Class XIIth Chemistry Electrochemistry 1

Class XII

26

Solutions

Lecture - I

Pre requisites Slide 3

Various types of solutions e.g., solid in liquid, gas mass of solute 100
(iii) Percent mass by volume =
in liquid, liquid in liquid, Solid in solid etc. volume of solution
Knowledge of Henry’s law. (iv) Strength or conc. =
___________________________________________ mass of solute gms
g L–1
Slide 1 volume of solution inL.
mass of solute
In every day life we deal with mixtures or (v) Parts per million = 106
mass of solution
solutions.
(vi) Mole fraction:
Some properties associated with solutions are of
nB
great practical importance. mole fraction of solute (B) = XB
nA nB
In this chapter we study all aspects for example
nA
the colligative properties. mole fraction of solvent (A) = XA
nA nB
The ways in which concentration can be
And XA + XB = 1.
expressed are as follows:- __________________________________________
__________________________________________ Slide 4
Slide 2
moles of solute
(vii) Molality (m) =
(i) Mass percentage or percent by mass:. kg of the solvent
mass of solute
100 WB 1000
mass of solution m
MB WA
mass of solute 100 WB and MB are wt. and molar mass of solute.
volume of solution density of solution WA is wt. in grams of solvent.
volume of solute 100 moles of solute
(ii) Percent by volume (viii) Molarity M
volume of solution –1
moles L Volume of solution inL.

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164 Solutions Chemistry (XII)

gram equivalents or Slide 7

equivalents of solute Illustration: 1
(ix) Normality N
g equiv L–1 Volume of soluioninL.
Henry’s law constant for the molality of methane in
__________________________________________
benzene at 298 K is 4. 27 × 105 mm Hg. Calculate the
Slide 5 (A)
solubility of methane in benzene, at 298 K under a
Solubility of Gases pressure of 760 mm Hg, in terms of its mole fraction in
The solubility of a gas at a given temperature is solution.
__________________________________________
directly proportional to the pressure at which it is
dissolved. Slide 8
(xB) mole fraction is taken as a measure of its Vapour Pressure:
solubility and p is the partial pressure of gas in
equilibrium with the solution. The pressure exerted by the vapours above the liquid
xB p or p xB surface in equilibrium with the liquid at a given
or p = KHxB. temperature is called vapour pressure of the liquid.
__________________________________________ __________________________________________
Slide 5 (B) Slide 9 (A)

Here KH is Henry’s constant. Raoult’s law

Different gases have different KH values at the (A) For Non-volatile solute
same temperature so KH is a function of the
The vap. Pressure of solution containing non-
nature of gas.
volatile solute is less than the vapour pressure
Higher the value of KH at a given pressure the
of pure solvent.
lower is the solubility of gas in liquid.
__________________________________________ It p1 is the vapour pressure of solvent in
solution and p1 is the vapour pressure of pure
Slide 6
solvent and x1 is the mole fraction of solvent
With rising temperature the solubility of gases in solution then lowering of vapour pressure is
decreases in liquids. equal to p1 – p1 p1 – p1 x1 since p1 x1p1
In solution the gas molecules are present in liquid
or p1 1 – x1
phase and the process of dissolution can be
considered as similar to condensation and heat is __________________________________________
evolved in the process. Slide 9 (B)
The process involves dynamic equilibrium.
or p1 – p1 p1 p1 x 2 where x2 is the mole
Since dissolution is exothermic the solubility will
decrease with increase in temperature (Le fraction of solute in solution.
chatelier’s rule)

