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Aditya vardhan
Solutions & Colligative properties 1 adichemadi @ gmail.com

SOLUTIONS

Solution : A homogeneous mixture of two or more substances.

E.g. Aqueous sugar solution formed by dissolving sugar in water.
Solvent : The components which is present in large quantity in a solution.
Solute : The component which is present in a lesser quantity in a solution.
Solution = solvent + solute
Binary solution : The solution which contains only two components.

* Based on the physical state of solvent and solute, the solutions are classified as
Solvent Solute Example
Solid Solid Copper in Gold
Solid Liquid Mercury in Gold
Solid Gas Occlusion of H2 in Pd

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Liquid Solid Sugar in water
Liquid Liquid Alcohol in water
Liquid Gas Soda water (CO2 in water)

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Gas Solid Camphor in air

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Gas Liquid Water vapour in air

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Gas Gas Air (O2 in N2 )

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* Based on the nature of the solvent, the solutions are classified into
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1) Aqueous solutions - in which water is the solvent.

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2) Nonaqueous solutions - in which the solvent is other than water

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E.g., CHCl3 , C6H6, CCl4 etc.,

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3) Alcoholic solutions - in which Ethyl alcohol is the solvent.

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* Based on the relative quantity of solute, the solutions are classified into
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Concentrated Solutions : The relative amount of solute is very high.

V.

Dilute Solutions : The relative amount of solute is very low.

Methods of expressing concentration :

Concentration or strength : The amount of solute present in specific amount of solution is gener-
ally referred to as
concentration or strength of solution.
Following are some methods which are used to measure the concentration of a solution.
1) Weight percentage
w
(i) % denotes weight of solute in 100 mL of solution.
V
w
(ii) % denotes weight of solute in 100 g of solution.
w
2) Molarity (M)
3) Normality (N)
4) Molality (m)
5) Mole fraction (  )
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Molarity (M) : The number of moles of a solute present in one litre of the solution.
no.of moles of solute  n 
M=
Volume of solution in litres  V 

n
M=
V  in L 

Weight of the solute W

n= 
Gram molecular Weight of thesolute GMW

w 1
M = x
GMW V  in L 

W 1000
M= x
GMW V  in mL 
Units : mole. Litre-1= Molar (M)

N
Note : Molarity depends on temperature.

HA
* When one mole of the solute is present in 1litre of solution,
then the molarity (M) = 1 M (one molar solution)

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* When 0.1 mole of the solute is present in 1 litre of solution,
by

then the molarity (M) = 0.1 M ( decimolar solution)

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VA
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Problems
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1) What is the molarity of 500 mL of solution made by dissolving 2 moles of glucose in water?
AN IOR
Pr

2) What is the molarity of 250 mL of an aqueous solution containing 10 grams of NaOH?

YA
AR N

3) Calculate the weight of solute in 100 mL of glucose solution.

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4) What is the molarity of 10.6% Na2CO3 solution?

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5) Calculate the molarity of 9.8% H2SO4 solution. The specific gravity of the solution is 1.12.
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Normality : The number of gram equivalent weights of the solute present in one litre of solution.
number gram equivalent weights of the solute (n e )
VA

N=
volume of the solution (V) in lit
V.

weight of the solute (w)

ne 
Gram equivalent weight of the solute (GEW)

W 1
N= x
GEW V(in L)
or
W 1000
N= x
GEW V(in mL)
Units : gram equivalent weights . Litre-1 = Normal (N)
The one litre of solution containing 1 gram equivalent weight of the solute is called one normal
solution.
If 0.1 gram equivalent weights are present, then that solution is called decinormal solution.
Calculation of Gram equivalent weights (GEW)
* Gram equivalent weight of a substance depends on it’s nature and the chemical reaction in which it
is participating. It can be calculated by using following formula.
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GMW
GEW 
Equivalent factor
Equivalent weights of acids :
Gram molecular weight  or  formula weight
GEW =
basicity
Basicity : Number of replaceable hydrogens present in an acid molecule is called basicity of acid.

