partially soluble and
highly soluble in water?(i) phenol (ii) toluene (iii) formic acid (iv) ethylene glycol (v)
chloroform (vi) pentanol. [NCERT]
36. Suggest the most important type of intermolecular attractive interaction in the
following pairs. (i) n-hexane and n-octane (ii) I2 and CCl4 (iii) NaClO4 and water (iv)
methanol and acetone (v) acetonitrile (CH3CN) and acetone (C3H6O). [NCERT]
37. State Henry’s law and mention some important applications? [NCERT]
38. Why do gases always tend to be less soluble in liquids as the temperature is raised?
[NCERT]
39. The partial pressure of ethane over a solution containing 6.56 × 10 –3 g of ethane is 1
bar. If the solution contains 5.00 ×10–2 g of ethane, then what shall be the partial
pressure of the gas? [NCERT].
40. At what partial pressure, oxygen will have a solubility of 0.05g/L in water at 293K.K H
for O2 in water at 293K is 34.86Kbar.Assume density of the solution to be same as that
of the solvent.

18
41. If N2 gas is bubbled through water at 293 K, how many millimoles of N 2 gas would
dissolve in 1 litre of water? Assume that N2 exerts a partial pressure of 0.987 bar. Given
that Henry’s law constant for N2 at 293 K is 76.48 kbar. [NCERT]
42. H2S, a toxic gas with rotten egg like smell, is used for the qualitative analysis. If the
solubility of H2S in water at STP is 0.195 m, calculate Henry’s law constant. [NCERT]
43. Henry’s law constant for CO2 in water is 1.67x108 Pa at 298 K. Calculate the
quantity of CO2 in 500 mL of soda water when packed under 2.5 atm CO2 pressure at
298 K. [NCERT].
44. The Henry’s constant for oxygen dissolved in water is 4.34×10 4 atm at 25ºC.If the
partial pressure of oxygen in air is 0.2atm under atmospheric conditions, calculate the
conc (moles/litre) of dissolved oxygen in water in equilibrium with air at 25ºC.
45. Henry’s law constant for the molality of methane in benzene at 298 K is
4.27 × 105mm Hg. Calculate the solubility of methane in benzene at 298 K under 760
mm Hg. [NCERT].
46. Air contains O2 and N2 in the ratio of 1:4.calculate the ratio of solubilities in terms of
mole fractions of O2 and N2 dissolved in water at atmospheric pressure and room
temperature at which Henry’s constant for O2 and N2 are 3.3 ×107 torr and 6.6 ×107 torr
respectively.
47. The air is a mixture of a number of gases. The major components are oxygen and
nitrogen with approximate proportion of 20% is to 79% by volume at 298K. The water is
in equilibrium with air at a pressure of 10 atm. At 298 K if the Henry’s law constants for
oxygen and nitrogen at 298 K are 3.30 × 107mm and 6.51 × 107mm respectively,
calculate the composition of these gases in water. [NCERT].
48. What is meant by positive and negative deviations from Raoult's law and how is the
sign of ΔmixH related to positive and negative deviations from Raoult's law? [NCERT]
49. What role does the molecular interaction play in a solution of alcohol and water?
[NCERT].
50. Heptane and octane form an ideal solution. At 373 K, the vapour pressures of the
two liquid components are 105.2 kPa and 46.8 kPa respectively. What will be the
vapour pressure of a mixture of 26 g of heptane and 35 g of octane? [NCERT].
51. 100 g of liquid A (molar mass 14 g mol–1) was dissolved in 1000 g of liquid B (molar
mass 180 g mol–1).The vapour pressure of pure liquid B was found to be 500 torr.
Calculate the vapour pressure of pure liquid A and its vapour pressure in the solution if
the total vapour pressure of the solution is 475 torr. [NCERT].
52.Two liquids X and Y form an ideal solution.At 30 ºC,the vapour pressure of the
solution containing 3 moles of X and 1 mole of Y is 550mmHg.When 4 moles of X and 1
mole of Y are mixed,vapour pressure is 560mmHg. Calculate vapour pressure of pure X
and pure Y at this temperature.
53. Benzene and toluene form a nearly ideal solution. The vapour pressures of pure
benzene and toluene are 160mm of Hg and 60mm of Hg respectively. Calculate the
partial pressure of Benzene and toluene and the total pressure over the following
solutions. a) Containing equal weights of benzene and toluene b) Containing 1 mole of
benzene and 4 moles of toluene. c) Containing equal molecules of benzene and
toluene.