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165 Solutions Chemistry (XII)

or relative lowering of vapour pressure PB XB Or PB = PB°XB

p1 – p1 n2 PA° and PB° are vapour pressure of pure
x2
p1 n1 n2 components A and B respectively.
Where n1 and n2 are the moles of solvent and __________________________________________
solute respectively. Slide 12 (B)
__________________________________________
PA and PB are partial vapour pressures of A and B in
Slide 10
solution
For dilute solutions neglecting n2 in the
denominator we get
p1 – p1 n2 W2 M1
Where W1 and W2 are
p1 n1 M2 W1
the masses and M1 and M2 are the molar masses
of solvent and solute respectively.
Knowing other quantities the molar mass of solute
can be calculated
This is known as Raoults law. That is for a
solution containing non-volatile solute, the relative
__________________________________________
lowering of vapour pressure is equal to mole
Slide 13
fraction of the solute.
__________________________________________
According to Dalton’s law of Partial Pressure
Slide 11 P = PA + PB
Illustration: 2 = PA°XA + PB°XB ( XA + XB = 1)
= PA°(1 – XB) + PB°XB
Vapour pressure of water at 293 K is 17.535 mm of = PA° – PA°XB + PB°XB
Hg. Calculate the vapour pressure of water at 293 K
P PB – PA XB PA
when 25 g of glucose is dissolved in 450 g of water.
___________________________________________

Slide 12 (A)

(B) Solution of two volatile liquids

Two volatile liquids A and B.
PA XA Or PA = PA°XA

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166 Solutions Chemistry (XII)

Slide 14 Slide 17 (A)

Illustration: - 3 A perfectly ideal solution is rare but a mixture of n-

Heptane and octane form an ideal solution. At 373 k
the vapour pressure of two liquids are 105.2 K Pa and
46.8 k Pa respectively. What will be the vapour
pressure of a mixture having 26.0 g heptane and 35.0
g of octane?
__________________________________________
Slide 15
Illustration:- 4
The vapour pressure of pure liquids A and B are 450
and 700 mm Hg respectively at 350 K. Find out the
hexane and n-heptane; bromoethane and
chloroethane; benzene and toluene etc, are
solutions which are nearly ideal in behaviour.
If the vapour pressure of solution is more than the
value predicted by Raoult’s law, it exhibits a
positive deviation as depicted in the following
figures:
__________________________________________
Slide 17 (B)
Vapour pressure Vapour pressure
of solution of solution

Vapour pressure
Vapour pressure
composition of the liquid mixture in terms of mole
fractions if the total vapour pressure is 600 mm Hg. p1 p2 p2 p1
Also find out the mole fractions of the two liquids in
vapour phase.
__________________________________________ x1 = 0 Mole fraction x1 = 1 x1 = 0 Mole fraction x1 = 1
Slide 16 x2 = 1 x1 x2 = 0 x2 = 1 x1 x2 = 0
x2 x2
The solutions which obey Raoult’s law over the (a) (b)
entire range of concentration are known are Ideal __________________________________________
solutions. Slide 18
Two more properties should hold true for ideal
solutions. i.e., Hmix = 0 and Vmix = 0. Molecular interactions are responsible for those
It means no heat should be evolved or absorbed deviations.
and there should be no volume change on mixing For positive deviation A – B < A – A or B – B.
the two components. Examples are ethanol and acetone or carbon
A third necessary condition for the solution to be disulphide and acetone.
ideal is, A – B = A – A and B – B. For negative deviation A – B > A – A or B – B.
Phenol and aniline; chloroform and acetone are
examples of this type.

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167 Solutions Chemistry (XII)

Slide 19

Some liquid solutions form azeotropes which are

binary mixtures.
These have same composition in liquid and
vapour phase and boil at a constant temperature.
It is not possible to separate the components by
fractional distillation.
Azeotropes can be minimum or maximum boiling.
__________________________________________
Slide 20

Ethanol-water mixtures show a large positive

deviations and form a minimum boiling azeotrope.
This azeotrope contains approx 95% ethanol and
5% water,
Similarly nitric acid and water have less vapour
pressure than the ideal value and show a negative
deviation and form a maximum boiling azeotrope.
It contains almost 68 percent nitric acid and 32%
water by mass.