Acid Basicity M.wt Eq.wt

36.5
HCl (Hydrochloric acid) 1 36.5  36.5
1

N
HO S OH 98
H2SO4 ( Sulfuric acid) 2 98  49

HA
2
O

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O
VA
AL O
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63
HNO3 ( Nitric acid) N 1 63  63
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HO O 1
AN IOR
Pr
YA
AR N

O
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98
AG T

H3PO4( Orthophosphoric acid) HO P OH

VI

3 98  32.9
3
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OH
AD

O
VA

82
H3PO3( orthophosphorous acid) H P OH
2 82 = 41
V.

2
OH

O
66
H3PO2 (Hypophosphorus acid) H P H
1 66  66
1
OH

O
60
CH3COOH (Acetic acid) H3C C 1 60  60
1
O H

Equivalent weights of bases :

Molecular weight  or  formula weight of base
GEW =
Acidity
Acidity : Total number of OH ions furnished by a base is called acidity of the base.
-

1) NaOH
GFW 40
GEW    40 g
Acidity 1
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2) KOH
GFW 56
GEW    56 g
Acidity 1
3) Ca  OH2
GFW 74
GEW    37 g
Acidity 1
Equivalent weight of Salts:
Formula Weight of the salt
GEW=
total amount of charge present on either cations  or  Anions

 Na   Cl 
(1) NaCl 
FW 58.5
 GEW    58.5 g

N
1 1

HA
 2 Na   CO3 2
(2) Na2CO3 
FW 106
 GEW    53g

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2 2
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 A l 3   3C l 
(4) AlC l3  
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VA
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FW 133.5
G C
 GEW    44.5 g
ep

3 3
AN IOR
Pr

Equivalent weight of oxidants and Reductants:

YA
AR N

GMW
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GEW =
Number of electrons lost or gained by a molecule
AG T
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A n+ + Bn-
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A + B  
AD

Reductant Oxidant
VA

 A n+ + ne  :
A  oxidation
V.

 n
B+ne 
B : Reduction
(1)KMnO 4
In acidic medium
+
Mn 7+ + 5e- 
H
 Mn +2
GMW 158
GEW = = = 31.6g
5 5
In basic medium
-
Mn 7+ + 3e- 
OH
 Mn 4+
GMW 158
GEW = = =52.66g
3 3
(2) K 2 Cr2 O7
+
Cr 6+ +3e- 
H
 Cr 3+
GMW 294
GEW = = =49g (since two chromium atoms gain 2 x 3 = 6 electrons)
6 6
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Relation between Molarity and Normality

n W 1
Molarity ( M )   X
V GMW V
ne W 1
Normality ( N )   X
V GEW V
GMW
But GEW 
Equivalent factor

 W 1
N  X  x equivalent factor
 GMW V 
N = M x equivalent factor

N
For acids N = M x basicity

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For bases N = M x acidity
For salts N = M x total charge either on cations or anions

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For oxidants or reductants N = M x loss or gain of electrons
by

Problems
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1) What is the normality of 100 mL of solution containing 5.3 g of Na2CO3 ?

VA
AL O
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G C
2) Calculate the weight of solute in 250 mL of 0.8 N H2SO4?
ep

AN IOR

3) What is the normality of 20% NaOH solution?

Pr
YA

4) The specific gravity of 2.45% H2SO4 solution is 1.245. Calculate its normality.
AR N
W JU

Law of Dilution :
AG T
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For a solution, let the

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initial Molarity = M1
AD

Initial Volume =V1

No of moles in solute = n1
VA
V.

n1
 M1 =  n1 = M1V1
V1
After adding small volume of solvent,
Final molarity =M2
Final volume = V2
No of moles in solute = n1
n1
 M2 =  n1 = M 2 V2
V2

 M 1V1  M 2V2
similarly
N1V1  N 2V2

Concentration of mixed solution

In the first solution In the second solution
Molarity = M1 Molarity = M2
Volume = V1 Volume = V2
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no. of moles of solute = n1 no of moles of solute = n2
For the mixed solution formed by above solutions,
n1  n2 M 1V1  M 2V2
M mix  
V1  V2 V1  V2

N1V1 +N 2 V2
similarly N Mix =
V 1  V2
Calculations involved in acid-base titrations
Formulae
1. NaVa = NbVb
Where Na = Normality of acid solution
Nb = Normality of base solution
Va = Volume of acid solution

N
Vb = Volume of base solution

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M a Va M b Vb
2. 
na nb

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Where M a = Molarity of acid solution
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by

M b = Molarity of base solution

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VA
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Va = Volume of acid solution

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Vb = Volume of base solution

AN IOR
Pr
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n a = Stoichiometric coefficient of acid in the balanced equation

AR N
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n b = Stoichiometric coefficient of base in the balanced equation

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Problems:
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1) How much water is to be added to 100 mL of 2 M H2SO4 to get 0.5 M H2SO4 ?