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54. Vapour pressure of chloroform (CHCl3) and dichloromethane (CH2Cl2) at 298 K are
200 mm Hg and 415 mm Hg respectively. (i) Calculate the vapour pressure of the
solution prepared by mixing 25.5 g of CHCl3 and 40 g of CH2Cl2 at 298 K and, (ii) mole
fractions of each component in vapour phase. [NCERT].
55. Benzene and toluene form a nearly ideal solution. At a certain temperature, the
vapour pressure of pure benzene and toluene are 150mmHg and 50mmHg respectively.
For this temperature calculate the vapour pressure of solution containing equal weights
of the two substances. Also calculate their composition in the vapour phase.
56. The vapour pressure of pure liquids A and B are 450 and 700 mm Hg respectively,
at 350 K .Find out the composition of the liquid mixture if total vapour pressure is 600
mm Hg. Also find the composition of the vapour phase. [NCERT]
57. Benzene and toluene form ideal solution over the entire range of composition. The
vapour pressure of pure benzene and toluene at 300 K are 50.71 mm Hg and 32.06 mm
Hg respectively. Calculate the mole fraction of benzene in vapour phase if 80 g of
benzene is mixed with 100 g of toluene. [NCERT].
58. The vapour pressure of benzene and toluene at 293K are 75mm and 22mm Hg
repectively.23.4g of Benzene and 64.4 g of toluene are mixed. If the two forms an ideal
solution, calculate the mole fraction of benzene in the vapour phase.
59. Two liquids A and B form an ideal solution. Their vapour pressures in pure state are
200 and 100 mm Hg respectively. What will be the mole fraction of B in the vapour
phase in equilibrium with an equimolar solution of the two.
60. Vapour pressures of pure acetone and chloroform at 328 K are 741.8 mm Hg and
632.8 mm Hg respectively. Assuming that they form ideal solution over the entire range
of composition, plot p total, p chloroform, and p acetone as a function of x acetone. The
experimental data observed for different compositions of mixture is:

Plot this data also on the same graph paper. Indicate whether it has positive deviation
or negative deviation from the ideal solution. [NCERT].
61. Vapour pressure of pure water at 298 K is 23.8 mm Hg. 50 g of urea (NH2CONH2) is
dissolved in 850 g of water. Calculate the vapour pressure of water for this solution and
its relative lowering. [NCERT]
62. Vapour pressure of water at 293 K is 17.535 mm Hg. Calculate the vapour pressure
of water at 293 K when 25 g of glucose is dissolved in 450 g of water. [NCERT].
63. An aq.solution of glucose is made by dissolving 10g of it in 90g water at 303K.If v.p
of pure water at 303K be 32.8mm of Hg,what would be the v.p of the solution.
64.The vapour pressure of water is 12.3 kPa at 300 K. Calculate vapour pressure of 1
molal solution of a non-volatile solute in it. [NCERT]
65. The vapour pressure of pure benzene at a certain temperature is 0.850 bar. A non-
volatile, non-electrolyte solid weighing 0.5 g when added to 39.0 g of benzene (molar
mass 78 g mol-1). Vapour pressure of the solution, then, is 0.845 bar. What is the molar
mass of the solid substance? [NCERT]

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66. An aqueous solution of 2% non-volatile solute exerts a pressure of 1.004 bar at the
normal boiling point of the solvent. What is the molar mass of the solute? [NCERT].
67. The v.p of 2.1% aq solution of a non-electrolyte at 373K is 755mm. Calculate the
molar mass of solute.
68.Calculate the mass of a non-volatile solute (molar mass 40 g mol–1) which should be
dissolved in 114 g octane to reduce its vapour pressure to 80%.[NCERT].
69. How much urea should be dissolved in 50g of water so that its v.p at room
temperature is reduced by 25%.
70. A solution containing 30 g of non-volatile solute exactly in 90 g of water has vapour
pressure of 2.8 kPa at 298 K. Further, 18 g of water is then added to the solution and
the new vapour pressure becomes 2.9 kPa at 298 K. Calculate :(i) molar mass of the
solute (ii) vapour pressure of water at 298 K. [NCERT].
71. Vapour pressure of an aq.solution of glucose is 750mm of Hg at 373K.Calculate
molality and mole fraction of solute.
72. At 50 ºC,v.p of pure CS2 is 85.4 torr. A solution of 2g of sulphur in 100g of CS2 has
v.p of 848.9 torr. Determine the formula of sulphur molecule.
73.18 g of glucose, C6H12O6, is dissolved in 1 kg of water in a saucepan. At what
temperature will water boil at 1.013 bar? Kb for water is 0.52K kg mol-1[NCERT].
74. Calculate the boiling point of a 1M aq.solution of KCl. (d=1.04g/ml). K b=0.52 K Kg
mol-1
75. The boiling point of benzene is 353.23 K. When 1.80 g of a non-volatile solute was
dissolved in 90 g of benzene, the boiling point is raised to 354.11 K. Calculate the molar
mass of the solute. Kb for benzene is 2.53K kg mol–1. [NCERT].
76.Calculate the molar mass of a substance 1.3g of which when dissolved in 169g of
water gave a solution boiling at 100.025ºC at a pressure of 1 atm.K b=0.52 ºC.
77. On dissolving 3.24g of sulphur in 40g of benzene,b.p of solution was higher than
that of benzene by 0.81K. Kb=2.53KKgmol-1.What is the molecular formula of sulphur.
(Atomic mass of sulphur=32gmol-1).
78. Boiling point of water at 750 mm Hg is 99.63°C. How much sucrose is to be added
to 500 g of water such that it boils at 100°C. [NCERT].
79. On a certain hill station pure water is found to boil at 95 ºC.How many grams of
NaCl should be added to 2Kg of water so that it boils at 100 ºC.
80. Calculate the molal elevation constant of water,it being given that 0.1 molal aqueous
solution boils at at 100.052ºC.
81. The vapour pressure of an aqueous solution of cane sugar is 732mm at 100 ºC.
Calculate the b.p of the solution. Kb=0.52 ºC.

