2.1. Define the term solution. How many types of solutions are formed?

Write briefly about each type

with an example.
Sol: A solution is a homogeneous mixture of two or more chemically non-reacting substances. Types of
solutions: There are nine types of solutions.
Types of Solution Examples
Gaseous solutions
(a) Gas in gas Air, mixture of 02 and N2, etc.
(b) Liquid in gas Water vapour
(c) Solid in gas Camphor vapours in N2 gas, smoke etc.
Liquid solutions
(a) Gas in liquid C02 dissolved in water (aerated water), and 02 dissolved in water, etc.
(b) Liquid in liquid Ethanol dissolved in water, etc.
(c) Solid in liquid Sugar dissolved in water, saline water, etc.
Solid solutions
(a) Gas in solid Solution of hydrogen in palladium
(b) Liquid in solid Amalgams, e.g., Na-Hg
(c) Solid in solid Gold ornaments (Cu/Ag with Au)

2.2. Suppose a solid solution is formed between two substances, one whose particles are very large
and the other whose particles are very small. What type of solid solution is this likely to be ?
Sol: The solution likely to be formed is interstitial solid solution.

2.3 Define the following terms:

(i) Mole fraction
(ii) Molality
(iii) Molarity
(iv) Mass percentage
Sol: (i) Mole fraction: It is defined as the ratio of the number of moles of the solute to the total number
of moles in the solution. If A is the number of moles of solute dissolved in B moles of solvent, then Mole
fraction of solute

(ii) Molality: It is defined as die number of moles of a solute present in 1000g (1kg) of a solvent.
NOTE: Molality is considered better way of expressing concentration of solutions, as compared to
molarity because molality does not change with change in temperature since the mass of solvent does
not vary with temperature,
(iii) Molarity: It is defined as the number of moles of solute present in one litre of solution.

NOTE: Molarity is the most common way of expressing concentration of a solution in laboratory.
However, it has one disadvantage. It changes with temperature because volume of a solution alters due
to expansion and contraction of the liquid with temperature.
(iv) Mass percentage: It is the amount of solute in grams present in 100g of solution.

2.4. Concentrated nitric acid used in the laboratory work is 68% nitric acid by mass in aqueous
solution. What should be the molarity of such a sample of acid if the density of the solution is 1·504 g
mL-1 ?
Sol: Mass of HNO3 in solution = 68 g
Molar mass of HNO3 = 63 g mol-1
Mass of solution = 100 g
Density of solution = 1·504 g mL-1

2.5. 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 m L-1, then what shall be
the molarity of the solution?
Sol: 10 percent w/w solution of glucose in water means 10g glucose and 90g of water.
Molar mass of glucose = 180g mol-1 and molar mass of water = 18g mol-1
2.6. How many mL of 0.1 M HCl are required to react completely with 1 g mixture of Na2C03 and
NaHCO3 containing equimolar amounts of both?
Sol: Calculation of no. of moles of components in the mixture.
2.7. Calculate the percentage composition in terms of mass of a solution obtained by mixing 300 g of a
25% and 400 g of a 40% solution by mass.
Sol:

2.8. An antifreeze solution is prepared from 222.6 g of ethylene glycol, (C2 H6O2 ) and200 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?
Sol:

2.9. 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.
Sol: 15 ppm means 15 parts in million (106) by mass in the solution.

2.10. What role does the molecular interaction play in solution of alcohol in water?
Sol: In case of alcohol as well as water, the molecules are interlinked by intermolecular hydrogen
bonding. However, the hydrogen bonding is also present in the molecules of alcohol and water in the
solution but it is comparatively less than both alcohol and water. As a result, the magnitude of attractive
forces tends to decrease and the solution shows positive deviation from Raoult’s Law. This will lead to
increase in vapour pressure of the solution and also decrease in its boiling point.

2.11. Why do gases always tend to be less soluble in liquids as the temperature is raised?
Sol: When gases are dissolved in water, it is accompanied by a release of heat energy, i.e., process is
exothermic. When the temperature is increased, according to Lechatlier’s Principle, the equilibrium
shifts in backward direction, and thus gases becomes less soluble in liquids.