AD

2) What is the normality of solution formed by adding 750 mL of water to 250 mL of 0.6 N solution
of acetic acid?
VA

3) 100 mL of 2 M HCl and 200 mL of 3 M HCl are mixed. What is the molarity of the mixture?
V.

4) Equal volumes of 0.8 N and 0.2 N Na2CO3 solutions are mixed. What is the final normality of
the solution formed?
5) 20 mL of 0.5 M NaOH solution is required to completely neutralize 40 mL of HCl. Calculate the
molarity of HCl solution.
6) Calculate the volume of 0.4 M NaOH solution required to completely neutralize 100 mL of 0.2
M H2SO4 solution.
7) 10 mL of Na2CO3 solution is required to neutralize 20 mL of 0.2 M HCl completely. What is the
strength of Na2CO3 solution? Calculate the amount of Na2CO3 in a 500 mL of solution.
8) Calculate the volume of 1.5 N acid solution required to completely neutralize 300 mL of 0.5 N
alkaline solution.

Molality (m)
The number of moles of solute present per kilogram of the solvent is called as Molality (m) of the
solution.
number of moles of the solute (n)
molality(m) =
weight of the solvent in kilograms (W1 )

n
i.e., m=
W1 (in Kg)
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w2
But n
GMW2
w2 1
 m= x
GM W 2 W1 (in Kg)
or
w2 1000
or m= x
GM W 2 W1 (in g)

Units : mole.Kg -1 = Molal (m)

Note: Molality does not change with temperature.
Problems
1) 4.6 g of ethyl alcohol is dissolved in 500 g of water. Calculate the molality of solution formed.

N
2) Calculate the molality of 20% NaOH solution.

HA
3) The specific gravity of 6.3% HNO3 solution is 1.063. What is the molality of solution?

E
Mole Fraction   :
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The ratio between the number of moles of one component of the solution to the total number of

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moles of all components of that solution is called as mole fraction of that component.
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The mole fraction of ith component in a solution containing ‘n’ components is given by
AN IOR
Pr
YA

ni
χi =
AR N

n1 +n 2 +............n i .........n n
W JU

For binary solutions

AG T
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W1
AD

n1 GMW1
the mole fraction of solvent  1  
n1  n2 W1 W2
VA


GMW1 GMW2
V.

W2
n2 GMW2
similarly mole fraction of solute   2  
n1  n2 W1 W2

GMW1 GMW2

* For dilute Solutions :

n2<<<<n1
 n1 + n 2  n1
w2

χ 2 = n 2 = MW2
n1 w1
MW1

w2 MW1
χ 2 = x
MW2 w1
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and χA  χB  1

Problems:
1) A solution containing 18 g of glucose and 178.2 g of water. What are the mole fractions of
glucose and water in this solution?

Vaporization : The spontaneous escaping of liquid molecules in to the space from the surface of the
liquid is called Vaporization of the liquid.

Rate of Vaporization : Number of molecules escaping in unit time from the surface of the liquid is
called rate of vaporization.
The factors affecting the rate of vaporization are
1. Area of the Surface
2. Nature of the liquid

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3. Temperature

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4. Velocity of gases flowing above the surface of the liquid

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Condensation : The spontaneous entry of vapour molecules into the liquid phase from vapor phase
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is called condensation.

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Rate of Condensation :The Number of molecules entering the liquid phase from the vapour phase
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in unit time is called rate of condensation.
ep

AN IOR

The state at which the rate of vaporization becomes equal to the rate of condensation is
Pr
YA

called equilibrium state.

AR N
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Vapour Pressure : The pressure exerted by vapour molecules over the surface of a liquid when
AG T
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both liquid and its vapour are in equilibrium with each other at a given temperature is called vapor
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pressure of the liquid. (at that temperature)

* Vapour pressure depends on the nature of liquid and temperature.
* The liquid with weak intermolecular forces has high vapor pressure.
VA

* The vapour pressure increases with increase in temperature as the average kinetic
V.

energy also increase.

Boiling Point : The temperature at which the vapour pressure of liquid becomes equal to the
atmospheric pressure is called boiling point.