82. The depression in freezing point of water observed for the same amount of acetic
acid, trichloroacetic acid and trifluoroacetic acid increases in the order given above.
Explain briefly. [NCERT]
83. Calculate the f.p of a solution containing 0.52g glucose in 80.2 g water.
Kf=1.86K/m.

21
84. 45 g of ethylene glycol (C2H6O2) is mixed with 600 g of water. Calculate (a) the
freezing point depression and (b) the freezing point of the solution. [NCERT]
85. Calculate the depression in the freezing point of water when 10 g
ofCH3CH2CHClCOOH is added to 250 g of water. Ka = 1.4 × 10–3, Kf = 1.86K kg mol–1.
[NCERT]
86. A 5% solution (by mass) of cane sugar in water has freezing point of 271K.
Calculate the freezing point of 5% glucose in water if freezing point of pure water is
273.15 K. [NCERT]
87. A 0.1539 molal solution of cane sugar has a f.p of 271K while f.p of pure water is
273.15K.what will be the f.p of an aqueous solution containing 5g of glucose per 100 g
of solution.
88. Assuming complete dissociation, Calculate the expected freezing point of a
solution prepared by dissolving 6g of Glauber’s salt (Na2SO4.10H2O) in 0.1 Kg of water.
89. Calculate the mass of ascorbic acid (Vitamin C, C6H8O6) to be dissolved in 75 g of
acetic acid to lower its melting point by 1.5°C. Kf= 3.9 K kg mol-1. [NCERT]
90. Calculate the amount of KCl which must be added to 1Kg of water so that the
freezing point is depressed by 3K. Kf=1.86 ºC/m.91.The temperature at a hill station is -
10ºC.Will it be suitable to add ethylene glycol to water in the radiator so that the solution
is 30% by mass. Kf=1.86K/m.
92.Ethylene glycol is used as an anti freeze agent. Calculate the minimum amount of
ethylene glycol that must be added to 6Kg of water to prevent it from freezing at -30ºC.
Kf=1.86K/m.
93. 100 g of a non-electrolyte solute dissolved in 50 g of benzene lowered the freezing
point of benzene by 0.40 K. The freezing point depression constant of benzene is 5.12
K kg mol–1. Find the molar mass of the solute. [NCERT]
94. Two elements A and B form compounds having formula AB2 and AB4. When
dissolved in 20 g of benzene (C6H6), 1 g of AB2 lowers the freezing point by 2.3 K
whereas 1.0 g of AB4 lowers it by 1.3 K. The molar depression constant for benzene is
5.1 K kg mol–1. Calculate atomic masses of A and B. [NCERT]
95. Two aqueous solutions containing respectively 7.5g urea (mol mass=60) and 42.75g
substance X in 100g water freeze at the same temperature.Calculate the molar mass of
X.
96. Pure solvent A has freezing point 16.5ºC.On dissolving 0.4g of B in 200g ofº A,the
solution freezes at 16.4ºC and on dissolving 2.24g of C in 100g of A,the solution has a
fº.p of 16ºC.If molar mass of A is 74gmol-1,what is the molar mass of C.
97. Addition of 0.643g of a compound to 50ml of benzene (d=0.8g/cm3) lowers the f.p
from 5.51ºC to 5.03ºC. If Kf=5.12K/m, calculate the molecular weight of the compound.
98. The freezing point depression of 0.1m acetic acid solution in benzene is
0.256K.What conclusion can be drawn about the molecular state of acetic acid in
benzene. Kf=5.12.