2.12. State Henry’s law and mention some of its important applications.
Sol:
Henry’s law: The solubility of a gas in a liquid at a particular temperature is directly proportional to the
pressure of the gas in equilibrium with the liquid at that temperature.
or
The partial pressure of a gas in vapour phase is proportional to the mole fraction of the gas (x) in the
solution. p = KHX
where KH is Henry’s law constant.
Applications of Henry’s law :
(i) In order to increase the solubility of CO2 gas in soft drinks and soda water, the bottles are normally
sealed under high pressure. Increase in pressure increases the solubility of a gas in a solvent according to
Henry’s Law. If the bottle is opened by removing the stopper or seal, the pressure on the surface of the
gas will suddenly decrease. This will cause a decrease in the solubility of the gas in the liquid i.e. water.
As a result, it will rush out of the bottle producing a hissing noise or with a fiz.
(ii) As pointed above, oxygen to be used by deep sea divers is generally diluted with helium inorder to
reduce or minimise the painfril effects during decompression.
(iii) As the partial pressure of oxygen in air is high, in lungs it combines with haemoglobin to form
oxyhaemoglobin. In tissues, the partial pressure of oxygen is comparatively low. Therefore,
oxyhaemoglobin releases oxygen in order to carry out cellular activities.

2.13. 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?
Sol:

2.14. According to Raoult’s law, what is meant by positive and negative deviaitions and how is the sign
of ∆solH related to positive and negative deviations from Raoult’s law?
Sol: Solutions having vapour pressures more than that expected from Raoult’s law are said to exhibit
positive deviation. In these solutions solvent – solute interactions are weaker and ∆solH is positive
because stronger A – A or B – B interactions are replaced by weaker A – B interactions. Breaking of the
stronger interactions requires more energy & less energy is released on formation of weaker
interactions. So overall ∆sol H is positive. Similarly ∆solV is positive i.e. the volume of solution is some what
more than sum of volumes of solvent and solute.
So there is expansion in volume on solution formation.
Similarly in case of solutions exhibiting negative deviations, A – B interactions are stronger than A-A&B-B.
So weaker interactions are replaced by stronger interactions so , there is release of energy i.e. ∆sol H is
negative.

2.15. An aqueous solution of 2 percent non-volatile solute exerts a pressure of 1·004 bar at the boiling
point of the solvent. What is the molecular mass of the solute ?
Sol:
According to Raoult’s Law,

2.16 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
26.0 g of heptane and 35.0 g of octane?
Sol.
2.17. 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
Sol: 1 molal solution of solute means 1 mole of solute in 1000g of the solvent.

2.18. Calculate the mass of a non-volatile solute (molecular mass 40 g mol-1) that should be dissolved
in 114 g of octane to reduce its pressure to 80%. (C.B.S.E. Outside Delhi 2008)
Sol: According to Raoult’s Law,
2.19. A solution containing 30g of non-volatile solute exactly in 90 g of water has a vapour pressure of
2.8 kPa at 298 K. Further, 18g of water is then added to the solution and the new of vapour pressure
becomes 2.9 kPa at 298 K. Calculate
(i) molar mass of the solute.
(ii) vapour pressure of water at 298 K.
Sol: Let the molar mass of solute = Mg mol-1
2.20. A 5% solution (by mass) of cane sugar in water has freezing point of 271 K. Calculate the freezing
point of 5% glucose in water if freezing point of pure water is 273.15 K.
Sol: Mass of sugar in 5% (by mass) solution means 5gin 100g of solvent (water)

2.21. Two elements A and B form compounds having formula AB2 and AB4. When dissolved in 20g 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.
Sol:

2.22. At 300 K, 36 g glucose present per litre in its solution has osmotic pressure of 4·98 bar. If the
osmotic pressure of the solution is 1·52 bar at the same temperature, what would be its
concentration?
Sol:
2.23. Suggest the most important type of intermolecular attractive interaction in the following pairs:
(i) n-hexane and n-octane
(ii) I2 and CCl4.
(iii) NaCl04 and water
(iv) methanol and acetone
(v) acetonitrile (CH3CN) and acetone (C3H60)
Sol: (i) Both w-hexane and n-octane are non-polar. Thus, the intermolecular interactions will be London
dispersion forces.
(ii) Both I2 and CCl4 are non-polar. Thus, the intermolecular interactions will be London dispersion forces.
(iii) NaCl04 is an ionic compound and gives Na+ and Cl04– ions in the Solution. Water is a polar molecule.
Thus, the intermolecular interactions will be ion-dipole interactions.
(iv) Both methanol and acetone are polar molecules. Thus, intermolecular interactions will be dipole-
dipole interactions.
(v) Both CH3CN and C3H6O are polar molecules. Thus, intermolecular interactions will be dipole-dipole
interactions.

2.24. Based on solute solvent interactions, arrange the following in order of increasing solubility in n-
octane and explain. Cyclohexane, KCl, CH3OH, CH3CN.
Sol: n-octane (C8H18) is a non-polar liquid and solubility is governed by the principle that like dissolve like.
Keeping this in view, the increasing order of solubility of different solutes is:
KCl < CH3OH < CH3C=N < C6H12 (cyclohexane).

