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Chapter

Liquid Solution & Surface Chemistry

Solution: A homogeneous mixture of two or more substances. (Solute + solvent = solution)


Saturated Solution : A solution that is in equilibrium with pure solid solute. No more solute can be dissolved
in it.1. Methods of expressing the concentration of a solution
The concentration of a solution can be expressed in a number of ways. The important meth-
ods are:
(i) Mass percentage or per cent by mass:
Mass of solute
%(w/w) Mass percentage of solute = x 100
Mass of solution
Mass of solute
=
Mass of solute Mass of solvent
Mass of solute
=
Volume of solution  Density of solution
(ii) Percent mass by volume:
Mass of solute
%(w/v) = x 100
Volume of soltuion
(iii) Parts per million (ppm) :
Mass of solute
ppm = x 106
Mass of solution
(iv) Mole fraction:
Let n moles of solute (A) and N moles of solvent (B) be presnet in a solution.
n N
Mole fraction of solute = = XA , Mole fraction of solvent = = XB
Nn Nn
In binary solution, XA + XB = 1
Mole fraction is independent of temperature of the solution.
(v) Molality
No. of moles of solute
Molality (m) =
weight (in kg) of solvent
Let wA grams of the solute of molecular mass mA be present in wB grams of the solvent,
then
wA
Molality (m) = x 1000
mA  wB
Relation between mole fraction and Molality :
X A 1000 wA  1000
= m =
X B  mB wB  mB
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Note: (i) Molality is the most convenient method to express the concentration because it
involves the mass of liquids rather than their volumes. It is also independent of the varia-
tion in temperature.
(vi) Molarity (Molar concentration)
No. of moles of solute
Molarity (M) =
Volume (in litre) of solution
wA
Molarity of the solution = x 1000
mA  V
Relation between molarity and % solute by mass :
Let d = density of solution in g/mL and let it contains x% (w/w) solute by mass.
Number of moles of solute in 1 litre
mass of solute in gram x  d  10
= = M
grams molecular mass of solute solute
x  d  10
M = mA
Molarity of dilution:
Before dilution After dilution
M1V1 = M2V2
Molarity of mixing:
M1V1 + M2V2 + M3V3 = MR(V1 + V2 + V3) MR = resultant molarity
Relationship between molality and molarity :
molarity 1000  M
Molality (m) = =
d  molarity  msolute 1000  d  M  M solute

Illustration 1. The density of a solution containng 13% by mass of sulphric acid is


1.09 g/mL. Calculate the molarity of the solution.
Solution: In solving such numericals, the following formula can be applied:
% strength of soln. density of soln. 10
Molarity =
Mol. mass
13  1.09  10
M = = 1.445 M
98
Illustration 2. The density of a 3 M sodium thiosulphate solution (Na 2S2O3) is 1.25 g/
mL. Calculate (i) the percentage by mass of sodium thiosulphate, (ii) the mole
fraction of sodium thiosulphate and (iii) molalities of Na + and S2 O3 2– ions.
x  d  10 x  1.25  10
Solution: M =  3 =
mA 158
 x = 37.92
474
(ii) No. of moles of Na2S2O3 = = 3
158
776
Mass of water = (1250 – 474) = 776 g , No. of moles of water = = 43.1
18
3 3
Mole fraction of Na2S2O3 = = = 0.065
43.1  3 46.1

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(iii) No. of moles of Na+ ions


= 2 × No. of moles of Na2S2O3 = 2 × 3 = 6
No. of moles of Na  ions
Molality of Na+ ion =
Mass of water in kg
6
= × 1000 = 7.73 m
776
No. of moles of S 2O32– ions = No. of moles of Na2S2O3
3
Molality of S2O32– ions = × 1000 = 3.86 m
776
Illustration 3. One litre of sea water weighs 1030 g and contains about 6 × 10–3g of dissolved O2.
Calculate the concentration of dissolved oxygen in ppm.
Solution: Mass of O2 in mg = 6 × 10–3g × 103 mg/g = 6mg
Mass of O in mg
2 6
ppm of O2  in 1030 g sea water =  Mass of sea water in kg  (1030 /1000)kg

6  1000
  5.8ppm
1030

2. Vapour Pressure

Thermostat Vapours
P

Liquid

Manometer
Physical equilibrium between
liquid vapours

The pressure exerted by the vapour (molecules in the vapour phase) over the surface of the liquid at the
equilibrium at given temperature is called the vapour pressure of the liquid.
Factors affecting vapour pressure
(i) Temperature :
Vapour pressure  Temperature

The temperature at which the vapour pressure of the


liquid becomes equal to the atmospheric pressure is
called its boiling point.
(ii) Nature of liquid:
1
Vapour pressure of liquid 
The strength of intermolec ular forces
acting between molecules
For example, ethyl alcohol has higher vapour pressure because of the weak intermolecular forces
acting between its molecules than water which has stronger intermolecular forces acting between water
molecules of volatile liquid has lower boiling point than a non-volatile liquid.
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(i) Vapour Pressure of a Solution Containing Non Volatile Solute - Raoult’s Law
:
Raoult’s Law : Acccording to this law, the partial pressure of any volatile constituent of a soltuion at a
constant temperature is equal to the vapour pressure of pure constituent multiplied by the mole fraction of that
constituent in the solution.
PA XA  PA = PA0 XA .......(1)

PA0

Vapour pressure
o XA
PA
=
PA

0 XA 1
1 XB 0

Relative Lowering of vapour pressure: For a solution of a non-volatile solute in a liquid, the
vapour pressure contribution by the non-volatile solute is negligible. Therefore, the partial vapour pressure of a
solution containing a non-volatile solute is equal to the product of vapour pressure of the pure liquid (solvent
PA ) and its mole fraction in the solution.
Let X A be the mole fraction of solvent A, then (Here pB0 = negligible as solute is non-volatile)
PA  PA X A
If X B be the mole fraction of the solute B, then
XA  X B  1  XA  1 – XB

hence PA  PA (1 – X B )  PA – PA X B  PAo XB  PAo  PA ......(2)


( PAo  PA is known as lowering of vapour pressure)

PAo  PA  P – P 
 X B  A  A is called relative lowering of vapour pressure, (RLVP) 
VP)  .....(3)
PAo  PA
 

 PA – PA 
Therefore, Raoult’s law states that the relative lowering of vapour pressure  P  , for a non-volatile
 A 
solute is equal to the mole fraction of the solute when the solvent alone is volatile.
Illustration 4: The vapour pressure of pure water at 37°C is 47.1 torr. What is the vapour pressure of
an aqueous solution at 37°C containing 20 g of glucose dissolved in 500 gm of water.
Also calculate vapour pressure lowering.
500 20
Solution: n H2O   27.78 mol , n(glucose)   0.11 mol
18 180
n H2 O 27.78 27.78
X H 2O     0.996
n H2O  n (glu cose) 27.78  0.11 27.89
According to Raoult’s law,
Vapour pressure of solution PH 2O  PHo2O X H 2O  47.1 0.996  46.9 torr

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Lowring of vapour pressure PHo 2O – PH2O  47.1 – 46.9  0.2 torr

Illustration 5. The vapour pressure of ethyl alcohol at 25°C is 59.2 torr. The vapour pressure of a
solution of urea in ethyl alcohol is 51.3 torr. What is the molality of the solution?
Solution: Given: PAo = 59.2 torr, pA = 51.3 torr
7. 9
By RLVP  Xsolute = = .1334
59.2
X 1000 XB 1000
 (molality) m = B  =  ( XA + XB = 1)
X A M solvent 1  X B  M solvent
0.1334 1000
m=  = 3.346 molal
0.8666 46
Illustration 6. Calculate relative lowering of vapour pressure of 0.161 molal aqueous solution.
X B  1000 X B  1000
Solution : we know Molality =  0.161 = 1  X   18
1  X B  msolvent B

XA = 0.00289  RLVP = XA = 0.00289

(ii) Vapour Pressure of a Solution Containing Two Volatile Liquids


Raoult’s law states that the partial vapour pressure of a component of a solution of two miscible liquids A and
B at a given temperature is equal to the product of the vapour pressure of the pure component at that temperature
and its mole fraction in the solution.

Mathematical Expression: Let us assume that a solution has nA moles of liquid A and n B moles of
liquid B. Let PA be the vapour pressure of the pure liquid A and PB is the vapour pressure of the pure liquid B.
nA nB
Mole fraction of A, X A  , Mole fraction of B, X B 
nA  n B nA  n B
According to Raoult’s law,
PA  PA X A (where PA is the partial vapour pressure of liquid A in the solution)
Similarly, PB  PB X B ( PB - partial vapour pressure of B in the solution)
The total vapour pressure of an ideal solution containing components A and B is the sum of partial vapour
pressures of all the components (Dalton’s law of partial pressures)
P  PA  PB  PAo X A  PBo X B ......(1)

o PAo
o P XB
P X A+ B
III. P= A
Vapour pressure

PBo o XA
= PA
I. P
A

II. P
B =Po
B XB

0 XA 1
1 XB 0

 XA + XB = 1  XA = 1– XB

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 P = PAo (1–XB) + PBo XB  PAo – PAo XB + PBo XB


P = PAo + ( PBo – PAo)XB ......(2)
About relation shows that graph between P and XB is a straight line having slope PBo – PAo and
intercept PAo
Similarly P = PBo + ( PAo – PBo)XA .......(3)

Above figure shows the relationship between partial vapour pressure and mole fraction of an ideal solution at
constant temperature.
1. Straight line I represents the plot of vapour pressure of liquid A (PA ) and its mole fraction (X A ) .
According to Raoult’s law this should be a straight line when
XA  0 PA  0 , X A  1, PA  PAo
When mole fraction of liquid A is X A  1 , the liquid A is pure and its vapour pressure is equal to PAo as
shown by line (I)
2. Straight line II represents the plot of partial vapour pressure of liquid (B) PB and its mole fraction
(X B ) . According to Raoult’s law, this should be a straight line. when
XB  0 PB  0 , X B  1, PB  PBo
When mole fraction of liquid B is X B  1 , the liquid B is pure and its vapour pressure is equal to PBo as
shown by line (II).
3. Straight line (III) represents the total vapour pressure, P, of the solution for any composition and is
given by the sum of the partial vapour pressure of liquids of A and B.
P  PA  PB

Illustration 7. An aqueous solution containing 28% by mass of a liquid A (mol. mass = 140) has a
vapour pressure of 160 mm at 37ºC. Find the vapour pressure of the pure liquid A. (The
vapour pressure of water at 37ºC is 150 mm.)
Solution : For two miscible liquids,
28
Ptotal = PA  PB  PAo X A  PBo X B nA = = 0.2,
140
72
Liquid B is water. Its mass is (100–28), i.e. 72. nB = = 4.0
18
Total number of moles = 0.2 + 4.0 = 4.2
Given Ptotal = 160 mm, PB0 = 150 mm
0.2 0 4.0
So 160 =  PA   5. 0
4.2 4.2
17.15  4.2
p 0A   360.15mm
0. 2
Dalton’s Law v/s Raoult’s Law:
The composition of the vapour in equilibrium with the solution can be calculated applying Daltons’ law
of partial pressures. Let the mole fractions of vapours A and B be YA and YB respectively. Let pA and
pB be the partial pressure of vaours A and B respectively and total pressure P.

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A B A B A B A B A B A vapours (Dalton's law)


yA = more fraction of A in vapour phase
yB = more fraction of B in vapour phase

(YA + YB = 1)

A B A B A B A B A B A solution (Raoult's law)


XA = more fraction of A in liquid phase
XB = more fraction of B in liquid phase
Solution of (A & B)
(XA + XB = 1)

From Raoult's law P = PoAXA + PBo XB


PA= PAXA and PB = PBo XB
o

From Dalton's law,


Partial pressure = Mole fraction × Total pressure
For A PA = yA × P
PAo X A
PoAXA = yA × P yA = .....(1)
P
Above formula is used for calculation of mole fraction of A in vapour phase
For B, PB = yB × P

PBo X B
PBo XB = yB × P yB = .....(2)
P
Above formula is used for calculation of mole fraction of B in vapour phase
P y A P y B
From (1) , XA = From (2) XB =
PAo PBo
P y A P y B
on adding XA + XB = + =1
PAo PBo
1 y yB
 = Ao + o .....(3)
P PA PB
Above formula is used to calculate total vapour pressure when mole fractions are given in vapoure
phase
Avoid confusion
P = PoAXA + PBoXB  This formula is used to calculate total pressure when mole fraction
are given in liquid phase

1 yA y
 o  Bo This formula is used to calculate total pressure when mole fraction
P PA PB
are given in vapour phase
Note: Thus, in case of ideal solution the vapour phase is phase is richer with more volatile component i.e., the
one having relatively greater vapour pressure.

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Illustration: 8. The vapour pressures of ethanol and methanol are 44.5 mm and 88.7 mm Hg respec-
tively. An ideal solution is formed at the same temperature by mixing 60 g of ethanol with 40
g of methanol. Calculate the total vapour pressure of the solution and the mole fracion of
methanol in the vapour.
60 40
Solution: No. of moles of C2H5OH = = 1.304, No. of moles of CH3OH = = 1.25
46 32
1.304
‘XA’ of ethyl alcohol = = 0.5107
1.304  1.25
1.25
‘XB’ of methyl alcohol = = 0.4893
1.304  1.25
Partial pressure of ethyl alcohol = XA.PA0 = 0.5107 × 44.5 = 22.73 mm Hg

Partial pressure of methyl alcohol = XB.PB0 = 0.4893 × 88.7 = 43.40 mm Hg


Total vapour pressure of solution = 22.73 + 43.40 = 66.13 mm Hg
Partial pressure of CH 3OH
Mole fraction of methyl alcohol in the vapour =
Total vapour pressure
43.40
= = 0.6563
66.13
(i) Ideal Solution
An ideal solution may be defined as the one which obeys Raoult’s law over all concentration ranges at
a given temperature. The total vapour pressure of an ideal solution containing liquids A and B is given
by the following equation.
P  PA  PB  PAo X A  PBo X B
In an ideal solution of two components A and B, all attractive forces between A and B molecules or
between A and A molecules or between B and B molecules (A–B, A–A and B–B) must be identical so
that the escaping tendency of an A or B molecule is independent of whether it is surrounded by A
molecules, B, molecules or varying proportions of A and B molecules. The escaping tendency of pure
liquid A in solution remains the same. Similarly the escaping tendency of B remains the same. Liquids
form ideal solution only when they have nearly same molecular size and related constitution so that they
have similar molecular environment in the pure state as well as in solution. A perfect ideal solution is
rare but many liquids form nearly ideal solution. Liquid heptane and hexane form an ideal solution
because the interaction between a hexane molecule and another hexane molecule is the same as the
interaction between two heptane molecules other examples of ideal solutions are:
benzene + toluene, chlorobenzene + bromobenzene;
ethyl bromde + ethyl iodide; n-butyl chloride + n-butyl bromide
ethyl alcohol + methyl alcohol

Conditions for Forming Ideal Solution: Two liquids on mixing form an ideal solution only when
1. both have similar structures and polarity so that they have similar molecular environment.
2. both have similar molecular sizes.
3. both have identical intermolecular forces.

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Characteristics Of Ideal Solution:


Mixing of two substances results in an ideal solution only when:
1. They obey Raoult’s Law
2. H mixing  0  that is no heat is absorbed or released during dissolution
3. Vmixing  0  that is the total volume of the solution is equal to the sum of the volume of the pure
liquids mixed to form the solution.

Graphical Representation of Vapour Pressure of Ideal Solutions:


Figure shows the relationship between partial vapour pressure and mole fraction of an ideal solution at constant
temperature.

o PAo
o P XB
P XA+ B
III. P= A
Vapour pressure

PBo o XA
=P
A

I. P
A

II. P
B =Po
B X
B

0 XA 1
1 XB 0

Note : Components of ideal solution can be saperated in pure form by fractional distillation
(ii) Non-Ideal Solutions
Solutions which do not obey Raoult’s law over all concentration ranges at constant temperature are
called non-ideal solutions.
Characteristic of nonideal solution
(i) PA  PAo X A + PB  PBo X B , P  PoAXA + PBo XB
(ii) Vmix  0 ,
(iii) Hmix  0
Types of Non-Ideal Solutions
1. Non ideal solutions showing +ve deviation
2. Non ideal solutions showing –ve deviation.

1. Non ideal solutions showing +ve deviation


Condition for forming non-ideal solution showing +ve deviation from Raoult’s law.
Tow liquids A and B on mixing form this type of solution when
1. A—B attractive force should be weaker than A—A and B—B attractive forces.
2. ‘A’ and ‘B’ have different shape, size and charater.
3. ‘A’ and ‘B’ escape easily showing higher vapour pressure than the expected value.
Characteristic of non-ideal solution showing +ve deviation
1. Do not obey Raoult’s law
2. Hmix > 0. (endothermic dissolution heat is absorbed.)
3. V mix > 0. (Volume is increased after dissolution)
4. pA > pA0 XA; pB > pBoXB ,  pA + pB > poAXA + pBoXB

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Example :
acetone + ethanol acetone + CS2 water + methanol;
water + ethanol; CCl4 + toluene; CCl4 + CHCl3; ac-
etone + benzene; CCl4 + CH3OH; cyclohexane + ethanol
Graphical representation of vapour of non-ideal solution showing +ve deviation

V.P.= max.
B.P. = min.
P>
PA +

Vapour pressure
PB

P
A >
P o
B
X
B

XA = 0 Mole fraction XA = 1
XB = 1 XB = 0

2. Non ideal solutions showing –ve deviation.


Condition for forming non-ideal solution showing +ve deviation from Raoult’s law.
Two liquids A and B on mixing form this type of solution when
1. A—B attractive force should be greater than A—A and B—B attractive forces.
2. ‘A’ and ‘B’ have different shape, size and character
3. Escaping tendency of both components ‘A’ and ‘B’ is lowered showing lower vapour pressure
than expected ideally.
Characteristic of non-ideal solution showing +ve deviation
1. Do not obey Raoult’s law.
2. Hmix < 0. (Exothermic dissolution; heat is evolved.)
3. Vmix < 0. (Volume is decreased during dissoluton)
4. pA < PA0 XA; pB < pB0XB,  pA + pB < poAXA + pBoXB
Example
acetone + aniline; CH3OH + CH3COOH;
chlorofrom + diethyl ether, acetic acid + pyridine;
chloroform + benzene H2O + HNO3;
water + HCl
Cl
CH 3
acetone + chloroform; Cl C H OC
CH 3
Cl

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Graphical representation of vapour of non-ideal solution showing +ve deviation

V.P.= min.