Volatile liquids : The liquids with high vapour pressure and low boiling points.
Eg., Ethers, Ethyl alcohol, Acetone etc.,
Non - Volatile Liquids : The liquids with low vapour pressure and high boiling points.
Ex : H2O, octane, Benzene, carbon tetrachloride etc.,.
Similarly solutes are also classified in to volatile solutes and nonvolatile solutes.
Problems
1. Calculate the vapour pressure of a solution containing 10 g of a nonvolatile solute in 80 g of
ethanol at 298 K. Given the M.W. of solute as 120 the vapour pressure of alcohol is 22.45 mm of
Hg at 298 K.
2.The vapour pressure of a solution containing 108.24 g of a nonvolatile solute in 1000 g at H2O at
20oC is 17.354 mm of Hg. The vapour pressure of H2O at 20oC is 17.54 mm Hg. Find the
molecular weight of the substance.
3.The vapour pressure of a 4% solution of a nonvolatile solute in H2O at 373K is 74.5 cm Hg.
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Calculate the molecular weight of the solute.
4.What is the vapour pressure of 3 M of solution at 23oC? Vapour pressure of H2O at 23oC is 19.8
mm of Hg.

COLLIGATIVE PROPERTIES
The properties of solutions which only depends on the number of solute particles in it and not on the
nature of the solute are called colligative properties.
1. Relative lowering of vapor pressure (R.L.V.P)
2. Elevation in Boiling point  ΔTb 
3. Depression in freezing point  ΔTf 
4. Osmotic pressure (  )

Relative Lowering of vapour pressure (R.L.V.P) and Raoult’s law :

Lowering of vapour pressure  ΔP  (L.V.P) :

N
The vapour pressure of a solution (p) containing a nonvolatile solute is always less than the vapour

HA
pressure of pure solvent (P0). This phenomenon is called Lowering of vapour pressure  ΔP  .
vapour pressure of pure solvent = P0

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vapour pressure of solution = P
by

Lowering of vapour pressure (L.V.P) =  ΔP  = P0 - P

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VA
Relative Lowering of vapour pressure (R.L.V.P): AL O
ar

G C
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The ratio of lowering of vapour pressure  ΔP  to the vapour pressure of pure solvent (Po) is called
AN IOR
Pr

Relative Lowering of vapour pressure (R.L.V.P)

YA
AR N

o
P P  P
W JU

R.L.V.P = =
Po Po
AG T
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RAOULT’S LAW :
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The relative lowering of vapour pressure of dilute solutions containing a nonvolatile solute is equal to
the mole fraction of that solute
VA

ΔP
= X2
V.

Po
Where X 2 = mole fraction of the solute
P o -P n2
=
Po n1 +n 2
for dilute solution
n1 >>>> n 2
 n1  n 2  n1
P o -P n 2
And =
Po n1

P W2 MW1
 o
 x
P M W2 W1
Where
Po = vapour pressure of the pure solvent
P = vapour pressure of the dilute solution
W2 = wt of the solute
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MW2 = M.wt of the solute
W1 = wt of the solvent
MW1 = M.wt of the solvent
Applications : The unknown molecular weight of substances can determined by using this law.
Limitations :
1. Only applicable to dilute solutions
2. Solute must be nonvolatile
3. Solute should not under goes any molecular association or dissociation in the solution.
4. There is should be no chemical interaction between solute and solvent.
Ideal solutions:- The solutions which obey Raoult’s law are called ideal solutions.
Problems:
1) What is the vapour pressure of solution formed by dissolving 6 g of urea in 92 g of ethanol at 298
K? (The vapour pressure of alcohol is 22.45 mm Hg at 298 K)
2) The vapour pressure of solution formed by dissolving 120 g of non volatile solute in 1800 g of

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water at 20oC is 17.24 mm Hg. What is the molecular weight of solute? ( The vapour pressure of

HA
water at 20oC is 17.54 mm Hg)
Elevation in Boiling point (ΔTb )

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As the vapour pressure of solution containing non volatile solute is less than that of pure
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solvent, the temperature at which the vapour pressure of solution becomes equal to the atmospheric

LL
pressure is always greater than the boiling point of solvent. i.e., the boiling point of solution (Tb) is
ed
VA
always greater than the boiling point of pure solvent (Tb0)
AL O
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Tb  Tb o
AN IOR
Pr
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Tb  Tb o  Tb is called elevation in boiling point.