2.25. 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
Sol: (i) Phenol (having polar – OH group) – Partially soluble.
(ii) Toluene (non-polar) – Insoluble.
(iii) Formic acid (form hydrogen bonds with water molecules) – Highly soluble.
(iv) Ethylene glycol (form hydrogen bonds with water molecules) Highly soluble.
(v) Chloroform (non-polar)- Insoluble.
(vi) Pentanol (having polar -OH) – Partially soluble.

2.26. If the density of lake water is 1·25 g mL-1, and it contains 92 g of Na+ ions per kg of water,
calculate the molality of Na+ ions in the lake. (C.B.S.E. Outside Delhi 2008)
Sol:
2.27. If the solubility product of CuS is 6 x 10-16, calculate the maximum molarity of CuS in aqueous
solution.
Sol:

2.28. Calculate the mass percentage of aspirin (C9H8O4 in acetonitrile (CH3CN) when 6.5g of CHO is
dissolved in 450 g of CH3CN.
Solution:
Mass of aspirin = 6.5 g
Mass of acetonitrile = 450 g
Then, total mass of the solution = (6.5 + 450) g = 456.5 g
Therefore, mass percentage of C9H8O4 = 6.5456.5 × 100%
= 1.424%

2.29. 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 1.5 x 10-3 m
aqueous solution required for the above dose.
Solution:
2.30. Calculate the amount of benzoic acid (C5H5COOH) required for preparing 250 mL of 0· 15 M
solution in methanol.
Solution:

2.31. 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.
Solution:

Fluorine being more electronegative than chlorine has the highest electron withdrawing inductive effect.
Thus, triflouroacetic acid is the strongest trichloroacetic acid is second most and acetic acid is the
weakest acid due to absence of any electron withdrawing group. Thus, F3CCOOH ionizes to the largest
extent while CH3COOH ionizes to minimum extent in water. Greater the extent of ionization greater is the
depression in freezing point. Hence, the order of depression in freezing point will be CH3COOH <
Cl3CCOOH < F3CCOOH.

2.32. Calculate the depression in the freezing point of water when 10g of CH3CH2CHClCOOH is added to
250g of water. Ka = 1.4 x 1o-3 Kg = 1.86 K kg mol-1.

Solution:
Mass of solute (CH3CH2CHClCOOH) = 10 g
Molar mass of
CH3CH2CHClC00H = 4 × 12 + 7 × 1 + 1 × 35.5 + 2 × 16 = 48 + 7 + 35.5 + 32
= 122.5 g mol-1
\frac{\text { Mass / Molar mass }}{\text { Mass of solvent (Kg) }} = Mass / Molar mass Mass of solvent
(Kg) [latex/latex]=[latex]10 g(122.5 g mol−1)×(0.25Kg)
= 0.326 m
Let α be the degree of dissociation of CH3CH2CHClCOOH then
Total no. of moles after dissociation = 1 – α + α + α
=1+α
Van’t Hoff factor
Total no. of moles after dissociation

∴ i = 1+α1
=1+α
= 1 + 0.0655
= 1.0655
Hence, the depression in the freezing point of water is given as:
ΔTf = i.Kfm
= 1.0655 × 1.86 kg mol-1 × 0.326 mol kg-1
= 0.65K

2.33. 19.5g of CH2FCOOH is dissolved in 500g of water. The depression in the freezing point of water
observed is 1.0°C. Calculate the van’s Hoff factor and dissociation constant of fluoroacetic acid.

Solution:
Calculation of Van’t Hoff factor (i)
Given, w1 = 500 g = 0.5 kg, w2 = 19.5 g, Kf = 1.86 K kg mol-1, ΔTf = 1 K
Molar mass of CH2FCOOH (M2)
= 2 × 12 + 3 × 1 + 1 × 19 + 2 × 16
= 24 + 3 + 19 + 32
= 78 g mol-1
ΔTf = i Kf m
2.34. 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.
Solution:
According to Raoult’s Law,

2.35. Henry’s law constant for the molality of methane in benzene at 298 K is 4.27 x 105 mm Hg.
Calculate the solubility of methane in benzene at 298 K under 760 mm Hg.

Solution:
Here, p = 760 mm Hg, KH = 4.27 × 105 mm Hg (at 298 K)
According to Henry’s law, p = KHχ
χ = pkH
= 760 mmHg4.27×105 mmHg
= 177.99 × 10-5
= 178 × 10-5
Hence, the mole fraction of methane in benzene is 178 × 10-5.