Vapour pressure
B.P. = max.

+P B
P < PA
o XA
P
<PA
A >P
PA
B o
X
B

XA = 0 Mole fraction XA = 1
XB = 1 XB = 0

(iii) Azeotropes
The non-ideal solution showing large deviations from Raoult’s law can not be purified by distillation. A
solution at certain composition which continues to boil at constant temperature without change in the
composition of the solution and its vapour is called an AZEOTROPE or constant boiling mixture.
Azeotropes are of two types:
1. Azeotropes with Max. vapour pressure and Min. BP : When liquid in a solution do
not have great chemical affinity for each other (+ve deviation from ideality) their higher escape tendencies
increase the vapour pressure much more than expected on the basis of Raoult’s law. In many cases, the
deviations are so extreme as to lead to a maximum in the curve. The point of maximum vapour pressure
means that the bp at this composition will be minimum and constant.
Example of Minimum Boiling Azeotrope
Components Boiling point (K)
A B Mass% of B A B Azeoterope
H2O C 2 H5 OH 95.57 373 351.3 351.10
H2O C3 H 7 OH 71.69 373 370.0 350.72
CHCl3 C 2 H5 OH 67.00 334 351.3 332.30

2. Azeotropes with Min. vapour pressure and Max. bp : When liquids in solution form
chemical bonds (–ve deviation from ideality), their escape tendencies and hence the vapour pressure
decreases than expected on the basis of Raoult’s law. In many cases, the maximum in the temperature
composition curve is obtained. The point of minimum vapour pressure in the curve means that the bp of
this composition will be max. and constant.
Examples of Max. Boiling Azeotrope
Components Boiling point (K)
A B Mass% of B A B Azeoterope
H2O HCl 20.3 373 188 383
H2O HNO3 58.0 373 359 393.5
H2O HClO 4 71.6 373 383 476

6. Colligative Properties

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The property of a solution which depends upon the fraction of solute particles and solvent particles and
not upon the chemical nature of solute is called a colligative property. Greater the no. of particles of
solute in solution, greater is the extent to which colligative property is affected.
Type of colligative properties
(i) Lowering of vapour pressure (ii) Elevation of Boiling point
(iii) Depression of Freezing point (iv) Osmotic Pressure

Factors that Affect the Colligative Property: The no. of solute particles in solution. To be more
accurate, the colligative property depends upon the fraction of solute and solvent particles in solution.
(1) Nature of the solvent
(2) Independent of the nature of the solute
(3) Extent of association and dissociation of solute particles in solution.
(i) Lowering of Vapour Pressure: Vapour pressure lowering of a solution has already been explained
under Raoult’ Law. It was derived that the relative lowering of vapour pressure is given by the equation
PAo – PA nB
o
 XB 
PA nA  n B

(ii) Elevation of Boiling Point: The boiling point of a liquid is the temperature at which its vapour
pressure becomes equal to the atmospheric pressure. When the atmospheric pressure is 1 atm, boiling
point is called the normal boiling point.

1 atm

en
t

olv
vapour pressure

e s
Pur ion
lut
So

Tb0 Tb
Temperture

Plot of variation of vapour pressure elevation of boiling point

The vapour pressure of a liquid decreases when a non-volatile solute is dissolved in it. The decreased
vapour-pressure means that the solution would have to be heated to a higher temperature so that its
vapour pressure becomes equal to the atmospheric pressure. In other words, the boiling point of the
solution Tb is higher than the boiling point of the pure solvent Tb0. The difference Tsb – Tb0 is called the
boiling point elevation and denoted by Tb.
Tb = Tb – Tb0 ......(1)
It is found that the elevation of boiling point is directly proportional to the number of moles of the solute
in a given amount of the solvent (m).
T  m  Tb = Kb.m ......(2)
where m is the molality of the solution and Kb is a constant for a given solvent known as boiling-point
elevation constant or molal boiling point elevation constant or ebullioscopic constant of solution.

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Molal Elevation Constant or Ebullioscopic Constant: When molality of the solution is 1m, (1
mole of the solute is dissolved in 1 kg of the solvent) the above equation reduces to
Tb  K b  1m  K b
This indicates that molal elevation constant of a liquid (Kb) is equal to elevation of boiling point when
molality of the solution is 1 m. the unit of Kb is Km–1. K (mol/kg)–1 = K kg mol–1.
Determination of Kb of solvent :

RTb2
Kb  .......(3)
1000L v
where R is molar gas constant, Tb is the boiling point of the solvent on Kelvin scale and Lv the latent
heat of vaporization of solvent in calories per gram.
2  (373) 2
For water Kb   0.515 K-kg/mol
1000  540
Illustration 9. Estimate the boiling point of a solution of 25.0g of urea NH 2CONH2 plus 25.0g of
thiourea NH2CSNH2 in 500g of chloroform, CHCl3. The boiling point of pure chloroform is
61.2°C, Kb of chloroform = 3.63 Km–1.
Mass of urea 25.0g
Solution: Moles of urea =   0.42mol
Molecular mass of urea 60g / mol
25.0
Moles of thiourea =  0.33mol  Total moles of solute = 0.42 + 0.33 = 075
76 g/mol
Moles of solute 0.75mol
Molality, m = Mass of solvent in kg  (500g /1000g)kg  1.50m
Tb = Tb – Tb0 = Kbm = 3.63 × 1.50 = 5.44K = 5.445°C
Tb = 5.445°C + Tb0     = 5.445°C + 61.2°C     = 66.645°C
(iii) Depression in Freezing Point: The freezing point of a liquid is the temperature at which it
begins to freeze and the crystallized solid and liquid are in equilibrium. At freezing point, the vapour
pressure of the solid is equal to the vapour pressure of the liquid. When a dilute solution is cooled to
freezing point, it is assumed that crystals of pure solvent always separate out first.

Solid solvent t
ve n
sol
on
u ti
sol
vapour pressure

Tf Tf0
Temperature
Plot of variation of vapour pressure of a solution
with temperature and depression in freezing point.

The vapour pressure of a liquid decreases when a non-volatile so lute is dissolved in it. Therefore,
a solid-liquid equilibrium exists only at a temperature lower than the freezing point of the pure solvent.
In other words, for a solid to have the same vapour pressure as that of the solution, the freezing point
should lower down. If Tf0 is the freezing point of the pure solvent and Tf that of the solution, the

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difference Tf0 – Tf is called the freezing point depression and denoted by Ts
Ts = Tf0 – Tf .......(1)
It is found that the depression in freezing point is directly proportional to the number of moles of the
solute in a solute given amount of the solvent.
Tf = Kfm .......(2)
where m is the molality of the solution and Kf is a constant for a given solvent known as molal depression
constant or cryoscopic constant.
Molal Depression Constant or Cryoscopic Constant: When molality of the solution is 1m,
(1 mole of the solute is dissolved in 1 kg of the solvent) the above equation reduces to
Tf = Kf × 1m = Kf
This indicates that molal depression constant of a liquid (Kf) is equal to depression of freezing point
when molality of the solution is 1 m. the unit of Kf is Km–1. K (mol/kg)–1 = K kg mol–1.
Determination of Kf of solvent
Kf is characteristic of a particular solvent and can be calculated from the thermodynamical relationship.
RTf2
Kf  ......(3)
1000L f
where Tf is the freezing point of solvent in absolute scale and Lf the latent heat of fusion in calories per
gram of the solvent. For water,
0.002  (273)2
Kf   1.86 K-kg/mole
80
Illustration 10. What is the percent by mass of iodine needed to reduce the freezing point of benzene
to 3.5°C? The freezing point and cryoscopic constant of pure benzene are 5.5°C and 5.12 K/
m respectively.
Solution: Tf = Tf0 – Tf = Kf . m
5.5°C – 3.5°C = 5.12 × m
2
m  0.39mmolal
5.12
 Mass of iodine needed for 1000g of benzene = m × molecular mass of iodine I2
= 0.39 mol/kg × 254 g/mol = 99.06 g/kg
 1000g + 99.06g solution contains 99.06g I2
99.06g  100
100g solution contains  9.01%
1099.06g

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(iv) Osmosis:
Spontaneous flow of solvent molecules through a semipermeable membrane from a pure solvent to the
solution (or from a dilute solution to a concentrated solution) is termed as osmosis.

Osmotic Semi
pressure permiable
membrane
Piston

Pure liquid
Solution
Solvent

Osmotic Pressure (): The hydrostatic pressure built up on the solution which just stops osmosis.
Alternatively, it may be defined as the pressure which must be applied to the concentrated solution in
order to stop osmosis.
For dilute solutions  = CRT = hg (hydrostatic pressure)
Where C is the total molar concentration of all the free species present in the solution, h is the height
developed by the column of the concentrated solution and  is the density of the solution in the column.
On the basis of osmotic pressure, the solutions can be classified in three classes.
(a) Hypertonic solution:When two solutions are being compared, then the solution with higher osmotic
pressure is termed as hypertonic.
(b) Hypotonic solution:When two solutions are being compared, then the solution with lower osmotic
pressure is termed as hypertonic.
(c) Isotonic solutions: Two solutions having same osmotic pressures at same temperature. (This implies
C1 = C2).
Note:-Osmotic pressures can be determined quite accurately, hence it is used in the determination molecular
weights of large proteins and similar substances.
Reverse Osmosis: If a pressure greater than the osmotic pressure is applied on the concentrated solution,
the solvent starts to flow from concentrated solution to dilute solution (or pure solvent). This is reverse
osmosis. One of its chief uses is desalination of sea water to get pure drinking water.

Illustration 11. Calculate osmotic pressure of 5% solution of cane sugar (sucrose) at 15ºC.
Solution: m = mol. mass of sucrose (C12H22O11) = 342
w = 5g V =- 100 mL = 0.1 litre
S = 0.082, T = (15 + 273) = 288 K
w
Applying the equation PV = ST,,
m
5 1
P= × = 0.082 × 288 = 3.453]
342 0. 1

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Illustration 12. Consider a vertical tube of corss-sectional area of 1cm 2. The bottom of the tube is
closed with a semipermeable membrane and 1 g glucose is placed in the tube. The closed end
of the tube is immersed in pure water. What will be the height of the liquid level in the tube
at equilibrium? The density of solution may be taken as 1g/cm 2. What is the osmotic pressure
at equilibrium at 25ºC? Assume negligible depth of immersion of tube.
Solution: Let height in tube = h cm
V = (h × 1) cm3  Cross-sectional area = 1cm2
V = nRT
 h 1  1
 ×   = × 0.0821 × 298
 1000  180
134.92
 = atm
h
 = h × d × g
134.92 h 1 9.8
= × 1 atm = 101.325 KPa
h 100 101.325
h = 375 cm = 3.75 m
 = h × d × g = 3.75 ×1 × 9.8 = 36.7 KPa
[Ans. 3.75 m; 36.7 KPa]
llustration 13. A 5% soltuion of cane sugar is isotonic with 0.877% soltuion of urea. Calculate the
molecular mass of urea if molecular mass of cansugar is 342.
Solution: Let the molecular mass of urea be m2
w1 5
Molarity of sugar = =
m1  V1 342  0.1
w2 0.877
Molarity of urea = m  V = m  0.1
2 2 2
For isotonic solutions,
w1 w2 5 0.877
m1  V1 = m 2  V2  =
342  0.1 m 2  0.1
0.877  342
m2 = = 59.987
5
7. Ab Vapour pressure lowering, boiling point elevation, freezing point depression and osmotic pressure are
colligative properties which depend upon the fraction of solute and solvent particles in solution and not
upon the chemical nature of the solute. If solute molecules dissociates in solution, there are more
particles in solution and therefore, lowering of vapour pressure shows an increased effect.
NaCl(s) Na +(aq) + Cl(aq)

If the solute molecules associates in solution, there are less particles in solution, and therefore lowering
of vapour pressure shows a decreased effect.
nAB (AB)n
2C 6 H5COOH (C6 H 5COOH)2

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The molecular mass of a solute is inversely proportional to its molality. If colligative


molality is 2 m, the calculated molecular mass is one-half of the actual molecular mass of the solute. If
colligative molality is 3 m, the calculated molecular mass is one third of the actual molecular mass of the
solute. The molecular mass of benzoic acid is 122 g/mol. But the molecular mass of benzoic acid
dissolved in benzene is found to be 244 g/mol by using a colligative property. Benzoic acid associates
to form a dimer and therefore its colligative molality is one-half of the molality of benzoic acid. As
molecular mass of a solute is inversely proportional to molality, the molecular mass of benzoic acid
determined using a colligative property is double the actual molecular mass of benzoic acid. We can
summarize the results as:
1. The extent of dissociation and colligative property. A solute dissociates completely
or partially in solution makes available more particles than would otherwise be present in solution and
therefore, a colligative property shows an increased effect. For example, molecular masses obtained
of strong acids, bases and salts are much less than their normal values. As an example, one particle of
potassium chloride on dissociation in water gives two particles, K+ and Cl– and therefore, the molecular
mass obtained by a colligative property is half of its normal molecular mass.
K  Cl(s)  nH 2 O  
 K (aq) 
 Cl(aq)
1 mol 1mol 1 mol

2. The extent of association and colligative property: A solute that associates in


solution provides less particles that would otherwise be present in solution and therefore, the colligative
property shows the decreased effect. For example, benzoic acid in benzene is found t o have
molecular mass which is just twice its normalmolecular mass.
It is found that compounds which are capable of forming hydrogen bonds, e.g., phenols, carboxylic
aids, alcohols: because of association show decreased effect of colligative property.
O H O
H5C6 C6H5
O H O
A dimer of benzoic acid

In 1886, Van’t Hoff, Jacobus Henricus (Dutch chemist, 1859,-1911) introduced a factor ‘i’ known as
Van’t Hoff factor to express the extent to association or dissociation of a solute in solution. It can be
calculated as:
number of solute particles actually present in solution
i=
number of solute particles dissolved
Observed colligativ e property observed molality normal molecular weight of solute
= = =
normal colligativ e property normal molality observed molecular weight of solute

The Van’t Hoff factor for a solute can be calculated by the following modified equations:
PA0  PA
(i) = i XB (ii) Tf = iKfm (iii) Tb = iKbm (iv)  = iCRT
PA0
where C is molarity of the solution.
Note: For non-electrolytes; i = 1
For electrolytes; i > 1 ( If solute particles undergo Dissociation in the solution)
i < 1 ( If solute particles undergo Association in the solution)

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Application of Van’t Hoff Factor:


i) Calculation of Degree of Dissociation of solute particles:
An nA
No. of moles dissolved 1 mol 0
No. of moles after dissociation 1– n
Total number of moles present in solution = (1 – ) + n
Moles of solute actually present in solution
Van’t Hoff factor, i 
Moles of solute dissolved
(1  )  n i 1
=  1  (n  1) or  
1 n 1
ii) Calculation of Degree of Association of solute particles: Let n moles of the solute,
A, associate to form (A)n. If  is the degree of association.
nA An
No. of moles dissolved 1 mol 0
No. of moles after dissociation 1– /n
Total number of moles present in solution = (1 – ) + /n
  1  i 1 n
i  1    1    Hence    (i  1) 
  n  1 1 n
1
n

Illustration 14. A solution is prepared by dissolving 26.3g of CdSO4 in 1000g water. The depression
in freezing point of solution was found to be 0.284K. Calculate the Van’t Hoff factor. The
cryoscopic constant of water is 1.86K kg solvent mol–1- solute.
Solution: Molecular mass CdSO4 = 112.4 +32 + 4 × 16 = 208.4 g/mol
Mass CdSO 4
Molality CdSO4 = Molecular mass CdSO  Mass solvent in kg
4

26.3g
= = 0.216m
 1000 
(208.4g / mol)   kg 
 1000 

f T 0.284K
Tf = iKfm or i  K m  1.86K / m  0.126m = 1.21
f

Illustration 15. Three particles of a solute, A, associate in benzene to form species A3. Calculate the
freezing point of 0.25 molal solution. The degree of association of solute A is found to be
0.80. the freezing point of benzene and its cryoscopic constant are 5.5°C and 5.12 Km –1
respectively.
Solution: 3A  A3
No. of moles dissolved 3 0
No. of moles after dissociation m(1–) m/3
Total moles present after dissociation
     2  3  2  0.8 
= m(1   )  m 3  m  1    3   m  1  3  = 0.25m   = 0.177m
     3 
0 –1
Tf = Kfm or Tf – Tf = 5.12 Km × 0.117 m = 0.6
Tf = Tf0 – 0.6°C = 5.5°C – 0.6°C = 4.9°C

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SOLVED PROBLEMS
SUBJECTIVE
Problem 1: Calculate the molecular weight of cellulose acetate if its 0.5% (wt./vol) solution in
acetone (sp. gr. = 0.9) shows an osmotic rise of 23 mm against pure acetone at 27°C.
Solution: 0.5% (wt. / vol) solution means 0.5 gm of cellulose acetate is dissolved in 100 ml solution.
Osmotic pressure = 23 mm of pure acetone
2.3  0.9
 = 2.3 Cm of pure acetone = cm of Hg = 0.1522 cm of Hg
13.6
0.1522
 = atm = 0.002 atm
76
0.5
Let the molecular weight of the cellulose acetate be M  ncellulose acetate =
M
Volume = v = 100 ml = 0.1 lit
R = 0.082 lit atm mol–1 K–1, T = ( 27 + 273) = 300 K
n 0.5 1
= RT  0.002 =   0.0821  300  M = 61575
v M 0.1

Problem 2: 1kg of an aqueous solution of Sucrose is cooled and maintained at –4°C. How much
ice will be separated out if the molality of the solution is 0.75? Kf (H2O) = 1.86 Kg mol–1K.
Solution: Since molality of solution is .75 ,
hence .75 moles of sucrose are present in 1000 g of solvent (i.e. water)
 msolution = mwater + msucrose = 1000 + .75 × 342 = 1256.5 gm
256.5
 msucrose (in kg) = × 1000 = 204.14 gm ,. mwatrer = 1000 – 204.14 = 795.86 gm
1256.5
204.14 / 342
Tf = Kf × m  4 = 1.86 ×  w = 277.15
W / 1000
 amount of ice = 795.86 – 277.15 = 518.31 gm