AR N
W JU

The increase in the boiling point of solution containing non volatile solute when compared to
AG T

the boiling point of pure solvent is called elevation in boiling point ( Tb ).
VI
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Relation between elevation in boiling point (ΔTb ) and molality (m) of the solution.
In the following diagram, the curves ABC, DEF & GHK show the relations between boiling points
and vapour pressure of pure solvent, solution-I and solution-II respectively.
VA
V.

t
en I
lv n II
So it o
i on
C lu t
So o lu
S
P0 B
F K
P1
E
Pressure

P2
H
A
D
G

T0 T1 T2
Temperature
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In the above graph
To, T1, T2 are boiling points of pure solvent, solution-I and solution-II respectively
Po, P1, P2 are vapour pressure of pure solvent, solution-I and solution-II at To

By considering above curves as almost straight lines,

From BFE & BKH triangles
BE BF

BH BK
Po  P1 T1  To
or P  P  T  T
o 2 2 o

P1 T1
or P  T
2 2

N
P  Tb

HA
From Raoult’s law
P
 X2

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Po
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by

where X2 = Mole fraction of solute

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ed

or P  Po X 2
VA
AL O
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so Tb  X 2
AN IOR
Pr
YA

or Tb  KX 2 ( where K= A proportionality constant)

AR N

But for dilute solutions

W JU
AG T

n2 W2 MW1
VI

X2   x
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n1 MW2 W1
AD

W2 1000
Molality (m) = MW x W
VA

2 1
V.

m x MW1
 X2 
1000
m x MW1
Tb = K x
1000
Now from the law of thermodynamics
RTo 2
K
v H

RT0 2 m x MW1
ΔTb = x
ΔvH 1000

or Tb  Kb m

RT0 2 x MW1 RT0 2

Where K b  = ( since  v H  lv x MW1 )
 v H x 1000 1v x 1000
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Where
Kb= molal elevation constant
R = Gas constant
To = boiling point of pure solvent
MW1 = molecular weight of solvent
 v H = Molar heat of vaporization of solvent
lv = latent heat of vaporization

Molal Elevation of boiling point constant or ebbulioscopic constant (Kb) : The elevation in
boiling point of one molal solution is called molal elevation constant.
Units: K. Kg. mol-1
Depression in freezing point of the solution ( T f )
The freezing point of solution (Tf) containing a non volatile solute is always less than the

N
freezing point of pure solvent (Tfo). This is called depression in freezing point ( T f ) .

HA
Tf  Tf o

T f o  T f  T f = depression in freezing point.

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by

* In the following diagram, the curves OP, ABC & DEF show the relations between freezing points
LL
ed

and vapour pressure of pure solvent, solution-I and solution-II respectively.

VA
AL O
ar

G C
ep

AN IOR
Pr

I II
nt n n
YA

e i o i o
lv ut ut
AR N

P so C Sol ol
W JU

F S
AG T
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Pressure

I
DE

O
AD

Po

A
P1 B
VA
V.

P2 D E
T2 T1 T0
Temperature

For dilute solutions, these curves are almost straight lines and hence from triangles ΔOAB & ΔODE
OB AB

OE DE
P0  P1 T0  T1

P0  P2 T0  T2
P1 T1

P2 T2
 P  T
From Raoult’s law
P
 X2
P0
or P  P0 X 2
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where X 2 = mole fraction of solute
P  X 2
 Tf  X 2
or Tf  KX 2
For dilute solutions
m x MW1
X2 
1000
m x MW1
 Tf  K x
1000
From the laws of thermodynamics
RT0 2
K
f H
RT0 2 m x MW1

N
  Tf  x
f H 1000

HA
or Tf  K f m

E
RT0 2 x MW1 RT0 2
RD
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by

where K f  
f H x1000 l f x1000

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Kf = Molal depression constant or Cryoscopic constant

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AL O
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R = Gas constant
AN IOR
Pr

T0 = Freezing point of solvent

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MW1 = Molecular weight of solvent

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 f H = Molar heat of freezing of solvent

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lf = latent heat of freezing

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Definition of Kf: Depression in freezing point of one molal solution containing a nonvolatile solute
is called molal depression in freezing point constant or cryoscopic constant.
Units: K. Kg. mol-1
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PROBLEMS
1. 0.1 moles of a nonvolatile and non-electrolytic solute is dissolved in 100 g of a solvent to elevate
it’s boiling point by 0.12oC. Calculate Kb of the solvent.
2. The elevation in boiling point of a solution containing 0.20 g of solute in 20 g of ether is 0.17oC.
Kb for ether is 2.16 K.kg/mol. Calculate the molar mass of solute.
3. 3 g of solute is dissolved in 22 g of water. The depression of freezing point shown by the solution
is 1.45 K. kf for H2O = 1.86 K kg mol-1. Calculate molar mass.