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168 Solutions Chemistry (XII)

Lecture Assignment
1 Mark Questions 3 Mark Questions
Q1. Give one example of Q9. The vapour pressure of a pure liquid A is 30
(i) Gas in liquid type solution mmHg at 320 K. The vapour pressure of this
(ii) Solid solution liquid in a solution with liquid B is 28 mmHg
Q2. Define molarity and molality of solutions. at the same temperature. What is the mole
Q3. Define the term mole fraction giving one fraction of B in the solution if it obey’s
example. Raoult’s law.
Q4. What do you understand by mass percent- Q10. What properties depend on the number of
age? particles dissolved in solution rather than
Q5. Why does the molality of a solution remain their chemical identity? Name two such
unchanged with temperature? properties.
2 Mark Questions Q11. Define osmosis.
Q12. Henry’s law constant for the molality of
Q6. State Henry’s law.
methane in benzene is 4.27 × 105 mmHg.
Q7. List the factors on which the Henry’s
Calculate the solubility of methane in
constant depends.
benzene at 298 K under 760 mmHg.
Q8. What are ideal liquid solutions?

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169 Solutions Chemistry (XII)

Lecture - II

Pre requisites Slide 23 (A)

Raoults law. Experiments have shown that for dilute solution

Deviations from Raoults law. Tb m
__________________________________________ or Tb = Kb.m
Slide 21 R.M.Tb2
Kb is called molal elevation
1000. Hvap.
Elevation in boiling point:
constant or molal ebullioscopic constant.
The temperature at which the vapour pressure Here R is gas constant, M is molar mass of
becomes equal to the atmospheric pressure is solvent, Tb is boiling point of pure solvent, Hvap. is
called boiling point. enthalpy of vapourisation.
On dissolving a non-volatile solute in the solvent __________________________________________
the boiling temperature of the solution goes up. Slide 23 (B)
The following figure depicts the boiling point of
Calculation of Molecular Mass
pure solvent and solution.
__________________________________________ WB 1000
Slide 22 m B
MB WA
Atmospheric pressure Here WB and MB and are weight and molar mass
1 atm. of solute and WA is weight of solvent
B D
ol ve nt Tb Kb m Kb
WB 1000
S n
A utio Tb MB WA
v.p. So l
C Kb WB 1000
or MB
WA Tb
__________________________________________
T0 T1 Slide 24
Temp
Depression in freezing point

Freezing point is defined as the temperature at

which its solid and liquid phase have the same
vapour pressure.

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170 Solutions Chemistry (XII)

C Slide 25 (B)
nt
nt S o lv e C’
olid olve B Calculation of Molecular Mass
S S tio n
P So lu
A’ WB 1000
D P’ m
MB WA
v.p. A
WB 1000
or Tf Kf
Tf MB WA
T1 T0 Kf
WB 1000
or MB
Temp WA Tf
__________________________________________ ___________________________________________
Slide 25 (A) Slide 26

Tf m Illustration: - 5
Tf = Kf × m
A very small amount of a non-volatile solute (that does
Kf = molal depression constant or cryoscopic constant.
not dissociate) is dissolved in 56.8 cm3 of
R.M.Tf2
Kf benzene (density 0.889g cm-3). At room temperature
1000. Hfus.
vapour pressure of this solution is 98.88 mm Hg while
Here R is gas constant, M is molar mass of solvent, Tf that of benzene is 100 mm Hg. Find the Molality of
is freezing point of solvent and Hf is enthalpy of this solution. If the freezing temperature of this
fusion. solution is 0.73 degree lower than that of benzene,
what is the value of molal freezing point depression
constant of benzene?