Problem 3: River water is found to contain 11.7% NaCl, 9.5% MgCl2, and 8.4%. NaHCO3 by
weight of solution. Calculate its normal boiling point assuming 90% ionization of NaCl,
70% ionization of MgCl2 and 50% ionization of NaHCO3 (Kb for water = 0.52)
11.7 9.5 8.4
Solution: nNaCl = = 0.2, n MgCl2 = = 0.1, n NaHCO3 = = 0.1
58.5 95 84
iNaCl = 1+  = 1+ 0.9 = 1.9, i MgCl2 = 1 + 2 = 1+ 0.7  2 = 2.4 ,
i NaHCO3 = 1+ 2 = 1+ 0.5  2 = 2.0
Weight of solvent = 100 – (11.7 + 9.5 + 8.4) = 70.4 g
(i NaCl  n NaCl  iMgCl2  n MgCl2  i NaHCO3  n NaHCO3 )  K b  1000
Tb = Weight of solvent

(1.9  0.2  2.4  0.1  2  0.1)  0.52  1000


= = 5.94°C
70.4
 Boiling point of solution = 100 + 5.94 = 105.95°C

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Problem 4: An aqueous solution containing 288 gm of a non–volalite compound having the


stochiometric composition CxH2xOx in 90 gm water boils at 101.24°C at 1.00 atmospheric
pressure . What is the molecular formula?
Kb(H2O) = 0.512 K mol–1 kg Tb (H2O) = 100°C
Solution: Elevation in B.P. = 101.24 – 100 = 1.24°C
288 1000
Tb = Kb  i  molality  1.24 = 0.512   ( i = 1)
m 90
 m = 1321.2 gm mol–1
molar mass of CxH2xOx = 12x + 1  2x + 16x = 30x
 30x = 1321.2  x = 44 Hence the molecular formula is = C44H88O44

Problem 5: 30 ml of CH 3 OH (d = 0.7980 gm Cm –3 ) and 70 ml of H 2 O (d = 0.9984 gm


cm–3) are mixed at 25°C to form a solution of density 0.9575 gm cm –3. Calculate the freezing
point of the solution. Kf (H2O) is 1.86 Kg mol–1 K. Also calculate its molarity
Solution: Weight of CH3OH (w1) = 30cm3  0.7980 gm/cm3 = 23.94 gm
Weight of solvent (H2O) (w2) = 70 cm3  0.9984 gm cm3 = 69.888 gm
23.94 1000
m=  = 10.7046 molal
32 69.88
Tf = Kf  i  molality, (for CH3OH, i = 1)
Tf = 1.86  10.7046°C = 19.91°C
Freezing point of the solution = 0– 19.91°C = –19.91°C
Weight of solution = weight of solute + weight of solvent = 23.94 + 69.888 = 93.828 gm
wt. of the solution 93.828
volume of the solution = density of the solution = = 97.99 ml
0.95751
23.94 1000
M (molarity) =  mol lit–1 = 7.63 M
32 97.99

Problem 6: A complex is represented as CoCl3.xNH3. Its 0.1 m solution in aqueous solution shows
Tf = 0.558° Kf(H2O) = 1.86 mol–1 K and assume 100% ionization and co–ordination number
of Co(III) is six . What is the complex?
Solution: Tf = i  Kf  m, 0.558 = 1.86  0.1  i
0.558
i= =3
0.186
or, i  3 indicates that complex ionize to form three ions since coordination number is 6 hence x = 5
i.e., CoCl3.5NH3  [Co(NH3)5Cl]++ + 2Cl–
 
1 Cation 2 anions
So, the complex is [Co(NH3)5Cl]Cl2

Problem 7: A solution comprising 0.1 mol of naphthalene and 0.9 mol of benzene is cooled until
some benzene freezes out. The solution is then decanted off from the solid and warmed to 353
K, where its vapour pressure is found to be 670 torr. The freezing and normal boiling point of
benzene are 278.5 K and 353 K, respectively. Calculate the temperature to which the solution
was cooled originally and the amount of benzene that must have frozen out. Assume conditions
of ideal solution. Kf for benzene = 5K kg mole–1.
Solution: Molality of the resulting solution (i.e. after the benzene freezes out) can be determined on the
basis Raoult’s law.

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(760  670)
X naph  1000 760
m  = 1.72 mol kg–1.
X benzene  78 0.88  78

 1000 
Weight of benzene in the resulting solution =   0.1 = 58.1 g
 1.72 
Amount of benzene frozen = 0.9  78 – 58.1 = 12.1 g
Tf = Kfm = 5  1.72 = 8.60 K
Hence the temp to which the solution was cooled = 278.5 – 8.60 = 269.9 K

Problem 8: Find Ka, the ionization constant of tartaric acid if a 0.100 molal aqueous solution of
tartaric acid freezes at –0.205°C. Assume that only the first ionization is of importance and
that 0.1 m = 0.1M. Kf = 1.86 kg mol–1 K.
Solution: Assuming that the tartaric acid be a monobasic as AH. It ionizes as
AH A + H+
Initially conc. C 0 0
Conc. after dissociationC(1–) C C,
C(1  )  C  C C(1  )
Here, i = , where  = degree of dissociation = = 1+
C C
Molal concentration = 0.1
Tf = Kf Cm  i  0.205 = 1.86  0.1  (1+)   = 0.1
[A  ][H  ] C  C  2 C  0.1
2
 0.1
Ka = = C(1  )  1   Ka = = 1.11  10–3
[AH] 1  0.1
 Ka = 1.11  10–3

Problem 9: The freezing point depression of a 0.109 M aq. solution of formic acid is –0.21°C.
Calculate the equilibrium constant for the reaction,
HCOOH (aq) H+ (aq) + HCOO– (aq)
Kf for water = 1.86 kg mol–1 K
Solution: HCOOH (aq) H+(aq) + HCOO– (aq)
Initially moles C 0 0
Moles after dissociation (1–) C C C
(1   )  C    C    C
i = 1 + ,
1 C
Tf = Kf  i  Cm
0.21 = 1.86  (1+)  0.109 ( for dilute solution molality molarity)
0.21
 1+ = = 1.0358   = 0.0358 = 0.036
1.86  0.109
2
[H  ][HCOO  ] C 0.109  (0.036) 2
Ka = = = 1.41 × 10–5
[HCOOH] 1    = 0.964
Problem 10: The freezing point of a solution of acetic acid (mole fraction is 0.02) in benzene
277.4 K. Acetic acid exists partly as a dimer 2A A2. Calculate equilibrium constant for
dimerisation. Freezing point of benzene is 278.4 k and (Kf for benzene is 5)
Solution: 2A A2
1 0 initially moles
1– /2 moles after dimer is formed
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1      2
i= = 1 – /2
1
XA = 0.02, XB = 0.98
xA 1000 0.02 1000
Molality of A in B = m  X =  = 0.262 mol kg–1 of Benzene
B B 78 0.98
Since, Tf = Kf  i  molality 278.4–277.4 = 5  i  0.262
1
or, 1 = 5  i  0.262 , i = = 0.763, 1– /2 = 0.763   = 0.47
5  0.262
Hence the molality of A after dimer is formed = (1–)  initial molality
= (1 – 0.48)  initial molality = 0.52  0.262
Molality of A2 after dimer is formed
 0.48
=  molality =  0.262 = 0.24  0.26 = 0.06288
2 2
A 
2 0.06288
The equilibrium constant Keq = 2 = (0.13624) 2 = 3.39 kg mol–1
 A

OBJECTIVE
Problem 1: A weak electrolyte, AB, is 5% dissociated in aqueous solution. What is the freezing point of a
0.100 molal aqueous solution of AB? Kf for water is 1.86 deg/molal.
(A) –3.8°C (B) –0.1953°C (C) –1.7°C (D) – 0.78°C
Solution: Ans (b)
ForAB, n = 2  i = 1 + (2–1)  = 1 +  = 1.05
Tf = i × Xf × m = 1.05 × 1.86 × .1 = .1953  Tf = – .1953ºC
Problem 2: Calculate the boiling point of a one molar aqueous so lution
(density = 1.04 g mL–1) of potassium chloride, Kb for water = 0.52 kg mol–1. Atomic masses of K =
39, Cl = 35.5
(A) 107.28°C (B) 103.68°C (C) 101.078°C (D) None of these
Solution: Ans. (c)
1000  1
m= =- 1.036
1000  1.04  1 74.5
Tb = 1 × Xb × m  Tb = 2 × 0.52 × 1.036 = 1.078  Tb = 101.078ºC
(KCl is an electrolyte having n = 2,  = 1 (if not given)
Problem 3: The vapour pressure of a solvent decreased by 10 mm Hg when a non volatile solute was
added to the solvent. The mole fraction of solute in solution is 0.2, what would be mole fraction of the
solvent if decrease in vapour pressure is 20 mm of Hg.
(A) 0.8 (B) 0.6 (C) 0.4 (D) 0.2
Solution: Ans.: (b)
P – P s = P o  XB
o
10 = Po  0.2
o
Again, 20 = P  XB Hence, n = 0.4,
so, mole fraction of solvent = 1 – 0.4 = 0.6
Problem 4: The molal freezing point constant for water is 1.86 K. molarlity–1. If 34.2 g of cane sugar
(C12H22O11) are dissolved in 1000g of water, the solution will freeze at
(A) –1.86°C (B) 1.86°C (C) –3.92°C (D) 2.42°C
Solution: Ans.: (a)

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1000  K f  w 1000  1.86  34.2


Tf =  = 1.86° Tf = 0 – 1.86 = –1.86° C
MW 100  342
Problem 5: 20 g of a binary electrolyte (mol.wt. = 100) are dissolved in 500 g of water. The freezing point
of the solution is –0.74°C, Kf = 1.86 K.molality–1. The degree of ionisation of the electrolyte is
(A) 50% (B) 75% (C) 100% (D) 0
Solution: Ans.: (d)
20 / 100
Tf = i ×Xf × m  .74 = (1 + ) × 1+=1 =0
500 / 1000
Problem 6: Y g of non - volatile organic substance of molecular mass M is dissolved in 250 g benzene.
Molal elevation constant of benzene is Kb. Elevation in its boiling point is given by
M 4K b Y KbY KbY
(A) (B) (C) (D)
KbY M 4M M

1000  K b  Y 4K b Y
Solution: Ans.: (b) T = =
250  M M
Problem 7: The values of observed and calculated molecular weights of silver nitrate are 92.64 and 170
respectively. The degree of dissociation of silver nitrate is
(A) 60% (B) 83.5% (C) 46.7% (D) 60.23%
Normal mol.wt 170
Solution: Ans.:(b) i for AgNO3 = =1+= –1 = 0.835 = 83.5 %
Observed mol.wt. 92.64
Problem 8: At 40°C, the vapour pressures in torr, of methyl alcohol - ethy alcohol solution is represented
by the equation. P = 119XA + 135 where XA is mole fraction of methyl alcohol, then the value of
PA
Lim
X A 1 X A is
(A) 254 torr (B) 135 torr (C) 119 torr (D) 140 torr
PA
Ans.: (a) P = 119XA + 135; Lim
Solution: X A 1 X A = 119 + 135 = 254

Problem 9: The amount of ice that will separate on cooling a solution containing 50g of ethylene glycol in
200g water to –9.3°C is : [Kf = 1.86 K molality–1]
(A) 38.71 g (B) 38.71 mg (C) 42 g (D) 42 mg
Solution: Ans.: (a)
1000  K f  w 1000  1.86  50
T =  9.3 =   W = 161.29
WM 62  W
 Ice separated = 200 – 161.29 = 38.71 g
Problem 10: The freezing point of aqueous solution contains 5% by mass urea, 1.0% by mass KCl and
10% by mass of glucose is : ( K f H2 O = 1.86K molality–1)
(A) 290.2 K (B) 285.5 K (C) 269.9 K (D) 250 K
Solution: Ans.: (c)
10 5 1
nglucose = , nurea = , nKCl = 2 , (electrolyte, i = 2)
180 60 74.5

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 10 5 2 
   
 180 10 74.5 
 Tf = Kf × m = 1.86 × = 3.7
84 / 1000
 Tf = 273 – 3.7 = 269.3 K

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EXERCISE I
Raoult’s law

Q.1 At 25°C, the vapour pressure of methyl alcohol is 96.0 torr. What is the mole fraction of CH3OH in a
solution in which the (partial) vapor pressure of CH3OH is 23.0 torr at 25°C?

Q.2 The vapour pressure of pure liquid solvent A is 0.80 atm. When a nonvolatile substance B is added to
the solvent its vapour pressure drops to 0.60 atm. What is the mole fraction of component B in the
solution?

Q.3 The vapour pressure of pure water at 26°C is 25.21 torr. What is the vapour pressure of a solution
which contains 20.0 glucose, C6H12O6, in 70 g water?

Q.4 The vapour pressure of pure water at 25°C is 23.76 torr. The vapour pressure of a solution containing
5.40 g of a nonvolatile substance in 90.0 g water is 23.32 torr. Compute the molecular weight of the
solute.

Raoult’s law in combinaton with Dalton’s law of P.P. and V.P. lowering

Q.5 The vapour pressure of ethanol and methanol are 44.5 mm and 88.7 mm Hg respectively. An ideal
solution is prepared at the same temperature by mixing 60 g of ethanol with 40 g of methanol. Calculate
total vapour pressure of the solution.

Q.6 Calculate the mole fraction of toluene in the vapour phase which is in equilibrium with a solution of
benzene and toluene having a mole fraction of toluene 0.50. The vapour pressure of pure benzene is
119 torr; that of toluene is 37 torr at the same temperature.

Q.7 What is the composition of the vapour which is in equilibrium at 30°C with a benzene-toluene solution
with a mole fraction of benzene of 0.40? With a mole fraction of benzene of 0.60?
Pb =119 torr and Pt = 37 torr

Q.8 At 90°C, the vapour pressure of toluene is 400 torr and that of -xylene is 150 torr. What is the
composition of the liquid mixture that boils at 90°C, when the pressure is 0.50 atm? What is the
composition of vapour produced?

Q.9 Two liquids A and B form an ideal solution at temperature T. When the total vapour pressure above the
solution is 400 torr, the mole fraction of A in the vapour phase is 0.40 and in the liquid phase 0.75.
What are the vapour pressure of pure A and pure B at temperature T?

Q.10 Calculate the relative lowering in vapour pressure if 100 g of a nonvolatile solute (mol.wt.100) are
dissolved in 432 g water.

Q.11 What weight of the nonvolatile solute, urea needs to be dissolved in 100 g of water, in order to
decrease the vapour pressure of water by 25%? What will be the molality of the solution?

Q.12 The vapour pressure of an aqueous solution of glucose is 750 mm Hg at 373 K. Calculate molality and
mole fraction of solute.

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Q.13 The vapour pressure of pure benzene at 25° C is 639.7 mm of Hg and the vapour pressure of a
solution of a solute in C6H6 at the same temperature is 631.7 mm of Hg. Calculate molality of solution.

Q.14 The vapour pressure of pure benzene at a certain temperature is 640 mm of Hg. A nonvolatile
nonelectrolyte solid weighing 2.175 g is added to 39.0 of benzene. The vapour pressure of the solution
is 600 mm of Hg. What is molecular weight of solid substance?

Q.15 The vapour pressure of water is 17.54 mm Hg at 293 K. Calculate vapour pressure of 0.5 molal
solution of a solute in it.

Q.16 Benzene and toluene form two ideal solution A and B at 313 K. Solution A (total pressure PA) contains
equal mole of toluene and benzene. Solution B contains equal masses of both (total pressure PB). The
vapour pressure of benzene and toluene are 160 and 60 mm Hg respectively at 313 K. Calculate the
value of PA/PB.

Boiling point elevation and freezing point depression

Q.17 When 10.6 g of a nonvolatile substance is dissolved in 740 g of ether, its boiling point is raised 0.284°C.
What is the molecular weight of the substance? Molal boiling point constant for ether is 2.11°C·kg/mol.

Q.18 A solution containing 3.24 of a nonvolatile nonelectrolyte and 200 g of water boils at 100.130°C at
1atm. What is the molecular weight of the solute? (Kb for water 0.513°C/m)

Q.19 The molecular weight of an organic compound is 58.0 g/mol. Compute the boiling point of a solution
containing 24.0 g of the solute and 600 g of water, when the barometric pressure is such that pure
water boils at 99.725°C.

Q.20 An aqueous solution of a nonvolatile solute boils at 100.17°C. At what temperature will this solution
freeze? [Kf for water 1.86°C/m ]

Q.21 Pure benzene freeze at 5.45°C. A solution containing 7.24 g of C2H2Cl4 in 115.3 g of benzene was
observed to freeze at 3.55°C. What is the molal freezing point constant of benzene?

Q.22 A solution containing 6.35 g of a nonelectrolyte dissolved in 500 g of water freezes at – 0.465°C.
Determine the molecular weight of the solute.

Q.23 The freezing point of a solution containing 2.40 g of a compound in 60.0 g of benzene is 0.10°C lower
than that of pure benzene. What is the molecular weight of the compound? (Kf is 5.12°C/m for benzene)

Q.24 The elements X and Y form compounds having molecular formula XY2 and XY4. When dissolved in 20
gm of benzene, 1 gm XY2 lowers the freezing point by 2.3°, whereas 1 gm of XY4 lowers the freezing
point by 1.3°C. The molal depression constant for benzene is 5.1. Calculate the atomic masses of X and
Y.

Q.25 Calculate the molal elevation constant, Kb for water and the boiling of 0.1 molal urea solution. Latent
heat of vaporisation of water is 9.72 kcal mol–1 at 373.15 K.

Q.26 Calculate the amount of ice that will separate out of cooling a solution containing 50g of ethylene glycol
in 200 g water to –9.3°C. (Kf for water = 1.86 K mol1 kg)

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Q.27 A solution of 0.643 g of an organic compound in 50ml of benzene (density ; 0.879 g/ml) lowers its
freezing point from 5.51°C to 5.03°C. If Kf for benzene is 5.12 K, calculate the molecular weight of
the compound.

Q.28 The cryoscopic constant for acetic acid is 3.6 K kg/mol. A solution of 1 g of a hydrocarbon in 100 g of
acetic acid freezes at 16.14°C instead of the usual 16.60°C. The hydrocarbon contains 92.3% carbon.
What is the molecular formula?