2.36. 100g of liquid A (molar mass 140 g mol-1) was dissolved in 1000g of liquid B (molar mass 180g
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.

Solution:
Number of moles of liquid A, nA = w1M1 = 100140 mol = 0.714 mol
Number of moles of liquid B,nB = w2M2 = 1000180 mol = 5.556 mol
Then, mole fraction of A, χA = nAnA+nB
= 0.714 mol(0.714+5.556)mol = 0.114
Mole fraction of B, χB = 1 – 0.114 = 0.886
Vapour pressure of pure liquid B, p0B = 500 torr
Therefore, vapour pressure of liquid B in the solution,
PB = p0BχB
= 500 × 0.886
= 443 torr
Total vapour pressure of the solution, ptotal = 475 torr
∴ Vapour pressure of liquid A in the solution,
PA = Ptotal – PB
= 475 – 443 = 32 torr
Now, PA = p0AχA
⇒ pAχA = 320.114
= 280.7 torr
Hence, the vapour pressure of pure liquid A is 280.7 torr.

2.37. 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 Ptotal,
Pchlroform and Pacetone as a function of χacetone. The experimental data observed for different compositions
of mixtures is:

Plot this data also on the same graph paper. Indicate whether it has positive deviation or negative
deviation from the ideal solution.

Solution:

It can be observed from the graph that the plot for the ptotai of the solution curves downwards.
Therefore, the solution shows negative deviation from the ideal behaviour.

2.38. 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 80g of benzene is mixed with 100g of
toluene.
Solution:
Molar mass of benzene (C6H6) = 6 × 12 + 6 × 1 = 78g mol-1
Molar mass of toluene (C6H5CH3 ) = 7 × 12 + 8 × 1 = 92 g mol-1
No. of moles present in 80 g of benzene = 8078 mol = 1.026 mol
No. of moles present in 100 g of toluene = 10092 mol = 1.087 mol
Mole fraction of benzene, χC6H6, = 1.0261.026+1.087 = 0.486
∴ Mole fraction of toluene,χC6H5CH35013 = 1 – 0.486 = 0.514
It is given that vapour pressure of pure benzene, p0C6H6 = 50.71 mm Hg
Vapour pressure of pure toluene, p0C6H5CH3 = 32.06 mm Hg
Therefore, partial vapour pressure of benzene,
Ptotal = χC6H6 × p0C6H6
= 0.486 × 50.71
= 24.645 mm Hg
Partial vapour pressure of toluene, PC6H5CH3 = χC6H5CH3 × P0C6H5CH3
= 0.514 × 32.06
= 16.479 mm Hg
Total vapour pressure of solution (p) = 24.645 + 16.479
= 41.124 mm Hg
Mole fraction of benzene in vapour phase
= χC6H6×p0C6H6ptotal
= 0.486×(50.71)mm(41.124)mm
= 0.599 ≅ 0.6

2.39. The air is a mixture of a number of gases. The major components are oxygen and nitrogen with
an approximate proportion of 20% is to 79% by volume at 298 K. The water is in equilibrium with air at
a pressure of 10 atm. At 298 K if Henry’s law constants for oxygen and nitrogen are 3.30 x 107 mm and
6.51 x 107 mm respectively, calculate the composition of these gases in water.

Solution:
Percentage of oxygen (O2) in air = 20%
Percentage of nitrogen (N2) in air = 79%
Also, it is given that water is in equilibrium with air at a total pressure of 10 atm that is, (10 × 760) mm =
7600 mm
Therefore, partial pressure of oxygen,
PO2 = 20100 x 7600 mm
= 1520 mm Hg
Partial pressure of nitrogen, pN2 = 79100 x 7600 mm
= 6004 mm Hg
Now, according to Henry’s law,
p = KH.χ
For oxygen:
6004 mm6.51×107 mm
(Given KH = 6.51 × 107 mm)
= 9.22 × 10-5
Hence, the mole fractions of oxygen and nitrogen in water are 4.61 × 10-5 and 9.22 × 10-5 respectively.

2.40. 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.

Solution:
We know that,
π = i RT
⇒ π = i RT
⇒w=
Given,
π = 0.75 atm
V = 2.5L
i = 2.47
T = (27 + 273)K = 300K
R = 0.0821 L atm K-1mol–
Molar mass of CaCl2(M) = 1 × 40 + 2 × 35.5 = 111 g mol -1
Therefore, w = 0.75×111×2.52.47×0.0821×300 = 3.42g
Hence the required amount of CaCl2 is3.42g

2.41. 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. (C.B.S.E. 2013)
Solution:
Step I. Calculation of Van’t Hoff factor (i)
K2SO4 dissociates in water as :