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171 Solutions Chemistry (XII)

Lecture Assignment
2 Mark Questions if total vapour pressure is 600 mmHg. Also,
find the composition of the vapour phase.
Q1. Calculate the mole fraction of ethyl alcohol
Q10. 100 g liquid A (molar mass 140 g/mol) was
(C2H5OH) and water in a solution in which 46
dissolved in 1000 g of liquid B (molar mass
g of ethyl alcohol and 90 g of water have been
180 g/mol). The vapour pressure of pure liquid
mixed.
B was found to be 500 torr. Calculate the V.P.
Q2. A 250 cm3 solution of sodium sulphate
of pure liquid A and its vapour pressure in the
contains 3.01 × 1022 sodium ions. What is the
solution if the total V.P. of solution is 475 torr.
molarity of the solution?
Q11. A solution was prepared by dissolving 0.915 g
Q3. When does a solution deviate from the ideal
of sulphur, S8, in 100.0 g of acetic acid,
behaviour?
CH3COOH. Calculate the boiling point of the
Q4. Define azeotropic mixture.
solution. The boiling point of pure acetic acid
Q5. What are the different types of azeotropes?
is 118.5°C. The value of kb is 3.08°C kg mol–1.
Give one example of each.
Q12. Solution A is obtained by dissolving 1g of urea
Q6. Which will have higher boiling point, 0.1 M
in 100 g of water and solution B is obtained by
NaCl or 0.1 M BaCl2 solution in water?
dissolving 1g of glucose in 100 g of water.
Q7. Which has the highest freezing point:
Which solution will have a higher boiling point
(a) 1 M glucose
and why?
(b) 1 M NaCl
5 Mark Questions
(c) 1 M CaCl2
(d) 1 M AlF3? Q13. Calculate the osmotic pressure in pascals
3 Mark Questions exerted by a solution prepared by dissolving
1.0 gram of polymer of molar mass 185,000 in
Q8. What happens when two solutions of the
450 ml of water at 37°C.
same solvent are separated by a
Q14. 0.6 mL of acetic acid (CH3COOH) having
semipermeable membrane?
density 1.06 g mL–1 is dissolved in 1 L of H2O.
Q9. The vapour pressure of pure liquids A and B
The depression in freezing point was
are 450 and 700 mmHg respectively at 350 K.
observed to be 0.0205°C. Calculate the Van’t
Find out the composition of the liquid mixture
Hoff factor and the dissociation constant of
acid. (kf = 1.86 K kg mol–1)

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Notes: -
172 Solutions Chemistry (XII)

Lecture - III
Pre requisites Slide 29

Abnormal Colligative Properties

Knowledge of various colligative properties.
Application in determining various constants. Colligative properties depend on the number of
__________________________________________ particles present in solution.
Slide 27 If the solute undergoes dissociation or association
in solution, the number of particles change and
Osmosis and Osmotic Pressure
the observed values of the colligative properties
The osmotic pressure of the solution at a would also change.
particular temperature may be defined as the __________________________________________
excess hydrostatic pressure that builds up when Slide 30
the solution is separated from the solvent by a
Vant Hoff introduced a factor i known as van’t Hoff
semi-permeable membrane.( )
factor to account for the extent of dissociation or
Isotonic: Two solutions having same osmotic
association. Thus
pressure.
Totalno.of particlesafter disso.or asso.
Hypertonic solution: Solution having higher i ;
Totalno.of particlesbefore disso.or asso.
osmotic pressure than some other is said to be
hypertonic w.r.t. other. observedcolligativeproperty
i ;
__________________________________________ Calculatedcolligativeproperty
Slide 28 Normalmolar mass
i
observedmolar mass.
Hypotonic solution: Solution having lower osmotic
__________________________________________
pressure relative to some other.
Reverse osmosis: Purification of sea water. Slide 31
Vant Hoff’s equation: In the case of association or dissociation of solute
V nRT particles the expressions are:
n p n
RT CRT i 2
V p n1
Calculation of molecular mass Tb iK b .m
nB Tf iK f .m
RT
V in2RT / V
WB RT WB RT
or MB n2 = moles of solute and n1 = mole of solvent
MB V V