Osmotic pressure

Q.29 Find the freezing point of a glucose solution whose osmotic pressure at 25oC is found to be 30 atm.
Kf(water) = 1.86kg.mol1.K.

Q.30 At 300 K, two solutions of glucose in water of concentration 0.01 M and 0.001 M are separated by semipermeable
membrane. Pressure needs to be applied on which solution, to prevent osmosis? Calculate the magnitude of this
applied pressure.

Q.31 At 10oC, the osmotic pressure of urea solution is 500 mm. The solution is diluted and the temperature is raised to
25°C, when the osmotic pressure is found to be105.3 mm. Determine extent of dilution.

Q.32 The osmotic pressure of blood is 7.65 atm at 37°C. How much glucose should be used per L for an intravenous
injection that is to have the same osmotic pressure as blood?

Q.33 What would be the osmotic pressure at 17°C of an aqueous solution containing 1.75 g of sucrose (C12H22O11)
per 150 cm3 of solution?

Q.34 A 250 mL water solution containing 48.0 g of sucrose, C12H22O11, at 300 K is separated from pure water by
means of a semipermeable membrane. What pressure must be applied above the solution in order to just prevent
osmosis?

Q.35 A solution of crab hemocyanin, a pigmented protein extracted from crabs, was prepared by dissolving 0.750 g in
125 cm3 of an aqueous medium. At 4°C an osmotic pressure rise of 2.6 mm of the solution was observed. The
solution had a density of 1.00 g/cm3. Determine the molecular weight of the protein.

Q.36 The osmotic pressure of a solution of a synthetic polyisobutylene in benzene was determined at 25°C. A sample
containing 0.20 g of solute/100 cm3 of solution developed a rise of 2.4 mm at osmotic equilibrium. The density of
the solution was 0.88 g/cm3. What is the molecular weight of the polyisobutylene?

Q.37 A 5% solution (w/v) of cane-sugar (Mol. weight = 342) is isotonic with 0.877%(w/v) of urea solution. Find
molecular weight of urea.

Q.38 10 gm of solute A and 20 gm of solute B are both dissolved in 500 ml water. The solution has the same
osmotic pressure as 6.67 gm of A and 30 gm of B dissolved in the same amount of water at the same
temperature. What is the ratio of molar masses of A and B?

Van’t Hoff factor & colligative properties

Q.39 A storage battery contains a solution of H2SO4 38% by weight. What will be the Van't Hoff factor if the
Tf(experiment) in 29.08. [Given Kf = 1.86 mol–1 Kg]
Q.40 A certain mass of a substance, when dissolved in 100 g C6H6, lowers the freezing point by 1.28°C.
The same mass of solute dissolved in 100g water lowers the freezing point by 1.40°C. If the substance
has normal molecular weight in benzene and is completely ionized in water, into how many ions does it
dissociate in water? Kf for H2O and C6H6 are 1.86 and 5.12K kg mol1.
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Q.41 2.0 g of benzoic acid dissolved in 25.0g of benzene shows a depression in freezing point equal to 1.62K.
Molal depression constant (Kf) of benzene is 4.9 K.kg.mol1. What is the percentage association of the
acid?

Q.42 A decimolar solution of potassium ferrocyanide is 50% dissociated at 300K. Calculate the osmotic
pressure of the solution.(R=8.314 JK1 mol1)

Q.43 The freezing point of a solution containing 0.2 g of acetic acid in 20.0g of benzene is lowered by
0.45°C. Calculate the degree of association of acetic acid in benzene. (Kf for benzene = 5.12 K mol
1 kg)

Q.44 0.85 % aqueous solution of NaNO3 is apparently 90% dissociated at 27°C. Calculate its osmotic
pressure. (R= 0.082 l atm K1 mol1 )

Q.45 A 1.2% solution (w/v) of NaCl is isotonic with 7.2% solution (w/v) of glucose. Calculate degree of
ionization and Van’t Hoff factor of NaCl.

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PROFICIENCY TEST
Q.1 Fill in the blanks with appropriate items :
1. Lowering of vapour pressure is ______ to the mole fraction of the solute.

2. The ratio of the value of any colligative property for NaCl solution to that of equimolal solution of sugar
is nearly______.

3. Semipermeable membrane allows the passage of ________through it.

4. A binary solution which has same composition in liquid as well as vapour phase is called______.

5. The molal elevation constant of solvent is also called _____.

6. The 0.1 M aqueous solution of acetic acid has boiling point _______ than that of 0.1 M aqueous
solution of KCl.

7. For ideal solutions, the plot of total vapour pressure v/s composition is ______.

8. A solution of CHCl3 and acetone shows________deviation.

9. Gases which react with water are generally _________ soluble in it.

10. Assuming complete dissociation, Van’t Hoff’s factor for Na2SO4 is equal to ________.

11. The osmotic pressure of a solution _______ with increase in temperature.

12. Water will boil at 101.5°C at pressure of _______76 cm of Hg.

13. Vant’s Hoff’s factor ‘i’ for dimerisation of CH3COOH in benzene is_________.

nB
14. = RT is known as_________.
V

15. The molal elevation constant is the ratio of the elevation in boiling point to _________.

Q.2 True or False Statements :


1. Relative lowering of vapour pressure is a colligative property.

2. Lowering of vapour pressure of a solution is equal to the mole fraction of the non-volatile solute present in it.

3. The components of an azeotropic solution can be separated by simple distillation.

4. Vapour pressure of a liquid depends on the size of the vessel.


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5. Addition of non-volatile solute to water always lowers it vapour pressure.

6. Reverse osmosis is generally used to make saline water fit for domestic use.

7. A 6% solution of NaCl should be isotonic with 6% solution of sucrose.

8. A real solution obeys Raoult’s law.

9. Boiling point is a characteristic temperature at which vapour pressure of the liquid becomes higher than
the atmospheric pressure.

10. Molal depression constant is independent of the nature of solute as well as that of solvent.

11. The real solutions can exhibit ideal behaviour at high concentrations.

12. The osmotic pressure decreases on addition of solvent to the solution.

13. For urea the value of Vant’s Hoff’s factor ‘i’ is equal to 1.

14. The unit of kb is kg K–1 mol–1.

15. 0.1 M solution of urea would be hypotonic with 0.1 M solution of NaCl.

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EXERCISE II

Single correct
Q.1 For an ideal binary liquid solution with PA > PB , which relation between XA (mole fraction of A in
liquid phase) and YA(mole fraction of A in vapour phase) is correct?
(A) YA < YB (B) XA > XB
YA X A YA X A
(C) Y  X (D) Y  X
B B B B

Q.2 Mole fraction of A vapours above the solution in mixture of A and B (XA = 0.4) will be
[Given : PA = 100 mm Hg and PB = 200 mm Hg]
(A) 0.4 (B) 0.8 (C) 0.25 (D) none of these

Q.3 The exact mathematical expression of Raoult’s law is


P 0  Ps n P 0  Ps N
(A) 0
 (B) 0

P N P n

P 0  Ps n P 0  Ps
(C)  (D) =n×N
Ps N P0

Q.4 A mixture contains 1 mole of volatile liquid A ( PA =100 mm Hg) and 3 moles of volatille liquid
B ( PB = 80 mm Hg). If solution behaves ideally, the total vapour pressure of the distillate is
(A) 85 mm Hg (B) 85.88 mm Hg (C) 90 mm Hg (D) 92 mm Hg

Q.5 Which of the following aqueous solution will show maximum vapour pressure at 300 K?
(A) 1 M NaCl (B) 1 M CaCl2 (C) 1 M AlCl3 (D) 1 M C12H22O11

Q.6 The Van’t Hoff factor for a dilute aqueous solution of glucose is
(A) zero (B) 1.0 (C) 1.5 (D) 2.0

Q.7 The correct relationship between the boiling points of very dilute solution oif AlCl3 (T1K) and
CaCl2 (T2K) having the same molar concentration is
(A) T1 = T2 (B) T1 > T2 (C) T2 > T1 (D) T2  T1

Q.8 A 0.001 molal solution of a complex [MA8] in water has the freezing point of –0.0054°C. Assuming
100% ionization of the complex salt and Kf for H2O = 1.86 km–1, write the correct representation for
the complex
(A) [MA8] (B) [MA7]A (C) [MA6]A2 (D) [MA5]A3

Q.9 The vapour pressure of a solution of a non-volatile electrolyte B in a solvent A is 95% of the vapour
pressure of the solvent at the same temperature. If the molecular weight of the solvent is 0.3 times the
molecular weight of solute, the weight ratio of the solvent and solute are
(A) 0.15 (B) 5.7 (C) 0.2 (D) 4.0

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Q.10 At a given temperature, total vapour pressure in Torr of a mixture of volatile components A and B is
given by
PTotal = 120 – 75 XB
hence, vapour pressure of pure A and B respectively (in Torr) are
(A) 120, 75 (B) 120, 195 (C) 120, 45 (D) 75, 45

Q.11 Assuming each salt to be 90 % dissociated, which of the following will have highest boiling point?
(A) Decimolar Al2(SO4)3
(B) Decimolar BaCl2
(C) Decimolar Na2SO4
(D) A solution obtained by mixing equal volumes of (B) and (C)

Q.12 The vapour pressure of a solvent decreased by 10 mm of Hg when a non-volatile solute was added to
the solvent. The mole fraction of solute in solution is 0.2, what would be mole fraction of the solvent if
decrease in vapour pressure is 20 mm of Hg
(A) 0.2 (B) 0.4 (C) 0.6 (D) 0.8

Q.13 Elevation of boiling point of 1 molar aqueous glucose solution (density = 1.2 g/ml) is
(A) Kb (B) 1.20 Kb (C) 1.02 Kb (D) 0.98 Kb

Q.14 What will be the molecular weight of CaCl2 determined in its aq. solution experimentally from depression
of freezing point?
(A) 111 (B) < 111 (C) > 111 (D) data insufficient

Q.15 1.0 molal aqueous solution of an electrolyte A2B3 is 60% ionised. The boiling point of the solution at 1
1
atm is ( K b( H 2O)  0.52 K kg mol )
(A) 274.76 K (B) 377 K (C) 376.4 K (D) 374.76 K

Q.16 Which of the following plots represents an ideal binary mixture?


(A) Plot of Ptotal v/s 1/XB is linear (XB = mole fraction of 'B' in liquid phase).
(B) Plot of Ptotal v/s YA is linear (YB = mole fraction of 'A' in vapour phase)
1
(C) Plot of P v/s YA is linear
total

1
(D) Plot of P v/s YB is non linear
total

Q.17 Pressure over ideal binary liquid mixture containing 10 moles each of liquid A and B is gradually
decreased isothermally. If PAo =200 mm Hg and PBo =100 mm Hg, find the pressure at which half of the
liquid is converted into vapour.
(A) 150 mm Hg (B) 166.5 mm Hg (C) 133 mm Hg (D) 141.4 mm Hg

Q.18 Two liquids A & B form an ideal solution. What is the vapour pressure of solution containing 2 moles
of A and 3 moles of B at 300 K? [Given : At 300 K, Vapour pr. of pure liquid A ( PAo ) = 100 torr,,
Vapour pr. of pure liquid B ( PBo ) = 300 torr ]

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(A) 200 torr (B) 140 torr (C) 180 torr (D) None of these
Q.19 Which of the following represents correctly the changes in thermodynamic properties during the formation
of 1 mol of an ideal binary solution.

(A) (B)

(C) (D)

Q.20 FeCl3 on reaction with K4[Fe(CN)6] in aqueous solution gives blue


colour. These are separated by a semipermeable membrane AB as
shown. Due to osmosis there is
(A) blue colour formation in side X.

(B) blue colour formation in side Y.


(C) blue colour formation in both of the sides X and Y.
(D) no blue colour formation.

Q.21 A liquid mixture having composition corresponding to point z in the


figure shown is subjected to distillation at constant pressure. Which of
the following statement is correct about the process
(A) The composition of distillate differs from the mixture
(B) The boiling point goes on changing
(C) The mixture has highest vapour pressure than for any other
composition.
(D) Composition of an azeotrope alters on changing the external pressure.

Q.22 The vapour pressure of a saturated solution of sparingly soluble salt (XCl3) was 17.20 mm Hg at
27°C. If the vapour pressure of pure H2O is 17.25 mm Hg at 300 K, what is the solubility of
sparingly soluble salt XCl3 in mole/Litre.
(A) 4.04 × 10–2 (B) 8.08 ×10–2 (C) 2.02 × 10–2 (D) 4.04 × 10–3

Q.23 At 300 K, the vapour pressure of an ideal solution containing 3 mole of A and 2 mole of B is 600 torr.
At the same temperature, if 1.5 mole of A & 0.5 mole of C (non-volatile) are added to this solution the
vapour pressure of solution increases by 30 torr. What is the value of PBo ?
(A) 940 (B) 405 (C) 90 (D) none of these

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Q.24 The following graph represents variation of boiling point with composition of liquid and vapours of
binary liquid mixture. The graph is plotted at constant pressure.
Which of the following statement(s) is incorrect. Here X & Y stands for mole fraction in liquid and
vapour phase respectively

(A) Xbenzene = 0.5 and Ytoluene = 0.2


(B) Xtoluene = 0.3 and Ybenzene = 0.6
(C) Xbenzene = 0.3 and Ytoluene = 0.4
(D) if Xbenzene = 0.7 than Ytoluene < 0.3

Q.25 The freezing point depression of a 0.1 M aq. solution of weak acid (HX) is –0.20°C.
What is the value of equilibrium constant for the reaction?
HX (aq) l H +(aq) + X¯ (aq)
[Given : Kf for water = 1.8 kg mol–1 K. & Molality = Molarity ]
(A) 1.46×10–4 (B) 1.35 × 10–3 (C) 1.21 × 10–2 (D) 1.35 × 10–4

Q.26 The van’t Hoff factor for 0.1 M Ba(NO3)2 solution is 2.74. The degree of dissociation is
(A) 91.3% (B) 87% (C) 100% (D) 74%

Q.27 The vapour pressure of an aqueous solution is found to be 750 torr at certain temperature 'T'. If 'T' is
the temperature at which pure water boils under atmospheric pressure and same solution show elevation
in boiling point Tb = 1.04 K, find the atmospheric pressure (Kb = 0.52 K kg mol–1 )
(A) 777 (B) 779 (C) 782 (D) 746
More than one may be correct
Q.28 Acetone and carbon disulphide form binary liquid solution showing positive deviation from Raoult law.
The normal boiling point (Tb) of pure acetone is less than that of pure CS2. Pick out the incorrect
statements among the following.
(A) Boiling temperature of mixture is always less than boiling temperature of acetone.
(B) Boiling temperature of Azeotropic mixture is always less than boiling temperature of pure CS2.
(C) When a small amount of CS2 (less volatile component) is added to excess of acetone boiling point
of resulting mixture increases.
(D) A mixture of CS2 and CH3COCH3 can be completely separated by simple fractional distillation.
Assertion & Reasoning type questions
Q.29 Statement-1 : The freezing of water is an endothermic process.
Statement-2 : Heat must be removed from the water to make it freeze.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.

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Q.30 Statement-1 : Additon of ethylene glycol (non-volatile) to water lowers the freezing point of
water hence used as antifreeze.
Statement-2 : Addition of any substance to water lowers its freezings point of water.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.

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EXERCISE III

Q.1 The van’t Hoff factor for 0.1 M Ba(NO3)2 solution is 2.74. The degree of dissociation is
(A) 91.3% (B) 87% (C) 100% (D) 74% [JEE 1999]

Q.2 In the depression of freezing point experiment, it is found that


(I) The vapour pressure of the solution is less than that of pure solvent.
(II) The vapour pressure of the solution is more than that of pure solvent.
(III) Only solute molecules solidify at the freezing point.
(IV) Only solvent molecules solidify at the freezing point.
(A) I, II (B) II, III (C) I, IV (D) I, II, III [JEE 1999]

Q.3 To 500 cm3 of water, 3×10–3 kg of acetic acid is added. If 23% of acetic acid is dissociated, what will
be the depression in freezing point ? Kf and density of water are 1.86 K kg–1 mol–1 and 0.997 g cm–
3 respectively. [JEE 2000]

Q.4 The vapour pressure of two miscible liquids (A) and (B) are 300 and 500 mm of Hg respectively. In a
flask 10 mole of (A) is mixed with 12 mole of (B). However, as soon as (B) is added, (A) starts
polymerising into a completely insoluble solid. The polymerisation follows first-order kinetics. After
100 minute, 0.525 mole of a solute is dissolved which arrests the polymerisation completely. The final
vapour pressure of the solution is 400 mm of Hg. Estimate the rate constant of the polymerisation
reaction. Assume negligible volume change on mixing and polymerisation and ideal behaviour for the
final solution.
[JEE 2001]

Q.5 During depression of freezing point in a solution, the following are in equilibrium
(A) liquid solvent-solid solvent (B) liquid solvent-solid solute
(C) liquid solute-solid solute (D) liquid solute-solid solvent [JEE 2003]

Q.6 Match the boiling point with Kb for x, y and z, if molecular weight of x, y and z are same.[JEE 2003]
b.pt. Kb
x 100 0.68
y 27 0.53
z 253 0.98

Q.7 A 0.004 M solution of Na2SO4 is isotonic with a 0.010 M solution of glucose at same temperature.
The apparent degree of dissociation of Na2SO4 is
(A) 25% (B) 50% (C) 75% (D) 85% [JEE 2004]

Q.8 1.22 g of benzoic acid is dissolved in (i) 100 g acetone (Kb for acetone = 1.7) and (ii)100 g benzene
(Kb for benzene = 2.6). The elevation in boiling points Tb is 0.17°C and 0.13°C respectively.
(a) What are the molecular weights of benzoic acid in both the solutions?
(b) What do you deduce out of it in terms of structure of benzoic acid? [JEE 2004]

Q.9 The elevation in boiling point, when 13.44 g of freshly prepared CuCl2 are added to one kilogram of
water, is [Some useful data, Kb (H2O) = 0.52 kg K mol–1, mol. wt. of CuCl2 = 134.4 gm]
(A) 0.05 (B) 0.1 (C) 0.16 (D) 0.21 [JEE 2005]

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Q.10 72.5 g of phenol is dissolved in 1 kg of a solvent (kf = 14) which leads to dimerization of phenol and
freezing point is lowered by 7 kelvin. What percent of total phenol is present in dimeric form?
[JEE 2006]

Q.11 When 20 g of naphtholic acid (C11H8O2) is dissolved in 50 g of benzene (Kf = 1.72 K kg mol–1), a
freezing point depression of 2 K is observed. The van’t Hoff factor (i) is
(A) 0.5 (B) 1 (C) 2 (D) 3 [JEE 2007]

Paragraph for Question No. Q.12 to Q.14


Properties such as boiling point, freezing point and vapour pressure of a pure solvent change when
solute molecules are added to get homogeneous solution. These are called colligative properties.
Applications of colligative properties are very useful in day-to-day life. One of its examples is the use
of ethylene glycol and water mixture as anti-freezing liquid in the radiator of automobiles.
A solution M is prepared by mixing ethanol and water. The mole fraction of ethanol in the mixture is
0.9.
Given : Freezing point depression constant of water K  = 1.86 K kg mol–1
water
f
Freezing point depression constant of ethanol   = 2.0 K kg mol–1
ethanol
K f
Boiling point elevation constant of water   = 0.52 K kg mol–1
water
K b

Boiling point elevation constant of ethanol   = 1.2 K kg mol–1


ethanol
K b
Standard freezing point of water = 273 K
Standard freezing point of ethanol = 155.7 K
Standard boiling point of water = 373 K
Standard boiling point of ethanol = 351.5 K
Vapour pressure of pure water = 32.8 mm Hg
Vapour pressure of pure ethanol = 40 mm Hg
Molecular weight of water = 18 g mol–1
Molecular weight of ethanol = 46 g mol–1
In answering the following questions, consider the solutions to be ideal dilute solutions and solutes to
be non-volatile and non-dissociative.