Osmotic pressure (  )

Osmosis : The flow of solvent from a dilute solution to a concentrated solution when both of these
solutions are separated by a semi permeable membrane is called osmosis.

Semipermeable membrane :The membrane which allows only solvent molecules to flow through
it and not the solute particles is known as semipermeable membrane.
Eg., Parchment paper,
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Cellophane paper,
Some animal membranes,
Membranes prepared by precipitating some inorganic salts like copper ferro cyanide.

Osmotic pressure ( ) : The pressure required to stop the flow of solvent molecules from solvent
to solution when both are separated by semi permeable membrane.

Reverse Osmosis : The flow of solvent from solution to solvent which are separated by a semi
permeable membrane by applying pressure greater than the osmotic pressure over the solution is
called reverse osmosis.

Isotonic Solution :The solutions with same osmotic pressure.

e.g. Blood is Isotonic with saline [ 0.9 % w v NaCl solution]

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Uses of Osmosis :

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1. Plants take up water from the soil by the phenomenon of osmosis through roots hairs.
2. If the osmotic pressure of the contents of the living cell is not equal to that of the contents sur-
rounding it outside, two phenomena may occur.

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a) If the out side concentration is higher, water may enter the cell. The cell bulges and finally
bursts. This is called Hemolysis.
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b) If the concentration in the cell is lower, water may come out of the cell and the cell
AL O
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G C
collapses. This is called Plasmolysis.
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Both are dangerous

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Van’t Hoff theory of dilute solution :

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According to Van’t Hoff, the solute in dilute solutions behaves as a gas and hence all the gas
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laws can be applied to dilute solutions.

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Boyle-Van’t Hoff’s law: The osmotic pressure (  ) of a dilute solution is directly proportional to the
concentration of the solution at constant temperature.
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C
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But the concentration of solution is inversely proportional to the volume.

1
C
V
1
    (1)
V
or  V = K  constant ---------> This is like Boyle’s law

Charle-van’t Hoff’s law:

The osmotic pressure of a dilute solution at constant concentration is directly proportional to the
absolute temperature.
  T - (2)
  K'T ---------> This is like Charle’s law

From equations (1) & (2)

T
π 
V
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T
or π  S ( S is constant)
V
1
But V 
C
   CST
But the value of ‘S’ is almost equal to gas constant ‘R’
Hence  = CRT

n number of moles of solute(n)

or  = RT ( C = )
V Volume of the solution(V)
 V  nRT
W
But n 
MW

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W.R.T

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 V 
MW
W.R.T

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MW 
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V

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or MW  XC ( V  )
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 C
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G C
Where W = weight of solute & MW = Molecular weight of solute
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Pr
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Problems
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1.An aqueous solution (1 litre) contained 6 g urea (mol.wt = 60). It’s osmotic pressure is found
W JU

equal to solution of glucose ( mol. wt = 180). How much weight of glucose is present in one litre of
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the solution.
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2.At 283 K, The osmotic pressure of 2% solution of X is 7.87 X 104 Nm-2. Calculate molar mass
of X.
3.An aqueous solution glucose containing 20 X 10-3 kg of glucose in a litre. Calculate the osmatic
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pressure of the solution at the temperature 250C.

Ostwald’s Dynamic Method :-

In this Experiment four bulbs which are connected to each other are taken. The fourth bulb
is connected to a U-shaped tube containing anhydrous CaCl2 The first two bulbs (A) are filled with
solution whereas the last two bulbs (B) contain pure solvent.