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Notes: -
173 Solutions
Slide 32
Illustration: - 6
Calculate the mass of a non-volatile solute (M = 40)
which should be dissolved in 114 g octane to reduce
its vapour pressure to 80%.
__________________________________________
Slide 33
Illustration: - 7
The elements ‘A’ and ‘B’ form compounds AB2 and
AB4. When dissolved in 20g of benzene 1.0 g of AB2
lowers the freezing point by 2.3 K where as 1.0 g of
AB4 lowers it by 1.3K. Kf for benzene is 5.1 K. Kg
mol–1. Calculate atomic mass of ‘A’ and ‘B’.
__________________________________________
Slide 34
Question 8
A 1.0 m aqueous solution of a monobasic acid (M =
20) freezes at –1.9°. Kf of water is 1.86 K.Kg. mol-1. If
the density of solution is 1.12 g/mL, find out Ka of the
acid
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Notes: -
Chemistry (XII)
Slide 35
Illustration: - 9
Urea dissolved in 250 g of water freezes at –0.744°C.
Solution was cooled when some ice was formed.
Solution was decanted and heated to 100°C when the
vap.pr. was found to be 752.7 mm of Hg. How much
ice was formed and find out the temperature to which
solution was cooled? Kf (H2O) = 1.86
__________________________________________
Slide 36
Illustration: - 10
Calculate the amount of NaCl which must be added to
100g water so that freezing point is depressed by 2 K.
For water Kf = 1.86 K kg mol–1
174 Solutions Chemistry (XII)

Lecture Assignment
2 Mark Questions 5 Mark Questions
Q1. Define formality. Q10. (i) What is osmotic pressure and how is it
Q2. If is the osmotic pressure and V is the related to the molecular mass of non-
volume in litres of solution containing one gm volatile substance?
mol of solute, what would be the value of V (ii) What advantage the osmotic pressure
at 273 K. method has over the elevation of boiling
Q3. What is relation between absolute point method for determining molecular
temperature and osmotic pressure? masses?
Q4. What do you understand by “colligative Q11. What is the molar concentration of solute
properties”? particles in the human blood if the osmotic
Q5. Define osmotic pressure. pressure is 7.2 atm at the body temperature of
3 Mark Questions 37°C? (R = 0.0821 L atm K–1 mol–1)
Q12. How much glucose must be dissolved in one
Q6. Why the osmotic pressure measurement is
litre of an aqueous solution so that its osmotic
preferred for the molar mass determination of
pressure is 2.57 atm at 300 K? (R = 0.0821 L
macromolecules over other colligative
atm K–1 mol–1)
properties?
Q13. Calculate the molar concentration of urea
Q7. Before giving intravenous injection what care
solution if it exerts an osmotic pressure of
is generally taken and why?
2.45 atm at 300 K.
Q8. When fruits and vegetables that have dried
(R = 0.0821 L atm mol–1 K–1)
are placed in water, they slowly swell and
return to original form, why? Would a
temperature increase accelerate the process?
Explain.
Q9. The solubility of Ba(OH)2.8H2O in water at 288
K is 5.6 g per 100 g of water. What is the
molality of the hydroxide ions in the saturated
solution of barium hydroxide at 288 K?
(Atomic Mass: Ba = 137, O = 16, H = 1).

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Notes: -
175 Solutions Chemistry (XII)