22
99. 2 g of benzoic acid (C6H5COOH) dissolved in 25 g of benzene shows a depression
in freezing point equal to 1.62 K. Molal depression constant for benzene is 4.9 K kg
mol–1. What is the percentage association of acid if it forms dimer in solution? [NCERT]
100. 2g of benzoic acid dissolved in 25g of benzene shows a depression in freezing
point equal to 1.62K. Kf=4.9K Kg mol-1. Calculate the % ionization of salt.
101. 0.5g KCl was dissolved in 100g water and the solution originally at 20ºC,froze at -
0.24 ºC. Calculate the % ionization of salt.
102. 0.01m aq.solution of K3 [Fe(CN)6] freezes at -0.062 ºC. What is the apparent % of
dissociation.
103. 19.5 g of CH2FCOOH is dissolved in 500 g of water. The depression in the freezing
point of water observed is 1°C. Calculate the van’t Hoff factor and dissociation constant
of fluoroacetic acid. [NCERT]
104. 0.6 mL of acetic acid (CH3COOH), having density 1.06 g mL–1, is dissolved in 1
litre of water. The depression in freezing point observed for this strength of acid was
0.0205°C. Calculate the van’t Hoff factor and the dissociation constant of acid.
[NCERT].
105. Phenol associates in benzene to form the dimer.The f.p of a solution containing 5g
of phenol in 250g of benzene is lowered by 0.70 º.Calculate the degree of association of
phenol in benzene.Kf=5.12 K Kg mol-1.
106. The f.p of a solution containing 0.3g of acetic acid in 30g of benzene is lowered by
0.45 ºC.Calculate the Vant-Hoff’s factor.
107. A solution of an organic compound is prepared by dissolving 34.2g in 500g of
water. Calculate the molar mass and f.p of the solution. Kf=1.86K/m.Kb=0.52K/m.B.p of
solution=100.104ºC
108. How many grams of sucrose should be dissolved in 100g of water to produce a
solution with 105ºC difference between its f.p and b.p.
109. Calculate the osmotic pressure in pascals exerted by a solution prepared by
dissolving 1.0 g of polymer of molar mass 185,000 in 450 mL of water at 37°C.
[NCERT].
110. Determine the osmotic pressure of a solution prepared by dissolving 25 mg of
K2SO4 in 2 litre of water at 25°C, assuming that it is completely dissociated. [NCERT]
111.200 cm3 of an aqueous solution of a protein contains 1.26 g of the protein. The
osmotic pressure of such a solution at 300 K is found to be 2.57 × 10-3 bar. Calculate
the molar mass of the protein. [NCERT]
112. At 300 K, 36 g of glucose present in a litre of its solution has an osmotic pressure
of 4.98 bar. If the osmotic pressure of the solution is 1.52 bars at the same temperature,
what would be its concentration? [NCERT]
113. Determine the amount of CaCl2(i = 2.47) dissolved in 2.5 litre of water such that its
osmotic pressure is 0.75 atm at 27° C. [NCERT]
114. Decinormal solution of NaCl developed an osmotic pressure of 4.6 atm at 300K.
Calculate its degree of dissociation.
115. A 5% solution of cane-sugar (mol mass=342) is isotonic with 0.877% solution of
urea.Find the molar mass of urea.
116. A solution containing 10.2g glycerine per litre of a solution is found te be isotonic
with 2% solution of glucose (molar mass=180).Calculate molar mass of glycerine.

23
117.A solution of an organic compound is prepared by dissolving 68.4g in 1000g of
water.Calculate the molecular mass of the compound and osmotic pressure of the
solution at 293K when elevation in b.p is 0.104 and Kb=0.52 ºC.
118. A solution containing 6g of a solute dissolved in 250cm 3 of water gave an osmotic
pressure of 4.5atm at 27 ºC.Calculate the b.p of the solution. Kb=0.52 ºC per 1000 g.
119. 68.4g 0f sugar is dissolved in 1000g water. Calculate a)f.p b)b.p c) osmotic
pressure at 20ºC.d)v.p at 20ºC. density of solution at 20ºC=1.024g/cm3.v.p of water at
20ºC is 17.633mm. Kf=1.86K/m. Kb=0.52K/m.
120. Arrange 0.1m NaCl, glucose and BaCl2 solutions in increasing orders of their
boiling and freezing points giving reason.

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