Dry air

A A B B

(Anhydrous)
CaCl2
solution solvent
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The weights of bulbs and U-tube are determined before the experiment. A current of dry air is
passed through the bulbs. It carries away the vapour of solvent while passing through the bulbs. The
loss of weight in first two bulbs (A) is proportional to vapour pressure of solution (P).
wt. loss in ‘A’ Bulbs  x   P
But the vapour pressure of solvent is greater than that of the solution, some more vapour
enters into the air while passing through the last two bulbs. Hence the loss in last two bulbs (B) is
proportional to (Po -P).
wt. loss in ‘B’ Bulbs (y) α Po -P
Gain in wt.of ‘U’ shaped tube  z  = total wt. loss in A and B bulbs ( x  y )
z =x+y = P + (Po -P) =Po
According to Raoult’s law
Po -P
=X 2
Po

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y

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i.e.,  X2
x+y

y W2 MW1

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 x
or
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x  y MW2 W1
by

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W2 x y
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i.e., MW2  x MW1 x AL O
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W1 y
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Where MW2=Molecular weight of solute

Pr
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W2 = weight of solute
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MW1 = Molecular weight of solvent

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W1 = weight of solvent
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PROBLEMS
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1. At a certain temperature dry air is sent into a solution & solvent continuously. The solution is
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prepared by dissolving 3.50 g of solute in 100 g of solvent. The loss in weights of containers con-
taining solution and solvent are 0.975 g, 0.025 g respectively. The molecular weight of solvent is 78.
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What is the molar mass of solute ?

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Cottrell’s Method
In this method, Beckman’s thermometer is used to determine the small magnitudes of eleva-
tion in boiling point or depression in freezing point accurately. It consists of a mercury reservoir at one
end and a bulb at the other end. These are connected by a capillary. The elevation or depression can
be measured in a range of -6oC to 300oC by adjusting the amount of mercury in the bulb with help of
reservoir.
The apparatus consists of a main tube provided with a side tube. The main tube contains
another inner tube through which the Beckman’s thermometer is inserted. A platinum wire is fused at
the bottom of the outer tube and heated during the boiling process.
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Cottrells apparatus

1. beckmann Thermometer
2.Condenser
2
3. Boiling tube
3 4.Solution
5. Inverted funnel
(Cottrell's device)
4
5
Beckmann Thermometer

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An inverted funnel called cottrell’s device is placed in the solution. The stem of this funnel is

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split into three symmetrical tubes. This device pumps the bubbles of the solution along with the vapour
on to the thermometer bulb so that the liquid and vapour will be in equilibrium on the surface of the bulb
at the boiling point. Thus this device helps in reducing super heating.

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A known weight (w1) of solvent is taken in the Cottrell’s tube and the boiling point (Tbo)is
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determined. Then a known weight of solute (w2) is dissolved in the solvent and the boiling point (Tb) is

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measured. The molar mass of the solute is determined using the following equation.
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W2 1000
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ΔTb  Tb -Tb o =K b x x
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MW2 W1
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Where MW2=Molecular weight of solute

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W2 = weight of solute
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W1 = weight of solvent
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Kb= Molal elevation constant of solvent.

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PROBLEMS
1. The boiling point of CHCl3 was raised by 0.325 K when 5.141 X 10-4 kg of anthracene is
dissolved in 3.5 X 10-3 kg of CHCl3. Calculate molar mass of anthracene.(kb = 3.9 K kg mol-1).
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Rast Method
This method is used to determines the depression in freezing point of a solution. As camphor
is used as solvent, this method is generally used for solid solutions.
A known weight (w1) of finely powdered camphor is mixed with a known weight (w2) of
solute and melted to form a homogeneous solution and then cooled and powdered.. This mixture is
taken in a capillary tube and the melting point (Tf) is determined accurately. The melting point (Tfo) of
pure camphor is determined separately. The molar mass of the solute is determined by using the
following equation.
W2 1000
ΔTf =K f x x
MW2 W1
Where MW2=Molecular weight of solute
W2 = weight of solute
W1 = weight of solvent
Kf= Molal freezing point constant of solvent (camphor)

Berkeley - Hartley Method

This method is used to determine the osmotic pressure. The apparatus consists of a porous
tube opened at both the ends. Copper ferrocyanide is precipitated in the pores as semi permeable
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membrane by electrolytic method. Then the two ends are closed with rubber corks. A thistle funnel
is fixed in one rubber cork and a capillary tube is introduced in another cork.
The porous tube is fixed in an outer cylindrical tube made up of gun metal. This outer tube
is provided with a manometer. Water is added into the porous tube through the funnel and the level
of water in the capillary is recorded. Then the space between the inner and outer tubes is filled with
the solution of known concentration (C) which is formed by dissolving W g of solute.