Chapter Assignment
2 Mark Questions
Q1. For which of the following van’t Hoff factor can
not be greater than unity:
(a) K4[Fe(CN)6]
(b) AlCl3
(c) NH2CONH2
(d) KNO3?
Q2. Osmotic pressure of a solution containing 7g
of dissolved protein per 100 cm3 of the
solution is 20 mm Hg at 310 K. calculate the
molar mass of protein.
[R = 0.082 L atom K–1 mol–1]
Q3. An electrolyte AB is 50% ionized in aqueous
solution. Calculate the freezing point of 1
molal aqueous solution.
Q4. What is molar concentration of solute particles
in a human blood if the osmotic pressure is
7.2 atm at the body temperature of 37°C?
(R = 0.0821 L atm K–1 mol–1)
Q5. In aqueous solution, NaCl is completely
ionized into Na+ and Cl– ions. Compute the
osmotic pressure of 0.255 M solution of NaCl
at 300 K.
3 Mark Questions
Q6. 45 g of ethylene glycol (C2H6O2) is mixed with
600 g of water. Calculate the
(i) Freezing point depression and
(ii) The freezing point of the solution. (kf for
water = 1.86 K kg mol–1)
Q7. In a solution of urea, 3.0 g of it is dissolved in
100 ml of water. What will be the freezing
point of this solution? State the approximation
made if any. [Kf for water = 1.86 K kg mol–1,
molar mass of urea = 60 g mol–1]
Q8. A solution of 3.800 g of sulphur in 100 g of
CS2 (boiling point = 46.30°C) boils at 46.66°C.
What is the formula of sulphur molecules in
this solution? (Atomic mass of sulphur = 32 g
mol–1 and Kb for CS2 = 2.40 K kg mol–1)
Q9. Calculate the osmotic pressure of a solution
obtained by mixing 100 cm3 of 0.25 M solution
of urea and 100 cm3 of 0.1 M solution of cane
sugar at 293 K. [R = 0.082 L atm mol–1 K–1]
Q10. An aqueous solution of glucose is made by
dissolving 10 g of glucose (C6H12O6) in 90 g of
water at 303 K be 32.8 mm Hg, what would be
the vapour pressure of the solution?
Q11. The solubility of Ba(OH)2.8H2O in water at 288
K is 5.6 g per 100 g of water. What is the
molality of the hydroxide ions in saturated
solution of Ba(OH)2.8H2O at 288 K?
Q12. Calculate molarity and molality of a 13%
solution (by weight) of sulphuric acid. Its
density is 1.020 g cm–3. (Atomic mass
H = 1, O = 16, S = 32 u)
Q13. 18 g of glucose, C6H12O6, is dissolved in 1 kg
of water in a saucepan. At what temperature
will water boil at 1.103 bar?
Q14. 45 g of ethylene glycol (C2H6O2) is mixed with
600 g of water. Calculate:
(a) Freezing point depression,
(b) Freezing point of the solution (Kf for water
= 1.86 K kg mol–1;
Atomic masses: C = 12, H = 1, O = 16 u)
Q15. A solution containing 18 g of non-volatile
solute in 200 g of water freezes at 272.07 K.
Calculate the molecular mass of solute.
(Kf = 1.86 K/m)

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Notes: -
176 Solutions
5 Mark Questions
Q16. An antifreeze solution is prepared from 222.6
g of ethylene glycol (C2H6O2), and 200 g of
water. Calculate the molality of the solution. If
the density of the solution is 1.072 g/mL, then
what is the molarity of the solutions?
Q17. If N2 gas is bubbled through water at 293 K,
how many millimoles of N2 gas would dissolve
in 1 L 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
K bar.
Q18. At 40°C, methanol and ethanol form nearly an
ideal solution with the pressure given by
p = 119 x + 135
Where x is the mole fraction of methanol and
P is the vapour pressure in torr. What are the
vapour pressures of the pure methanol and
pure ethanol at this temperature?
Q19. What is meant by positive and negative
deviations from Rault’s law and how is the
sign of Hsol related to positive and negative
deviations from Rault’s law?
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Notes: -
Chemistry (XII)
Q20. Ethylene glycol (C2H6O2) is used as antifreeze
and is non-volatile and has density of 1.109
g/cm3.
How many litres of ethylene glycol should be
used per litre of water to protect it from
freezing at – 3.7°C?
Q21. The molal freezing point depression constant
of benzene (C6H6) is 4.90 K kg mol–1.
Selenium exists as a polymer of the type Sex.
When 3.26 g of selenium is dissolved in 226 g
of benzene, the observed freezing point is
0.112°C lower than for pure benzene. Deduce
the molecular formula of selenium.
(Atomic mass of Se = 78.8 g mol–1)
Q22. Assuming complete ionization, calculate the
expected freezing point of solution prepared
by dissolving 6.00 g of Glauber’s salt,
Na2SO4.10H2O in 0.1 kg of H2O. (Kf for H2O =
1.86 K kg mol–1) [At. mass of Na = 23, S = 32,
O = 16, H = 1 u]
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