Q.12 The freezing point of the solution M is [JEE 2008]


(A) 268.7 K (B) 268.5 K (C) 234.2 K (D) 150.9 K

Q.13 The vapour pressure of the solution M is [JEE 2008]


(A) 39.3 mm Hg (B) 36.0 mm Hg (C) 29.5 mm Hg (D) 28.8 mm Hg

Q.14 Water is added to the solution M such that the mole fraction of water in the solution becomes 0.9. The
boiling point of this solution is [JEE 2008]
(A) 380.4 K (B) 376.2 K (C) 375.5 K (D) 354.7 K

Q.15 The Henry’s law constant for the solubility of N2 gas in water at 298 K is 1.0 × 105 atm. The mole
fraction of N2 in air is 0.8. The number of moles of N2 from air dissolved in 10 moles of water at 298
K and 5 atm pressure is
[JEE 2009]
(A) 4.0 × 10–4 (B) 4.0 × 10–5 (C) 5.0 × 10–4 (D) 4.0 × 10–5

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ANSWER
EXERCISE I

Q.1 0.24 Q.2 0.25 Q.3 24.5 torr Q.4 57.24 g/mol

Q.5 66.13 mm Hg Q.6 0.237 Q.7 0.682, 0.318; 0.829, 0.171

Q.8 92 mol% toluene; 96.8 mol % toluene Q.9 PA = 213.33 torr, PB = 960.0 torr

Q.10 0.04 Q.11 111.1g, 18.52 molal Q.12 0.741 m, 0.013

Q.13 0.162 m Q.14 65.25 Q.15 17.38 Q.16 0.964

Q.17 106 g/mol Q.18 64.0 g/mol Q.19 100.079°C Q.20 – 0.62°C

Q.21 5.08°C/m Q.22 50.8 g/mol Q.23 2050 g/mol Q.24 x = 25.6, y = 42.6

Q.25 Kb= 0.512 kg mol K–1, Tb = 373.20 K Q.26 38.71 g Q.27 156.06

Q.28 C6H 6 Q.29 Tf = –2.28oC Q.30 P = 0.2217 atm should be applied

Q.31 (Vfinal = 5.Voriginal) Q.32 54.2 g Q.33 0.81 atm Q.34 13.8 atm

Q.35 5.4 × 105 g/mol Q.36 2.4 × 105 g/mol Q.37 59.99

Q.38 MA/MB = 0.33 Q.39 i = 2.5 Q.40 3 ions Q.41  = 99.2%

Q.42 7.482 ×105 Nm–2 Q.43 94.5 % Q.44 4.64 atm Q.45 0.95; 1.95

PROFICIENCY TEST
Q.1
1. proportional 2. 2 : 1 3. solvent molecules 4. azeotropic mixture

5. Ebullioscopic constant 6. lesser 7. straight line with slope  0

8. negative 9. more 10. 3 11. increases

12. greater than 13. less than 1 14. Van’t Hoff’s solution equation
15. molality

Q.2
1. T 2. F 3. F 4. F 5. T 6. T
7. F 8. F 9. F 10. F 11. F 12. T
13. T 14. F 15. T

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EXERCISE II

Q.1 C Q.2 C Q.3 C Q.4 B Q.5 D Q.6 B


Q.7 B Q.8 C Q.9 B Q.10 C Q.11 A Q.12 C
Q.13 D Q.14 B Q.15 D Q.16 C Q.17 D Q.18 D
Q.19 C Q.20 D Q.21 D Q.22 A Q.23 C Q.24 B
Q.25 B Q.26 B Q.27 A Q.28 A,C,D Q.29 D Q.30 C

EXERCISE III

Q.1 B Q.2 C Q.3 0.229 Q.4 1.0 × 10–4 Q.5 A

Q.6 Kb(x) = 0.68, Kb(y) = 0.53, Kb(z) = 0.98 Q.7 C

Q.8 (a)122, (b) It means that benzoic acid remains as it is in acetone while it dimerises in benzene
O H O
as C C
O H O
Q.9 C Q.10 35% phenol is present in dimeric form

Q.11 A Q.12 D Q.13 B Q.14 B Q.15 A

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Surface Chemistry

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COLLOIDAL SOLUTION
PARTICLE SIZE :
–5
>10 cm 10–5-10–7 cm < 10–7 cm
suspension colloidal solution True solution

PHASE OF COLLOIDS :
A colloidal system is heterogeneous in character. It consists of two phases, namely a dispersed phase
and a dispersion medium.
(a) Dispersed Phase : It is the component present in small proportion and is just like a solute in a true
solution. For example, in the colloidal state of sulphur in water, the formeracts as a dispersed phase.
(b) Dispersion Medium : It is normally the component present in excess and is just like a solvent in a
solution.
The particles of the dispersed phase are scattered in the dispersion medium in a colloidal system.
CLASSIFICATION OF COLLOIDS :
Colloids can be can be classified in a number of ways based upon some of their important characteristics.
(1) Physical state of Dispersed Phase & Dispersion Medium:
Depending upon whether the dispersed phase and the dispersion medium are solids, liquids or gaseous,
eight types of colloidal system are possible. A gas mixed with another gas forms a homogeneous
mixture and not a colloidal system. Typical examples of various type alongwith their characteristic
names are given in table.

Common Colloidal System

Dispersed Phase Dispersion medium Colloidal system Examples

Gas Liquid Foam or froth Soap sols, lemonade froth,


whipped cream.
Gas Solid Solid foam Pumice stone, styrene, foam,
foam rubber.
Liquid Gas Aerosols of Fog, clouds, fine insecticide
Liquids sprays.
Liquid Liquid Emulsions Milk
Liquid Solid Gels Cheese, butter, boot polish,
table jellies, curd.
Solid Gas Aerosols of Smoke, dust
Solid
Solid Liquid Sols Must paint, starch dispersed in
water, gold sol, muddy water, inks.
Solid Solid Solid sols Ruby glass, some gem stones.

* A colloidal system in which the dispersion medium is a liquid or gas are called sols. They are called
hydrosols or aqua sols, if the dispersion medium is water. When the dispersion medium is alcohol or
benzene , they are accordingly called alcosols or benzosol.
* Colloidal systems in which the dispersion medium is a gas are called aerosols.

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* Colloids in which the dispersion medium is a solid are called gels, e.g. cheese etc. They have a more
rigid structure. Some colloids, such as gelatin, can behave both as a sol and a gel. At high temperature
and low concentration of gelatin, the colloid is a hydrosol. But at low temperature and high gelatin
concentration, the hydrosol can change into a gel.
(2) Based on interaction or affinity of phases : On the basis of the affinity or interaction between the
dispersed phase and the dispersion medium, the colloids may be classified into two types :
(i) Lyophilic Colloids : The colloidal system in which the particle of dispersed phase have great affinity
for the dispersion medium, are called lyophilic (solvent-loving) colloids. In such colloids, the dispersed
phase does not get easily precipitated and the sols are more stable. Such colloidal systems, even if
precipitated, may be reconverted to the colloidal state by simply agitating them with the dispersion medium.
Hence lyophilic colloids are reversible. When the dispersion medium is water, these are called hydrophilic
colloids. Some common examples of lyophilic colloids are gum, gelatin, starch, rubber, proteins, etc.
(ii) Lyophobic colloids : The colloidal system in which the dispersed phase have no affinity for the
dispersion medium are called lyophobic (solvent hating) colloids. They are easily precipitated (or
coagulated) on the addition of small amounts of the electrolyte, by heating or by shaking. They are less
stable and irreversible. When the dispersion medium is water, these are known as hydrophobic colloids.
Examples of lyophobic colloids include sols of metals and their insoluble compounds like sulphides and
oxides.
The essential differences between the lyophilic and lyophobic colloids are summarised in table.
Difference between Lyophilic and Lyophobic sols

Property Lyophilic sols Lyophobic sols


1. Nature Reversible Irreversible
2. Preparation They are prepared very easily by They are difficult to prepare, Special
shaking or warming the substance methods are used. Addition of stabiliser
with dispersion medium. They do is essential for their stability.
not required any electrolyte for
stabilization.
3. Stability They are very stable and are not They are generally unstable and get easily
easily coagulated by electrolytes. coagulated on addition of electrolytes.
4. Charge Particles carry no or very little Colloidal particles have characteristic
charge depending upon the pH charge (positive or negative)
of the medium.
5. Viscosity Viscosity is much higher than that Viscosity is nearly the same as that of
of the medium. the medium
6. Surface Tension Surface tension is usually less than Surface tension is nearly the same as that
that of the medium. of the medium.

7. Migration in The particles may or may not The colloidal particles migrate either
electric field migrate in an electric field. towards cathode or anode in an electric
field.
8. Solvation Particles are heavily solvated. Particles are not solvated.
9. Visibility The particles cannot be seen under The particles though invisible, can be seen
ultra microscope. under ultra microscope.
10. Tyndall effect Less distinct. More distinct.
11. Action of Large amount of electrolyte is Small amount of electrolyte is sufficient
electrolyte required to cause coagulation. to cause cogulation.
12. Examples Mostly organic substances Generally inorganic substance e.g., metal

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e.g. starch, gums, proteins, sols, sulphides and oxides sols.


gelatin etc.
Origin of charge : Various reasons have been given regarding the original of charge on the colloidal
particles. These are given below :
(i) Frictional electrification : It is believed to be frictional due to the rubbing of the dispersed phase
particles with medium molecules.
(ii) Dissociation of the surface molecules : It leads to electric charge on colloidal particles. For example,
an aqueous solution of a soap (sodium palmitate) dissociates into ions.
C15H31COONa l C15H31COO— + Na+
sod. palmitate
The Na+ ions pass into the solution while C15H31COO— ions have a tendency to form aggregates due
to weak attractive forces present in the hydrocarbon chains. Thus, the anions which are of colloidal
size bear negative charge.
(iii) Preferential adsorption of ions from solution : The charge on the colloidal particles is generally
acquired by preferentially adsorbing positive or negative ions from the electrolyte. Thus AgCl particles
can adsorb Cl— ions from chloride solutions and Ag+ ions from excess Ag+ ions solutions; the sol. will
be negatively charged in the first case and positively charged in the second case.
(iv) Capture of electron : It is from air during preparation of sol. by Bredig's arc method.
(v) Dissociation of molecular electrolytes on the surface of particles : H2S molecules get adsorbed
on sulphides during precipitation. By dissociation of H2S, H+ ions are lost and colloidal particles become
negatively charged.

Electrical charged sols.

Positively charged sols Negatively charged sols


1. Ferric hydroxide, aluminium hydroxide Metals such as Pt, Au, Ag, Metals sulphides,
e.g. arsenius sulphide.
2. Basic dyes such as methylene blue Starch, clay, silicic acid.
3. Haemoglobin Acid dyes, such as eosin.

(3) Based on type of particles of the dispersed phase : Depending upon the molecular size, the colloidal
system has been classified into three classes :
(i) Multimolecular colloids : The multimolecular colloidal particles consists of aggregate of atoms of
small molecules with diameters less than 10–9 m or 1 nm.
For example, a sol. of gold contains particles of various sizes having several atoms. A sol. of sulphur
consists of particles containing a thousand or so S2 molecules. These particles are held together by
vander Waal's forces. These are usually lyophobic sols.
(ii) Macromolecular colloids : The macromolecular colloidal particles themselves are large molecules.
They have very high molecular weights varrying from thousands to millions. These substances are
generally polymers. Naturally occurring macromolecules are such as starch, cellulose and proteins.
Artificial macromolecules are such as polyethylene, nylon, polysyrene, dacron, synthetic rubber, plastics,
etc. The size of these molecules are comparable to those of colloidal particles and therefore, their
dispersion known as macromolecular colloids. Their dispersion also resemble true solutions in some
respects.
(iii) The associated colloids or miscelles : These colloids behave as normal electrolytes at low
concentrations but colloids at higher concentrations. This is because at higher concentrations, they
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form aggregated (associated) particles called miscelles. Soap and synthetic detergents are examples of
associated colloids. They furnish ions which may have colloidal dimensions.
RCOONa l RCOO— + Na+
Sod. Stearate soap (R = C17H35)

The long-chain RCOO ions associates or aggregate at higher concentrations and form miscelles and
behave as colloids. They may contain 100 or more molecules.
Sodium stearate C17H35COONa is an example of an associated colloid. In water it gives Na+ and
sterate, C17H35COO— ions. These ions associate to form miscelles of colloidal size.
Colloids which behave as normal electrolytes at low concentration, but exhibit colloidal properties
at higher concentration due to the formation of aggregated particles called micelles are referred
to as associated colloids. The micelles are formed by the association of dispersed particles above
a certain concentration and certain minimum concentration is required for the process of
aggregation to take place. The minimum concentration required for micelle formation is called
micellisation concentration (CMC) and its value depends upon the nature of the dispersed phase.
For soaps CMC is 10–3 mole L–1.
Mechanism of Micelle Formation :
Micelles are formed by surface active molecules called surfactants such as soaps and detergents.
These molecules have lyophilic group at one end and a lyphobic group at the other end. Let us take the
example of a soap (say sodium oleate, C17H33COO—Na+). The long hydrocarbon part of oleate
r a d i c a l

(C17H33 –) is lyophobic end while COO part is lyophilic end. When the concentration of the solution
is below its CMC, sodium oleate behaves as a normal electrolyte and ionises to give C17H33COO—
and Na+ ions. When the concentration exceeds CMC, the lyophobic part starts receding away from
the solvent and tends to approach each other. However, the polar COO— ends tends to interact with
the solvent (water). This finally leads to the formation of bigger molecules having the dimensions of
colloidal particles. Thus 100 or more oleate ions are grouped together in a spherical way keeping their
hydrocarbon parts inside and the –COO— part remains projected in water.

LIST OF SURFACTANTS AND THEIR CRITICAL MICELLE CONCENTRATION (CMC)

Surfactant CMC (g/1) Temp.(°C)


Anionic
CH3 (CH2)6COONa 6.5 × 101 20
CH3 (CH2 )10 COONa 5.6 20–70
CH3(CH2 )7OSO3Na 3.0 ×101 25–50
CH3 (CH2)11 OSO3Na 2.6 25–60
CH3(CH2)5 C6H4 SO3Na 9.8 75
CH3(CH2 )11C6H4SO3Na 4.0 ×10–1 50–75

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Cationic
CH3(CH2)9NH2.HCl 8.5 25
CH3(CH2)11NH2HCl 2.7 30–50
CH3(CH2)7N(CH3)3Br 7.8 × 101 25
CH3(CH2)11N(CH3)3Br 5.4 25
Non-ionic
CH3(CH2)7C6H11O6 7.3 25
C12 H20 O9(C16 H31 O2)2 1.1. × 10–2 20
CH3(CH2)10COOC12H21 O10 7.1 × 10–3 50

PREPARATION OF COLLOIDAL SOLUTIONS


(1) Preparation of lyophilic sols : The colloidal solutions of lyophilic colloids like starch, glue, gelatin
etc., can be readily prepared by dissolving these substances in water either in clod or on warming.
Solutions of colloidal electrolytes such as soaps and dye stuffs can also be prepared similarly.
(2) Preparation of lyophobic sols : To get a substance in colloidal form either the substance in bulk is
broken down into fine particles of colloidal dimension (1Å to 103 Å ) or increasing the size of molecular
particles as to form larger aggregates. In some cases, a third substance as to form larger aggregates. In
some cases, a third substance is usually added to increase the stability of the sol. These substances are
called stabilizers. Thus, there are two ways by which the lyophobic sols can be prepared :
(i) Dispersion methods : By splitting coarse aggregates of a substance into colloidal size.
(ii) Condensation methods : By aggregating very small particles (atoms, ions or molecules) into
colloidal size.
S. No. Dispersion methods Condensation methods
1. Mechanical dispersion 1. Exchange of solvents
2. Electro–dispersion 2. Change of physical state
3. Ultrasonic dispersion 3. Chemical methods :
(i) Double decomposition (ii) Oxidation
(iii) Reduction (iv) Hydrolysis
Dispersion Methods
(1) Mechanical dispersion : Solid material is first finely ground by usual methods. It is then mixed with
dispersion medium which gives a coarse suspension. The suspension is now introduced into the colloid
mill. The simplest form of colloid mill consists of two metal discs held at a small distance apart from one
another and capable of revolving at a very high speed (about 7000 revolutions per minute) in opposite
directions. The particles are ground down to colloidal size and are then dispersed in the liquid . Astabilizer
is often added to stabilize the colloidal solution. Colloidal graphite (a lubricant) and printing ink

Suspension

Driving belt

Discharge Discharge
Discs Metal disc

are made by this method. Tannin is used as a stabilizer in the preparation of colloidal graphite and gum
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arabic in lampblack colloidal solution (Indian ink).