1 Berkeley-Hartley method
5
6 1.Solvent reservoir
2.Semipermeable
4 3.Solution
4. Capillary tube

5.Piston

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7 6. Pressure guage

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2 7. Solvent
3

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As osmosis starts, the level of liquid in the capillary decreases. Now the pressure is applied

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externally to adjust the level of water in the capillary to original position. This external pressure

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applied is taken as osmotic pressure(  ) and the molar mass (MW) of the solute is calculated by
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using the following equation.

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MW  xC
Pr


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Abnormal molar mass and van’t Hoff factor (i):

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Solutions which obey Raoult’s law are called ideal solutions. But these solutions deviate from
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ideality when the concentration is increased or when the solute undergoes either dissociation or asso-
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ciation or when there is interaction between solute and solvent. The colligative properties measured for
these non-ideal solutions are termed as abnormal colligative properties.
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Van’t Hoff factor (i): It is the ratio of experimentally determined abnormal colligative property to that
of theoretically calculated colligative property is called van’t Hoff factor.
experimental value of colligative propery
i=
Calculated value of colligative property
The colligative property is inversely proportional to the molar mass of the solute and hence
Calculated molar mass of solute
i=
experimental molar mass of solute
For ideal solutions i = 1
For non-ideal solutions
i < 1 when solute undergoes dissociation.
i > 1 when solute undergoes association.

The equations for calculating different colligative properties can be modified to correct non ideality
as given below.
ΔP
= i.X 2
Po
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Tb  i.K b m

Tf  i.Kf m

 = i.CRT

The relation between ‘i’ and degree of dissociation or association ‘ ’ can be calculated as follows.

Relation between ‘i’ and ‘  ’ when solute undergoes dissociation:

If one mole of ‘A’ ionize by giving ‘n’ moles of ions and the degree of dissociation is ‘ ’ ,
then
A  nB
initial 1 mole 0
At equilibrium (1-  ) n

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 Total no.of particles in the solution = (1-  ) + n 
= 1+n  - 

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= 1+  (n-1)
Total no.of particles in the solution 1    n  1

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van't Hoff factor (i) 
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no.of particles taken 1

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i = 1+  (n-1)
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i-1=  (n-1)
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i-1
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 
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dissociation
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n-1
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Relation between ‘i’ and ‘  ’ when solute undergoes association:

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If ‘n’ moles of A combine to give A n molecules and the degree of association is ‘  ’,

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then,
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nA A 
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n
initial 1 mole 0

at equilibrium (1- )
n
  1
Total no.of particles in the solution = (1- ) + = 1+   = 1+ ( -1)
n n n
no.of particles in the solution
 van't Hoff factor (i) =
no.of particles taken
1
1+ ( -1)
 n
1
1
i.e., i = 1+ ( -1)
n
1
i-1= ( -1)
n
i-1
 =
association 1
1
n
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TEST YOUR UNDERSTANDING

State whether the following statements are true or false.

1) Molarity is the number of moles of solute dissolved in 1 litre of solvent.

2) 1 litre of 1M HCl solution is added with 1 litre of water. The molarity of final solution will be 2M.
3) The equivalent weight of H2SO4 in the following reaction is 49 g.
H 2SO 4 + KOH 
 KHSO 4 + H 2O
4) The molality of an aqueous solution is 2 m at 270C. The molality of same solution will be 2 m
only, at 1270C.
5) Vapour pressure of H2O at 200C is 17.54 mm Hg. The vapour pressure is increased to 17.60
mm Hg when 0.1 moles of urea is added.
6) Depression in freezing point of one molal solution containing a nonvolatile solute is called molal

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depression in freezing point constant or cryoscopic constant.
7) The osmatic pressure of 1M NaCl is equal to the osmatic pressure of 1M sucrose solution.

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8) The basicity of H3PO2 is equal to 3
9) An aqueous solution of 0.1M urea has same boiling point as that of aqueous solution of 0.1M

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sucrose solution.
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10) The Van’t - Hoff factor (i) of aqueous solution of Acetic acid is greater than 1, whereas it’s

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value is less than 1 in benzene solution.

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Pr
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