(2) Electro-dispersion (Bredig's arc method) : This method is suitable for the preparation of colloidal
solutions of metals like gold, silver, platinum, etc. An arc is struck between the metal electrodes under
the surface of water containing some stabilizing agents such as a track of KOH. The water is cooled by
immersing the

+ –
Metal rod
Ice bath
Water + KOH
Electric arc

container in an ice bath. The intense heat of the arc vaporises some of the metal which condenses under
cold water.

Note : (1) This method is not suitable when the dispersion medium is an organic liquid as considerable charring
occurs.
(2) This method comprises both dispersion and condensation.

(3) Ultrasonic dispersion : The sound waves of high frequency are usually called ultrasonic waves.
These waves can be produced when quartz crystal discs are connected with a high frequency generator.
The application of ultrasonic waves for the preparation of colloidal solutions was first introduced by
wood and Loomis, in 1927. Various substances like oils, mercury, sulphur, sulphides and oxides of
metals can be dispersed into colloidal state very easily with the help of ultrasonic waves.

(4) Peptization : The dispersion of a freshly precipitated material into colloidal solution by the action of
an electrolyte in solution is termed peptization. The electrolyte used is called a peptizing agent.
A few examples of sols obtained by peptization are :
(i) Freshly prepared ferric hydroxide on treatment with a small amount of ferric chloride solution at
once forms a dark reddish brown solution. Ferric chloride acts as a peptizing agent.
(ii) Freshly prepared stannic oxide on treatment with a small amount of dilute hydrochloric acid forms
a stable colloidal solution of stannic oxide.
(iii) Freshly precipitated silver chloride can be converted into a colloidal solution by a small amount of
hydrochloric acid.
(iv) Cadmium sulphide can be peptized with the help of hydrogen sulphide.
The process of peptization thus involves the adsorption of suitable ions (supplied by the
electrolyte added––particularly a common ion) and electrically charged particles then split from the
precipitate as colloidal particles.

Condensation Methods
(1) By exchange of solvents : If a solution of sulphur or phosphorus prepared in alcohol is poured into
water, a colloidal solution of sulphur or phosphorus is obtained due to low solubility of sulphur or
phosphorus is obtained due to low solubility in water. Thus, there are a number of substances whose
colloidal solutions can be prepared by taking a solution of the substance in one solvent and pouring it
into another solvent in which the substance is relatively less soluble.

(2) By change of physical state : Colloidal solutions of certain elements such as mercury and sulphur are
obtained by passing their vapour through cold water containing a stabilizer (an ammonium salt or a
citrate)

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(3) Chemical methods : The chemical methods involve chemical reactions in a medium in which the
dispersed phase is sparingly soluble. A condition of supersaturation is produced but the actual precipitation
is avoided. Some familiar reactions used are :
(a) Double decomposition : (i) Arsenious sulphide sol : A 1% solution of arsenious oxide is prepared
is hot water. The solution is cooled, filtered and is then gradually in hot water saturated with hydrogen
sulphide. This is continued till an intense yellow-coloured solution is obtained. Excess of H2S is removed
by bubbling hydrogen through the solution.
As2O3 + 3H2S As2S3 + 3H2O
Yellow sol
(ii) Antimony sulphide sol : A 0.5% solution of potassium antimonyl tartarate is added drop by drop to
water saturated with H2S, whilst H2S is being passed through the solution. Orange coloured solution
of antimony sulphide is obtained.
CH(OH)COOK CH(OH)COOK
2 + 3H2S 2
CH(OH)COO(sbO) CH(OH)COOH + Sb2S3 + 2H2O
Orange sol
(b) Oxidation : A colloidal solution of sulphur is obtained by passing H2O into a solution of sulphur
dioxide.

2H 2S  SO 2 3S
2H2O + Sol
Sulphur sol can also be obtained when H2S is bubbled through an oxidising agent (bromine water or
nitric acid).
(c) Reduction : Colloidal solutions of metals like gold, silver, platinum, lead, etc., can be obtained
when their salts solutions are acted upon by reducing agents.
2AuCl3 + 3SnCl2 3SnCl4 + 2Sol
Au

Organic reducing agents such as formaldehyde, phenyl hydrazine, tannic acid, etc., can also be used.
AgNO3 + tannic acid Silver sol
AuCl3 + tannic acid Gold sol
(d) Hydrolysis : Colloidal solutions of some salts can be prepared by hydrolysis. A colloidal solution
of ferric hydroxide is obtained by boiling a dilute solution of ferric chloride.]

FeCl3 + 3H2O Fe (OH)3  3HCl


Re d sol
The colloidal solution of silicic acid is also obtained by hydrolysis of dilute solution of sodium silicate
with 4N hydrochloric acid which is added drop by drop with constant stirring.
PURIFICATION OF COLLOIDAL SOLUTIONS
Colloidal solutions prepared by above methods generally contain excessive amount of electrolytes and
some other soluble impurities. The presence of traces of electrolyte is essential for the stability of the
colloidal solution but larger quantities coagulate it. It is, therefore, necessary to reduce the concentration
of these soluble impurities to a requisite minimum. The process used for reducing of these impurities to
a requisite minimum is known as purification of colloidal solution. The purification of colloidal solution
is carried out by the following methods.
(i) Dialysis* : It is a process of removing a dissolved substance from a colloidal solution by means of
diffusion through suitable membrane. Since, particles in true solution (ions or smaller molecules) can
pass through animal membranes (bladder) or parchment paper or cellophane sheet but colloidal particles
do not, the above can be used for dialysis. The apparatus used for this purpose is called dialyser. A bag
of suitable membrane containing the colloidal solution is suspended in a vessel through which fresh
water is continuously flown figure. The molecules and ions diffuse through the membrane into the outer

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water and pure colloidal solution is left behind.

Dialysing membrane

Water + Crystalloid
Water Crystalloid
Sol particle
(ii) Electro-dialysis : Ordinarily, the process of dialysis is quite slow. It can be made faster
by applying an electric field if the dissolved substance in the impure colloidal solution is only electrolyte.
The process is then named electro-dialysis. The colloidal solution is placed between two electrodes
while pure water is taken in a compartment on each side. Electrodes are fitted in the compartment as
shown in figure the ions present in the colloidal solution migrate out to the oppositely charged electrodes.

Dialysing membrane

– Water + Electrolyte
+
Anode Cathode
Water Crystalloid
Sol particle
(iii) Ultrafiltration : Ultrafiltration is the process of separating the colloidal particles from
the solvent and soluble solutes present in the colloidal solution by especially prepared filters, which are
permeable to all substances except the colloidal particles.
Colloidal particles can pass through ordinary filter paper because the pores are too large.
However, the pores of filter paper can be reduced in size by impregnating with collodion solution and
subsequently hardened by soaking in formaldehyde. The usual colloidion is a 4% solution of nitro-
cellulose in a mixture of alcohol and ether. An ultrafilter paper may be prepared by soaking the filter
paper in a colloidion solution and hardened by formaldehyde and finally drying it. Thus, by using
ultrafilter paper, the colloidal particles are separated from rest of the materials. Ultrafiltration is a slow
process. To speed up the process, pressure or suction is used.
The colloidal particles left on the ultrafilter paper are then stirred with fresh dispersion medium
(solvent) to get a pure colloidal solution.

PROPERTIES OF COLLOIDAL SOLUTIONS :


(1) Physical properties :
(i) Heterogeneity : Colloidal solutions are heterogeneous in nature consisting of two phases viz, the
dispersed phase and the dispersion medium. Experiments like dialysis and ultra filteration clearly indicate
the heterogeneous character of colloidal system. Recent investigations however, shown that colloidal
solutions are neither obviously homogeneous nor obviously heterogeneous.
(ii) Filterability : Colloidal particles readily pass through orginary filter papers. It is because the size of
the pores of the filter paper is larger than that of the colloidal particles.
(iii) Non-settling nature : Colloidal solutions are quite stable as the colloidal particles remain suspended
in the dispersion medium indefinitely. Thus there is no effect of gravity on the colloidal particles.
(iv) Colour : The colour of the colloidal solution is not always the same as the colour of the substances in
the bulk. The colour of the colloidal solution depends upon the following factors :
(a) Size and shape of colloidal particles.
(b) Wavelength of the source of light.
(c) Method of preparation of the colloidal solution.
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(d) Nature of the colloidal solution.


(e) The way an observer receives the light, i.e., whether by reflection or by transmission.
(f) Stability : Colloidal solutions are quite stable. Only a few solutions of larger particles may settle but
very slowly.

Examples :
(i) Finest gold is red in colour. As the size of particles increases, it becomes purple.
(ii) Dilute milk gives a bluish tinge in reflected light whereas reddish tinge in transmitted light.
(2) Mechanical Properties :
(a) Brownian movement : Colloids particles exhibit a ceaseless random and swarming motion. This
kinetic activity of particles suspended in the liquid is called Brownina movement.
Robert Brown first observed this motion with pollen grains suspended in water.
Cause of movement : Brownian movement is due to bombardment of the dispersed particles by
molecules of the medium. The Brownian movement (figure) depends upon the size of sol. particles.
With the increase in the size of the particle, the chance of unequal bombardment decrease, and the
Brownial movement too disappears. It is due to the fact that the suspension fails to exhibit this
phe-nomenon.
It should be noted that Brownian movement does not change with time but changes with temperatures.

Importance :
(i) Brownian movement is a direct demonstration of the assumption that the molecules in a gas or solution
are in a state of constant ceaseless motion. Thus it confirms kinetic theory.
(ii) Brownian movement does not allow the colloidal particles to settle down due to gravity and thus is
responsible for their stability.
(iii) Brownian movement helps to calculate the Avogadro's number (Detail beyond the scope of the book).
(b) Sedimentation : Heavier sol. particle tend to settle down very slowly under the influence of gravity.
This phenomenon is called sedimentation.
(3) Optical Properties (Tyndal Effect) :
When a strong and converging beam of light is passed through a colloidal solution, its path becomes
visible (bluish light) when viewed at right angles to the beam of light (figure). This effect is called Tyndall
effect. The light is observed as a bluish cone which is called Tyndall cone.
The Tyndall effect is due to scattering of light by the colloidal particles. The scattering of light cannot be
due to simple reflection, because the size of the particles is smaller than the wave, length of the visible
light and they are unable to reflect light waves. In fact, colloidal particles first absorb light and then a
part of the absorbed light is scattered from the surface of the colloidal particles as a light of shorter
wavelength. Since maximum scattering of light takes place at right angles to the place of incident light,
it becomes visible when seen from that direction.

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The Tyndall effect is observed under the following conditions :


(i) The diameter of the dispersed particles must not be much smaller than the wavelength of light employed.
(ii) The refractive indices of the dispersed phase and the dispersion medium must differ widely. This condition
is fulfilled by lyophobic colloids.
It is important to note that Tyndall effect is not shown by true solutions as their particles are too small
to cause scattering. Tyndall effect has been used in devising ultramicroscope and in determining the
number of colloidal particles in a colloidal solution.
(4) Electrical Properties :
The two electrical properties of colloidal solutions are :
(a) Electrophoresis or Cataphoresis and (b) Electro-osmosis
(a) Electrophoresis or Cataphoresis : In a colloidal solution, the colloidal particles are electrically
charged and the dispersion medium has equal but opposite charge. Thus colloidal solution on the
whole is electrically neutral. When an electric current is passed through a colloidal solution, the charged
particles move towards the oppositely charged electrode where coagulate due to loss of charge.

The phenomenon involving the migration of colloidal particles under the influence of electric field towards
the oppositively charged electrode, is called electrophoresis or cataphoresis.
This phenomenon is used to determine the charge on the colloidal particles. For example, when a sol.
of ferric hydroxide is taken in a U-tube and subjected to electric field, the ferric hydroxide (sol.)
particles get accumulated near the cathode (figure). This shows that ferric hydroxide sol. particles are
positively charged.
The sol. particles of metals and their sulphides are found to be negatively charged while those of metal
hydroxides are positively charged. Basic dyes such as methylene blue haemoglobin are positively
charged while acid dyes like are negatively charged.
(b) Electro-osmosis : The phenomenon involving the migration of the dispersion medium and not the
colloidal particles under the influence of an electric field is electro-osmosis.
Take the pure solvent (dispersion medium) in two limbs of U-tube. In the lower middle portion of
U-tube, a porous diaphragm containing the colloidal system is present which divides the U-tube in two
sections. In each section of U-tube, an electrode is present, as shown in figure. When the electrode
potential is applied to the electrodes, the solid phase of sol. (colloidal system) cannot move but the

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solvent (dispersion medium) moves through the porous diaphragm towards one of the electrodes. The
direction of migration of dispersion medium due to electro-osmosis determines the charge on sol.
particles e.g., if the dispersion medium moves towards the cathode (negative electrode), the sol. particles
are also negatively charged because the dispersion medium is positively charged as on the whole
colloidal solution is neutral.

(c) Coagulation : the colloidal sols are stable due to the presence of electric charges on the colloidal
particles. Because of the electrical repulsion, the particles do not come close to one another to form
precipitates. The removal of charge by any means will lead to the aggregation of particles and hence
precipitation will occur immediately.
This process by means of which the particles of the dispersed phase in a sol. are pecipitated
is known as coagulation.
If the coagulated particles instead of settling at the bottom of the container, float on the surface of the
dispersion medium, the coagulation is called flocculation.
Most of the sols are coagulated by adding an electrolyte of opposite sign. This is due to the fact that the
colloidal particles take up the ions of electrolyte whose charges are opposite to that on colloidal
particles with the result that charge on the colloidal particles is neutralized. Thus coagulation takes
place. For example, arsenius sulphide sol. (negatively charged) precipitated by adding barium chloride
solution. It is due to the fact that the negatively charged particles of the sol. take up barium ions and get
neutralized which lower the stability. As a result precipitation takes place.
It is observed that different amounts of different electrolytes is required to bring coagulation of a
particular solution.
The minimum amount of an electrolyte required to cause precipitation of one litre of a colloidal solution
is called coagulation value or flocculation value of the electrolyte for the sol.
The reciprocal of coagulation value is regarded as the coagulating power.
For example, the coagulation values of NaCl, BaCl2 and AlCl3 for arsenic sulphide sol. are 51, 0.69
1 1 1
and 0.093 millimoles/litre respectively. Thus their coagulating powers are , and i.e.,
51 0.69 0.093
0.0196, 1.449 and 10.75 respectively.
The coagulation values of a few electrolytes for negatively charged arsenic sulphide and positively
charged ferric hydroxide sol. are given in table given below. The valency of the coagulation ion (the ion
whose charge is opposite to that of the colloidal particles) is also give.
Coagulation values of different electrolytes
Arsenic sulphide sol. Ferric hydroxide sol.
Electrolyte Valency of coagulation Electrolyte Valency of coagulation
coagulating value coagulating value
cation (millimoles/litre) cation (millimoles/litre)

K2 SO 4 1 63 KBr 1 138
NaCl 1 51 KNO 3 1 132
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KNO 3 1 50 KCl 1 103


MgSO4 2 0.81 K2 CrO4 2 0.320
BaCl2 2 0.69 K2 SO 4 2 0.215
AlCl3 3 0.093 K3Fe(Cn)6 3 0.096

From the above table, it is clear that the coagulating power of Al3+ ions in precipitating the arsenic
sulphide sol. is approximately 550 times more than that of sodium (Na+) or potassium (K+) ions.
Again, it is observed that the negatively charged arsenic sulphide sol. is coagulated by cations while
positively charged ferric hydroxide sol. is coagulated by anions.
Hardy-Schulz rules : H. Schulze (1882) and W.B. Hardy (1900) suggested the following rules to
discuss the effect of electrolytes of the coagulation of the sol.
(1) Only the ions carrying charge opposite to the one present on the sol. particles are effective to cause
coagulation, e.g., the negative charged sol. is best coagulated by cations and a positive sol. is coagulated
by anions.
(2) The charge on coagulating ion influences the coagulation of sol.
In general, the coagulating power of the active ion increases with the valency of the active ion.
After observing the regularities concerning the sing and valency of the active ion, a law was proposed
by Hardy and Schulz which is termed as Hardy-Schulze law which is stated as follows:
"Higher is the valency of the active ion, greater will be its power to precipitate the sol."
Thus, coagulating power of cations is in the order of Al3+ > Ba2+ or Mg2+ > Na+ or K+.
Similarly, to coagulating the positively charged sol. the coagulating power of anion is in the order of
[Fe(CN)6]4– > PO43– > SO42– > Cl–
Some other methods of coagulation :
Apart from the addition of electrolyte, coagulation can also be carried out by following methods:
(i) By persistent dialysis : It has been observed that traces of electrolytes are associated with the
solution due to which it is stable. If the solution is subjected to prolonged dialysis, the traces of electrolytes
are removed and coagulation takes place.
(ii) By mutual coagulation of colloids : When two sols of oppositively charges are mixed together in
a suitable proportion, the coagulation takes place. The charge of one is neutralized by the other. For
example, when negatively charged arsenic sulphide sol. is added to positively charged ferric hydroxide
sol., the precipitation of both occurs simultaneously.
(iii) By electrical method : If the electrical charge of lyophobic sol. is removed by applying any electric
field such as in electrophoresis, they also precipitate out.
(iv) By excessive cooling or by excessive heating.
(5) Colligative properties : Colloidal solutions too exhibit colligative properties such as osmotic pressure,
lowering of vapour pressure, depression in freezing point and elevation in boiling point. But the effect of
colloidal particles on colligative properties except osmotic pressure is very small. This is due to the
large size of colloidal particles. The number of colloidal particles produced by a given mass of colloid
is much less than the number produced in a molecular solution, containing the same mass of solute.
Hence the colligative effect in colloidal solutions is too less.
* PROTECTIVE COLLOIDS :
Lyophilic sols are more stable than the lyophobic sols. This is because, lyophilic colloids are extensively
hydrated and these hydrated particles do not combine to form large aggregates.
Lyophobic sols are more easily coagulated by the addition of suitable electrolyte. To avoid the
precipitation of lyohobic sol. by the addition of electrolyte, some lyophilic colloid is added to it. Such
lyophilic colloid is called protective colloid and the action of lyophilic colloid by the electrolytes is
known as protective anion. The substances commonly used as protective colloids are gelating, albumin,

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gum arabic, casein, starch, glue etc. A gold sol. containing a little gelatin as protective colloid needs a
very large amount of sodium chloride to coagulate the sol.

Explanation : The particles of the protective colloid get adsorbed on the particles of the lyophobic
colloid, thereby forming a protective layer around it (figure). The protective layer prevents the precipitating
ions from coming in contact with the colloidal particles.
According to a recent view, the increase in stability of the lyophobic colloid is due to the mutual
adsorption of the lyophilic and lyophobic colloids. It is immaterial which is adsorbed on which. In fact
the smaller particles, whether of the protective colloid or the lyophobic colloid, are adsorbed on the
bigger particles.
Gold number of a protective colloid is a minimum weight of it in milligrams which must be
added to 10 ml of a standard red gold sol so that no coagulation of the gold sol. (i.e. change of colour
from red to blue) takes place when 1 ml of 10 % sodium chloride solution is rapidly added to it.
Obviously, smaller the gold number of a protective colloid, the greater is the protective action.
Isoelectric Point of Colloid :
The hydrogen ion concentration at which the colloidal particles are neither positively charged nor
negatively charged (i.e. uncharged) is known as isoelectric point of the colloid. At this point lyophilic
colloid is expected to have minimum stability because at this point particles have no charge. The
isoelectric point of gelatin is 4.7. This indicates that at pH = 4.7, gelating has no electrophoretic motion.
Below 4.7, it moves towards the cathode and above 4.7 it moves forwards the anode. It is not always
true, e.g., silicic acid has been found to have maximum stability at the isoelectric point.
Electric double layer :
The surface of a colloidal particle acquires a positive or a negative charge by selective adsorption
of ions carrying +ve or – ve charges respectively. The charged layer attracts counter ions from
the medium which forms a second layer. Thus, an electrical double layer is formed on the surface
of the particles i.e., one due to absorbed ions and the other due to oppositely charged ions
forming a diffused layer. This layer consists of ion of both the signs, but its net charge is equal
and opposite to those absorbed by the colloidal particles. The existence of charges of opposite
signs on the fixed and diffused parts of the double layer creates a potential between these
layers. This potential difference between the fixed charge layer and diffused layer of opposite
change is called electrokinetic potential or zeta potential.

EMULSIONS
An emulsion is a colloidal solution of a liquid. It may be defined as a heterogeneous system consisting
of more than one immiscible liquids dispersed in one another in the form of droplets whose diameter, in
general, exceeds 0.1 .
For example, milk is an emulsion in which small drops of liquid fat are dispersed in aqueous medium.
Cod liver oil is an emulsion in which the water drops are dispersed in the oil. This means in most of the
emulsions one of the liquid is water and the other liquid is oil. Here the term 'oil' is used to represent all
organic substances which are soluble in water.

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The emulsion are classified as :


(1) Oil in water type emulsion (O/W): In this emulsion, oil is the dispersed phase and water is the
dispersion medium. It is denoted by O/W or O in W. For example, milk (liquid fat dispersed in water),
vanishing cream, etc.
(2) Water in oil type : In this emulsion, water is the dispersed phase and oil is the dispersion medium. It
is denoted by W/O or W in O. For example, butter, cod liver oil, cold cream, etc.
The type of emulsion obtained by agitating two immiscible liquids depends upon the relative amounts of
two components liquids. The liquid that is in excess forms the dispersion medium. Thus, the two types
of emulsions can be interconverted into each other by changing the concentration of one of the liquids.
Distinction between two types of emulsions : the two types of emulsions may be distinguished
from each other in a number of ways.
(1) Dye test : It involves the addition of oil soluble dye to the emulsion under experiment. If the emulsion
acquires the colour of the dye readily, it is water-in-oil type emulsion and it the emulsion remains
colourless, it is oil-in-water type emulsion.
(2) Conductivity test : It involves the addition of electrolyte to the emulsion under experiment. If the
conductivity of the emulsion increases appreciably with the addition of electrolyte, it is
oil-in-water type emulsion and it conductivity is very small, it is water-in-oil type emulsion.
(3) Dilution test : As a general rule, an emulsion can be diluted with the dispersion medium while the
addition of the dispersed phase forms a separate layer. Thus, if an emulsion can be diluted with oil, it is
water-in-oil type.
Preparation of emulsion (Emulsification) : Emulsification is the process which involves the
preparation of emulsion. Generally, an emulsion is prepared by subjecting a mixture of the immiscible
liquid to a distinct layers upon standing. The oil globules rise to form an upper layer while aqueous
medium forms lower layers. To prevent the separation of layers and to get the stable emulsion, a small
quantity of the third substance is added. This substance which stabilizes the emulsion is called emulsifier
or emulsifying agent. The commonly used emulsifying agents are soaps, detergents and lyophilic
colloids. Casein, a lyophilic colloid present in milk, acts as an emulsifier as it forms a protective layer
around fat molecules dispersed in water. Hence milk is a fairly stable emulsion.
Function of emulsifier : The main function of emulsifier or emulsifying agents is to lower the interfacial
tension between oil and water and thus helps the intermixing of two liquids. For example, a molecule of
a soap or detergent (emulsifier) gets concentrated at the interface between oil and water. The polar end
of the emulsifier is in water and non-polar end is in oil as shown in figure.
In a soap, RCOONa, R is the non-polar end, whereas COO— Na+ is the polar end.
Properties of emulsion :
(i) The size of particles of the dispersed phase of an emulsion is usually larger than in sols.
(ii) Like colloidal particles, emulsions exhibit properties such as Tyndall effect, Brownian movement
(provided the particles are not too large), electrophoresis, coagulation, etc.

Demulsification : The process which involves the breaking of an emulsion into two separate liquid
layers is called demulsification. The following methods may be used to bring demulsification:
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(1) Chemical Methods : An emulsion may be demulsified by adding a chemical substance whose action
on the dispersed phase and the dispersion medium is opposite to that of the original emulsifying agent
used to produce the stable emulsion.
(2) Centrifugation : Cream is separated from milk by the centrifugal method.
(3) Cooling : Fat can be removed from milk by keeping it in a refrigerator for a few hours.
Demulsification :
Besides the above noted methods of demulsification, the following methods have also been
developed :
(i) Suitable centrifugal action-milk cream is separated from milk by centrifugation.
(ii) Application of electric field-electrophoresis.
(iii) Addition of an electrolyte having multivalent opposite charge than that on the dispersed phase.
(iv) Chemical destruction of stabiliser.
(v) Distilling off of one of the components, usually water.
(vi) Addition of demulsifiers like alcohol, phenol etc.

Oil in water type emulsion (O/W) Use of emulsion :

(1) Many pharmaceutical preparations-medicines, ointments, creams and various lotions are emulsions. It
is believed that medicines are more effective and easily assimilated by the body tissues when they are
in colloidal form i.e., emulsion.
(2) All paints are emulsions.
(3) The digestion of fat in the intestines is helped by emulsification. A little of the fat forms a medium soap
(emulsifier) with the alkaline solution of the intestine and this soap emulsifier the rest of the fats, thus
making it easier for the digestive enzymes to do their metabolic functions.
(4) Soaps and detergents remove dust and dirt from the dirty piece of cloth by making an oil in water
emulsion.
(5) Milk is an emulsion of liquid fats in water.
(6) In the process of metallurgy, one of the important steps is the concentration of ore which is usually done
by froth floatation process in which an oil is added to the finely-divided ore taken in water. The particles
of ore go on the surface due to formation of foams while the other impurities are left at the bottom of the
vessel.
(7) The emulsion of asphalt in water is used in road making and building.

GELS
Colloidal system in which liquids are the dispersed phase and solid act as the dispersion medium are
called gels. The common examples are : boot polishes, jelly, gum arabic, agar agar, processed cheese
and silicic acid.
When the gels are allowed to stand for a long time, they give out small quantities of trapped liquids with
accumulate on its surface. This action of gels is known as Synresis or Weeping. Some gels such as
silica, gelatin and ferric hydroxide liquify on shaking and reset on allowing to stand. This phenomenon
o f
Sol-gel transformation is called thixotropy.
Gels are divided into two categories i.e. elastic gels and non elastic gels. The two categories differ from
their behaviour towards dehydration and rehydration as under.

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Elastic gels Non-elastic gels


1. They change to solid mass on dehydration 1. They change to solid mass on dehydration
which can be changed back to original which cannot be changed back to original
form by addition of water followed by warming. form with water.
2. They absorb water when placed in it with 2. They do not exhibit imbibation.
simultaneous swelling. This phenomenon is
called imbibation.

USES OF COLLOIDS :
(1) Medicines : The medicines containing gold, silver or calcium etc. in colloidal form are more effective
and easily assimilated by the human systems.
(2) Dyes : In dyeing, mordants colloidal substances are used in textile dyeing industry to fasten dyes.
(3) Rubber industry : Latex is a colloidal solution of negatively charged particles. The article to be
rubber plated is made the anode. Under the influence of electric field the rubber particles get deposited
on the anode and the article gets rubber plated.
(4) Smoke screens : Smoke screens which consist of titanium dioxide dispersed in air are used in warfare
for the purpose of concealment and camouflage.
(5) Formation of delta : The river waver carries with it charged clay particles and many other substances in
the form of colloidal solution. When the sea water comes in contact with these particles, the colloidal particles
in river water are coagulated by the electrolytes present in sea water to form deltas.
(6) Purification of water : The turbidity in water is due to the presence of negatively charged clay particles.
The addition of potash alum, i.e., Al3+ ions neutralizes the negative charge on the colloidal particles and thus
causes their coagulation. The coagulated matter settles down and thus becomes clear.
(7) Artificial rain : Artificial rain can be caused by throwing electrified sand on clouds which are colloidal
solutions or charged particles of water in air.
(8) Smoke precipitation : Smoke coming out of the chimney is industrial area is a nuisance and health
hazard. It is a colloidal particles are charged particles and thus they are removed from fuel gases by
electrical precipitation (Cottrell Precipitator).

In cottrell precipitator, the smoke is made to pass through chambers fitted with highly electrically
charged plates which precipitate the carbon and dust particles leaving in the gases to escape through
chimney (figure).

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(9) Sewage disposal : Sewage water consists of particles of dirt, rubbish, mud, etc., which are of colloidal
dimensions and carry an electric charge and thus do not settle down easily. These particles can thus be
removed by cataphoresis. A system of two tanks fitted with metallic electrodes is used for this purpose.
When electric field is created, then the dust particles are coagulated on he oppositely charged electrodes.
The deposit may be utilized as a manure.
(10) Cleansing action of soap and detergent : Soap solution may be used to wash off the dirt sticking to
the fabric, in the presence
(i) If forms a collodial solution in water forms (miscelles), removes dirt by simple adsorption of oily
substance and thus washes away.
(ii) It decreases the interfacial tension between water and grease, and it causes the emulsification of grease
in water. By mechanical action such as rubbing, the dirt particles are also detached alongwith the only
material.
(11) In Photography : Various colloidal system are used in photographic process. In the preparation of
photographic plates, the silver bromide in gelatin is coated on thin glass plates. In developing and
fixation, various colloidal substances are used. In different kinds of colour printing, gelatin and other
colloidal mixtures are used.
(12) Blue colour of the sky : Colloidal particles scatter only blue light and the rest of is absorbed. In sky
there are a number of dust and water particles. They scatter blue light and, therefore, sky looks bluish.
If there were no scattering, the sky would have appeared totally dark.
ADSORPTION
INTRODUCTION
This tendency of accumulation of molecular species at the surface than in the bulk of a solid (or liquid)
is termed adsorption. The molecular species or substance which concentrates or accumulates at the
surface is termed adsorbate and the material on whose surface the adsorption has taken place is called
adsorbent.

DISTINCTION BETWEEN ADSORPTION AND ABSORPTION


In adsorption the concentration of the adsorbate increases only at the surface of the adsorbent, while
in absorption the concentration is uniform throughout the bulk of the solid.

× × ××× ×××××××××
×××× ×× ×× ×
× ×× ×
×
× × × ×
× × ×× ×
×
× × × × ×
×
×× ×××××× ×
×××××××× ×
×
×
× ×××
Adsorption Absorption Sorption

Adsorption is due to the fact that the surface particles of the adsorbent are in different state than the
particles inside the bulk. Inside the adsorbent all the force acting between the particles are mutually
balanced but on the surface the particles are not surrounded by atoms or molecules of their kind on all
sides and hence they possess unbalanced or residual attractive forces. These forces of the adsorbent
are responsible for attracting the adsorbate particle on its surface.

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TYPES OF ADSORPTION
There are two main types of adsorption of gases on solids.
If accumulation of gas on the surface of a solid occurs on account of weak van der Walls’ force, the
adsorption is termed as physical adsorption or physi-sorption. When the gas molecules or atoms are
held to the solid surface by chemical bonds, the adsorption is termed chemical adsorption or
chemisorption. The chemical bonds may be covalent or ionic in nature. Chemisorption has a rather high
energy of activation and is, therefore, often referred to as activated adsorption. Sometimes these two
processes occur simultaneously and it is not easy to ascertain the type of adsorption. A physical
adsorption at low temperature may pass into chemisorption as the temperature is increased. For example,
hydrogen is first adsorbed on nickel by van der Walls’ force. Molecules of hydrogen then dissociate
and hydrogen atoms are held on the surface by chemisorption.
COMPARISON OF PHYSI-SORPTION AND CHEMISORPTION
Physical adsorption Chemical adsorption
1. It is caused by intermolecular van der Walls’ It is caused by chemical bond formation.
forces.
2. It is not specific. It is highly specific.
3. It is reversible. It is irreversible.
4. It depends on the nature of gas. More easily It depends on the nature of gas. Gases which form
com liquefiable gases are adsorbed readily. pounds with the adsorbent exhibit chemi-sorption.
5. Heat of adsorption is low. Heat of adsorption is high.
6. Low temperature is favourable. It decreases High temperature is favourable. It increases with
increase with increase of temperature. of temperature.
7. No appreciable activation energy is involved. High activation energy is involved.
8. High pressure is favourable. Decrease of High pressure is favourable. Decrease of pressure does
pressure causes desorption. not cause desorption.
9. It depends on the surface area. It increases It also depends on the surface area. It increases with
with increase of surface area. increase of surface area.
10. It forms multilayers on adsorbent surface It forms unimolecular layer.
under high pressure.

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FREUNDLICH ADSORPTION ISOTHERM


Freundlich, in 1909, gave an empirical relationship between the quantity of gas adsorbed by unit mass
of solid adsorbent and pressure at a particular temperature. The relationship can be expressed by the
following equation.

Amount of gas adsorbed per


–78°C

gm of adsorbent (a)
–29°C
0°C

Adsorption isotherm
x
= k · p1/n ....(i)
m
where ‘x’ is the mass of the gas adsorbed on a mass ‘m’ of the adsorbent at a pressure P. k and n are
constants which depend on the nature of the adsorbent and the gas at a particular temperature.
Y
1
 b Slope = –n
a
Log m
x

log k (Intercept)

O X
Log P

Langmuir Adsorption Isotherm :- Freundlich isotherm

x aP
=
m 1  bP

SUMMARY :
(1) Molecules at the surface of a solid, a metal, or a liquid experience in net inward force of attraction with
free valencies.
(2) The phenomenon of attracting and retaining the molecules of a substance on the surface of a solid or a
liquid resulting in the higher concentration of the molecules on the surface is called adsorption.
(3) The substance adsorbed on the surface is called adsorbate and the substance on which it is adsorbed
is called adsorbent.
(4) The reverse process i.e. removal of adsorbed substance from the surface is called desorption.
(5) The adsorption of gases on the surface of metals is called occlusion.
(6) The term sorption is employed when adsoption as well as absorption take place simultaneously.
(7) Adsorption is a surface phenomenon, whereas absorption is a bull phenomenon. Adsorption occurs
only at the surface of adsorbent, whereas absorption occurs throughout the body of the material.
(8) When the concentration of the adsorbate is more on the surface of the adsorbent than in the bulk, it is
called positive adsorption.

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(9) When the concentration of the adsorbate is less relative to its concentration in the bulk, it is called
negative adsorption.
(10) When a gas is adsorbed at the surface of a solid by week forces (Vander Waal’s forces), it is called
physical adsorption.
(11) When a gas is held on the surface of a solid by forces similar to those of a chemical bond, it is called
chemical adsorption or chemiosorption.
(12) Adsorption is accompanied by evolution of heat. The amount of heat evolved when one mole of a gas is
adsorbed on a solid, is known as molar heat of adsorption. Its magnitude depends upon the nature of the
gas.
(13) The magnitude of gaseous adsorption depends upon temperature, pressure, nature of the gas and the
nature of the adsorbent.
(14) Adsorption decreases with increase in temperature, since it is accompanied by evolution of heat.
(15) The adsorption increases with increase in pressure, since adsorption of gas leads to decrease in pressure.
(16) The variation of adsorption with pressure at a constant temperature is called isotherm.
(17) At low pressure, the amount of the gas adsorbed per unit quantity of adsorbent is proportional to the
pressure. At high pressure, the amount of adsorbed gas is independent of pressure. At intermediate
pressures, Freundlich adsorption isotherm is expected to hold
(18) More readily soluble and easily liquefiable gases HCl, Cl2 , SO2 and NH3 are adsorbed more than the
so called permanent gases such as H2 , O2 , N2 etc. because Vander Waal’s forces involved in adsorption
are much predominant in the former gases than the latter category of gases.
PROFICIENCY TEST
Q.1 Fill in the blanks with appropriate items:

1. The substance on whose surface adsorption takes place is called an _____________.

2. Removal of adsorbate from the surface of adsorbent is called _____________.

3. Migration of colloidal particles under the effect of electric field is called _____________.

4. The heat of adsorption in case of physisorption is approximately _____________.

5. The phenomenon of zig-zag motion of colloidal particles is known as _____________.

6. Lyophilic sols are _____________ stable than lyophobic sols.

7. Electrical properties of a colloidal solution are demonstrated by _____________.

8. Tyndall effect takes place due to _____________ of light by collloidal particles.

9. The liquid-liquid colloidal dispersions are called _____________.

10. The movement of dispersion medium under the influence of an electric field is called _____________.

11. Smoke is a colloidal solution of _____________ in _____________.

12. The adhering of the molecules of a gas on the surface of a solid is called _____________.

13. The protective action of different colloids is compared in terms of _____________.

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14. The colloidal dispersion of a liquid in a liquid is called _____________.

15. The colloidal dispersions of liquids in solid media are called _____________.

Q.2 True/False statements

1. Physisorption is non-specific.

2. Chemisorption needs activation energy.

3. A graph of x/m vs temperature at constant pressure is called adsorption isotherm.

4. Suspensions have solute particles with size less than 1 nm.

5. Fe(OH)3 sol contains positively charged colloidal particles.

6. Chemisorption is irreversible.

7. Adsorption isobars of chemisorption and physisorption are of the same type.

8. Milk is an example of water in oil emulsions.

9. Gold sol can be prepared by Bredig's arc method.

10. Gel is a system in which liquid is the dispersed phase and solid is the dispersion medium.
Select the correct alternative. (Only one is correct)

Q.1 Which gas will be adsorbed on a solid to greater extent.


(A) A gas having non polar molecule
(B) A gas having highest critical temperature (Tc)
(C) A gas having lowest critical temperature.
(D) A gas having highest critical pressure.

Q.2 Which of the following factors affects the adsorption of a gas on solid?
(A) Tc(critical temp.) (B) Temperature of gas
(C) Pressure of gas (D) All of them

Q.3 The volume of gases NH3, CO2 and CH4 adsorbed by one gram of charcoal at 298 K are in
(A) CH4 > CO2 > NH3 (B) NH3 > CH4 > CO2
(C) NH3 > CO2 > CH4 (D) CO2 > NH3 > CH4

Q.4 The heat of physisorption lie in the range of


(A) 1 – 10 kJ mol–1 (B) 20 to 40 kJ mol–1
(C) 40 to 200 kJ mol–1 (D) 200 to 400 kJ mol–1

Q.5 Adsorption is multilayer in case of


(A) physical adsorption (B) chemisorption
(C) in both (D) none of the these

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Q.6 Reversible adsorption is


(A) chemical adsorption (B) physical adsorption
(C) both (D) none

Q.7 Which of the following is not a gel?


(A) Cheese (B) Jellies (C) Curd (D) Milk

Q.8 An emulsion is a colloidal system of


(A) two solids (B) two liquids
(C) one gas and one solid (D) one gas and one liquid

Q.9 Which of the following is a lyophobic colloid?


(A) Gelatin (B) Sulphur (C) Starch (D) Gum

Q.10 The nature of bonding forces in adsorption


(A) purely physical such as Van Der Waal's forces
(B) purely chemical
(C) both chemical and physical always
(D) none of these

Q.11 The Tyndall effect associated with colloidal particles is due to


(A) presence of electrical charges (B) scattering of light
(C) absorption of light (D) reflection of light

Q.12 Which one of the following is not applicable to chemisorption?


(A) Its heat of adsorption is high (B) It takes place at high temperature
(C) It is reversible (D) It forms mono-molecular layers

Q.13 In the colloidal state the particle size ranges


(A) below 1 nm (B) between 1 nm to 100 nm
(C) more than 100 nm (D) none of the above

Q.14 All colloids


(A) are suspensions of one phase in another
(B) are two-phase systems
(C) contain only water-soluble particles
(D) are true solutions

Q.15 Colloids can be purified by


(A) condensation (B) peptization (C) coagulation (D) dialysis

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Q.16 Milk is an example of


(A) emulsion (B) suspension (C) foam (D) sol.

Q.17 Colloidal particles in a sol. can be coagulated by


(A) heating (B) adding an electrolyte
(C) adding oppositely charged sol (D) any of the above methods

Q.18 Emulsifier is an agent which


(A) accelerates the dispersion (B) homogenizes an emulsion
(C) stabilizes an emulsion (D) aids the flocculation of an emulsion

Q.19 Fog is a colloidal system of


(A) gas in liquid (B) liquid in gas (C) gas in gas (D) gas in solid

Q.20 Given below are a few electrolytes, indicate which one among them will bring about the coagulation of
a gold sol. quickest and in the least of molar concentration?
(A) NaCl (B) MgSO4 (C) Al2(SO4)3 (D) K4[Fe(CN)6]

Q.21 When a lyophobic colloidal solution is observed , we can see


(A) light scattered by colloidal particle
(B) size of the colloidal particle
(C) shape of the colloidal particle
(D) relative size of the colloidal particle
Q.22 Colloidal solutions are classified on the basis of
(A) molecular size (B) orgainc or inorganic
(C) surface tension value (D) pH value

Q.23 The electrical charge on a colloidal particle is indicated by


(A) Brownian movement (B) electrophoresis
(C) ultra microscope (D) molecular sieves

Q.24 The minimum concentration of an electrolyte required to cause coagulation of a sol is called
(A) flocculation value (B) gold number (C) protective value (D) none of these

Q.25 Smoke precipitator works on the principle of


(A) distribution law (B) neutralization of charge on colloids
(C) Le-Chaterlier's principle (D) addition of electrolytes
Q.26 Which one of following statements is not correct in respect of lyophilic sols?
(A) There is a considerable interaction between the dispersed phase and dispersion medium
(B) These are quite stable and are not easily coagulated
(C) They need stabilizing agent
(D) The particle are hydrated

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Q.27 As2S3 sol is


(A) positive colloid (B) negative colloid (C) neutral colloid (D) none of the above

Q.28 At the critical micelle concentration (CMC) the surfactant molecules


(A) decompose (B) dissociate
(C) associate (D) become completely soluble

Q.29 Alums purify muddy water by


(A) dialysis (B) absorption (C) coagulation (D) forming true solution

Q.30 Solute dispersed in ethanol is called


(A) emulsion (B) micelle (C) hydrophilic sol. (D) alcosols

Q.31 Which one of the following is lyophillic colloid?


(A) Milk (B) Gum (C) Fog (D) Blood

Q.32 Small liquid droplets dispersed in another liquid is called


(A) suspension (B) emulsion (C) gel (D) true solution

Q.33 The process which is catalysed by one of the product is called


(A) acid-base catalysis (B) autocatalysis
(C) negative catalysis (D) homogeneous catalysis

Q.34 Tyndall effect would be observed in a


(A) solution (B) solvent (C) precipitate (D) colloidal sol.

Q.35 Crystalloids differ from colloids mainly in respect of


(A) electrical behaviour (B) particle size
(C) particle size (D) solubility

Q.36 A liquid is found to scatter a beam of light but leaves no residue when passed through the filter paper.
The liquid can be described as
(A) a suspension (B) oil (C) a colloidal sol. (D) a true solution

Q.37 The ability of an ion to bring about coagulation of a given colloid depends upon
(A) its charge (B) the sign of the charge alone
(C) the magnitude of the charge (D) both magnitude and sign of charge

Q.38 An arsenious sulphide sol. carries a negative charge. The maximum precipitating power of this sol. is
possessed by
(A) K2SO4 (B) CaCl2 (C) Na3PO4 (D) AlCl3

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Q.39 Which of the following is an example of associated colloid?


(A) Protein + water (B) Soap + water (C) Rubber + benzene (D) As2O3 + Fe(OH)3

Q.40 Adsorption of gases on solid surface is generally exothermic because


(A) enthalpy is positive (B) entropy decreases
(C) entropy increases (D) free energy increases

Q.41 Among the following, the surfactant that will from micelles in aqueous solution at the lowest molar
concentration at ambient conditions is
(A) CH3(CH2)15N+(CH3)3Br¯ (B) CH3(CH2)11OSO3¯Na+
(C) CH3(CH2)6COO¯Na+ (D) CH3(CH2)11N+(CH3)3Br¯

Q.42 The disperse phase in colloidal iron (III) hydroxide and colloidal gold is positively and negatively
charged respectively. Which of the following is not correct ?

(A) Magnesium chloride solution coagulates the gold sol more readily than iron (III) hydroxide sol.
(B) Sodium sulphate solution cause coagulation in both sols.
(C) Mixing of the sols has no effect.
(D) Coagulation in both sols can be brought about by electrophoresis.
Question No. 43 to 45 (3 questions)
Whenever a mixture of gases is allowed to come in contact with a particular adsorbent under the same
conditions, the more strong adsorbate is adsorbed to greater extent irrespective of its amount present,
e.g. H2O is adsorbed to more extent on silica gel than N2 and O2. This shows that some adsorbates
are preferentially adsorbed. It is also observed that preferentially adsorbable adsorbents can displace
a weakly adsorbed substance from the surface of an adsorbent.
Q.43 Which of the following gases is adsorbed to maximum extent:
(A) He (B) Ne (C) Ar (D) Xe
Q.44 Which of the gas can displace remaining all the gases
(A) O2 (B) N2 (C) CO (D) H2
Q.45 When temperature is increased
(A) extent of adsorption increases
(B) extent of adsorption decreases
(C) no effect on adsorption
(D) extent of adsorption first decreases, then increases
Question No. 46 to 49 (4 questions)
In macromolecular type of colloids, the dispersed particles are themselves large molecules (usually
polymers). Since these molecules have dimensions comparable to those of colloidal particles, their
dispersions are called macromolecular colloids. Most lyophilic sols belong to this category. There are
certain colloids which behave as normal strong electrolytes at low concentrations, but exhibit colloidal
properties at higher concentrations due to the formation of aggregated particles. These are known as
micelles or associated colloids. Surface active agents like soaps and synthetic detergents belong to this
class.

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· Critical micelle concentration (CMC) is the lowest concentration at which micelle formation
appears. CMC increases with the total surfactant concentration. At concentration higher than
CMC, they form extended parallel sheets known as lamellar micelles which resemble biological
membranes. With two molecules thick, the individual molecule is perpendicular to the sheets
such that hydrophilic groups are on the outside in aqueous solution and on the inside is a
non-polar medium.
· In concentrated solutions, micelles take the form of long cylinders packed in hexagonal arrays
and are called lytotropic mesomorphs.
· In an aqueous solution (polar medium), the polar group points towards the periphery and the
hydrophobic hydrocarbon chains point towards the centre forming the core of the micelle.
· Micelles from the ionic surfactants can be formed only above a certain temperature called the
Kraft temperature.
· They are capable of forming ions
· Molecules of soaps and detergents consist of lyophilic as well as lyophilic parts which associate
together to form micelles.
· Micelles may contain as many as 100 molecules or more.
Q.46 Select incorrect statement(s):
(A) Surface active agent like soaps and synthetic detergents are micelles
(B) Soaps are emulsifying agents
(C) C17H35 (hydrocarbon part) and –COO– (carboxylate) part of stearate ion (C17H35COO–) both
are hydrophobic
(D) All are incorrect statements

Q.47 Which part of the soap (RCOO–) dissolves grease and forms micelle?
(A) R part (called tail of the anion) (B) –COO– part (called head of the anion)
(C) both (A) and (B) (D) none of these

Q.48 In multimolecular colloidal sols, atoms or molecules are held together by:
(A) H-bonding (B) van der Waals forces
(C) ionic bonding (D) polar covalent bonding

Q.49 Cleansing action of soap occurs because:


(A) oil and grease can be absorbed into the hydrophobic centres of soap micelles and washed away
(B) oil and grease can be absorbed into hydrophilic centres of soap micelles acid washed away
(C) oil and grease can be absorbed into both hydrophilic and hydrophobic centres but not washed
away
(D) cleansing action is not related to micelles

Question No.50 to 52 (3 questions)


The protective power of the lyophilic colloids is expressed in terms of gold number a term introduced
by Zsigmondy.Gold number is the number of milligram of the protective colloid which prevent the
coagulation of 10 ml of red gold sol. when 1 ml of a 10 percent solution of sodium chloride is added to
it. Thus, smaller the gold number of lyophilic colloid, the greater is the protective power.

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Q.50 On addition of one mL of solution of 10% NaCl to 10 mL of red gold sol in presence of 0.025 g of
starch, the coagulation is just prevented. The gold number of starch is
(A) 0.025 (B) 0.25 (C) 2.5 (D) 25

Q.51 Which of the following statement(s) is/are correct


(A) Higher the gold number, more protective power of colloid
(B) Lower the gold number, more the protective power
(C) Higher the coagulation value, more the coagulation power
(D) Lower the coagulation value, higher the coagulation power

Q.52 Gold number gives an indication of


(A) protective nature of colloids (B) purity of gold in suspension
(C) the charge on a colloidal solution of gold (D) g-mole of gold per litre

Question No. 53 & 57 (5 questions)


These questions consist of two statements each, printed as assertion and reason, while answering these
questions you are required to choose any one of the following responses.
(A) If assertion is true but the reason is false.
(B) If assertion is false but the reason is true.
(C) If both assertion and reason are true and the reason is a correct explanation of assertion.
(D) If both assertion and reason are true but reason is not a correct explanation of assertion.

Q.53 Assertion : Isoelectric point is pH at which colloidal can move towards either of electrode
Reason : At isoelectric point, colloidal particles become electrically neutral.

Q.54 Assertion : When AgNO3 is treated with excess of potassium iodide, colloidal particles gets
attracted towards anode.
Reason : Precipitate adsorb common ions (excess) and thus become charged.

Q.55 Assertion : For adsorption G, H, S all have –ve values
Reason : Adsorption is a spontaneous exothermic process in which randomness decreases
due to force of attraction between adsorbent and adsorbate.

Q.56 Assertion : A gas with higher critical temperature gets adsorbed to more extent than a gas
with lower critical temperature.
Reason : The easily liquifiable gases get adsorbed to more extent.

Q.57 Assertion : Micelles are formed by surfactant molecules above the critical micellar
concentration (CMC).
Reason : The conductivity of a solution having surfactant molecules decreases sharply at
the CMC.

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Q.58 Assertion : The micelle formed by sodium stearate in water has –COO¯ groups at the surface.
Reason : Surface tension of water is reduced by the addition of stearate.

Q.59 Assertion : Fe3+ can be used for coagulation of As2S3 sol.


Reason : Fe3+ reacts with As2S3 to give Fe2S3.

Q.60 Assertion : The conversion of fresh precipitate to colloidal state is called peptization.
Reason : It is caused by addition of common ions.

Select the correct alternative. (More than one are correct)

Q.61 Which of the following is/are correct statements


(A) Hardy Schulz rule is related to coagulation
(B) Brownian movement and Tyndall effect are shown by colloids
(C) When liquid is dispersed in liquid, it is called gel.
(D) Gold number is a measure of protective power of lyophillic colloid.
Q.62 Which statements is/are correct?
(A) Physical adsorption is multilayer non-directional and non specific
(B) Chemical adsorption is generally monolayer and specific in nature
(C) Physical adsorption is due to free valence of atoms
(D) Chemical adsorption is stronger than physical adsorption

Q.63 Which of the following is/are correct for lyophillic sols?


(A) Its surface tension is lower than that of H2O
(B) Its viscosity is higher than that of water
(C) Its surface tension is higher than that of water
(D) Its viscosity is equal to that of water

Q.64 Which statement/s is/are correct


(A) A solution is prepared by addition of excess of AgNO3 solution in KI solution. The charge
likely to develop on colloidal particle is positive.
(B) The effects of pressure on physical adsorption is high if temperature is low.
(C) Gold number is the index for extent of gold plating done.
(D) None

Q.65 Colloidal solution can be purified by


(A) Dialysis (B) Electrodialysis (C) Electrophoresis (D) Ultrafiltration

Q.66 Coagulation of colloids can be achieved by


(A) Centrifugation (B) Adding electrolyte (C) Change in pH (D) Adding water

Q.67 When –vely charged colloid like As2S3 sol is added to + vely charged Fe(OH)3 sol in suitable amounts
(A) Both the sols are precipitated simultaneously
(B) This process is called mutual coagulation
(C) They becomes + vely charged colloid
(D) They become – vely charged colloid
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Q.68 Which of the following is not lyophillic


(A) Gelatin sol (B) Silver sol (C) Sulphur sol (D) As2S3 sol

Q.69 Colloidal Gold can be prepared by


(A) Bredig’s are method (B) Reduction of AuCl3
(C) Hydrolysis (D) Peptization

Q.70 Which of the following are colloids?


(A) Milk (B) Ice cream (C) Urea solution (D) Blood

Q.71 Which are the properties of sols?


(A) Adsorption (B) Tyndall effect (C) Flocculation (D) Paramagnetism

Q.72 The migration of colloidal particles under the influence of an electrical field is known as
(A) electro osmosis (B) electrophoresis (C) electrodialysis (D) None

Q.73 Among the electrolytes Na2SO4, CaCl2, Al2(SO4)3 and NH4Cl, the most effective coagulation agent
for Sb2S3 sol is [JEE 2009]
(A) Na2SO4 (B) CaCl2 (C) Al2(SO4)3 (D) NH4Cl

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ANSWER KEY
PROFICIENCY TEST

Q.1
1. adsorbent 2. desorption 3. electrophoresis 4. 20–40 kJ-mol–1

5. Brownian movement 6. more 7. elecrophoresis

8. scattering 9. emulsions 10. electro-osmosis 11. solid in gas


12. adsorption 13. gold number 14. emulsion 15. gel

Q.2
1. [T] 2. [T] 3. [F] 4. [F] 5. [T]

6. [T] 7. [F] 8. [F] 9. [T] 10. [T]

Select the correct alternative. (Only one is correct)

Q.1 B Q.2 D Q.3 C Q.4 B Q.5 A Q.6 B


Q.7 D Q.8 B Q.9 B Q.10 D Q.11 B Q.12 C
Q.13 B Q.14 B Q.15 D Q.16 A Q.17 D Q.18 C
Q.19 B Q.20 C Q.21 A Q.22 A Q.23 B Q.24 A
Q.25 B Q.26 C Q.27 B Q.28 C Q.29 C Q.30 D
Q.31 B Q.32 B Q.33 B Q.34 D Q.35 C Q.36 C
Q.37 D Q.38 D Q.39 B Q.40 B Q.41 A Q.42 C
Q.43 D Q.44 C Q.45 B Q.46 C, D Q.47 A Q.48 B
Q.49 A Q.50 D Q.51 B; D Q.52 A Q.53 B Q.54 C
Q.55 C Q.56 C Q.57 D Q.58 A Q.59 C Q.60 B

Select the correct alternative. (More than one are correct)

Q.61 A; B; D Q.62 A; B; D Q.63 A; B Q.64 A; B Q.65 A; B; D


Q.66 A; B; C Q.67 A; B Q.68 B; C; D Q.69 A; B
Q.70 A; B; D Q.71 A; B; C Q.72 B Q.73 C

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