Chemistry

Solutions

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Table of Content

1. Solubility.
2. Kinds of solutions.
3. Methods of expressing concentration of solution.
4. Colligative properties.
5. Lowering of vapor pressure.
6. Ideal and Non-Ideal solution.
7. Azeotropic mixture.
8. Osmosis and Osmotic pressure of the solution.
9. Elevation in boiling point of the solvent (Ebullioscopy).
10. Depression in freezing point of the solvent (Cryoscopy).
11. Colligative properties of electrolytes.
12. Abnormal molecular masses.

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A solution is a homogenous mixture of two or more substances, the composition of which may vary within
limits. “A solution is a special kind of mixture in which substances are intermixed so intimately that they
cannot be observed as separate components”. The dispersed phase or the substance which is to be
dissolved is called solute, while the dispersion medium in which the solute is dispersed to get a
homogenous mixture is called the solvent. A solution is termed as binary, ternary and quaternary if it
consists of two, three and four components respectively.

1. Solubility.

Solubility of as substance in the solvent is the measure of the capacity of the latter to dissolve the former
at a given temperature and pressure. “Solubility of a substance may be defined as the amount of solute
dissolved in 100gms of a solvent to form a saturated solution at a given temperature”. A saturated
solution is a solution which contains at a given temperature as much solute as it can hold in presence of
dissolved solvent. Any solution may contain less solute than would be necessary to to saturate it. Such a
solution is known as unsaturated solution. When the solution contains more solute than would be
necessary to saturate it then it is termed as supersaturated solution. It is metastable.

2. Kinds of solutions.

All the three states of matter (gas, liquid or solid) may behave either as solvent or solute. Depending on
the state of solute or solvent, mainly there may be following nine types of binary solutions.

Solvent Solute Example

Gas Gas Mixture of gases, air.

Gas Liquid Water vapors in air, mist.

Gas Solid Sublimation of a solid into a gas, smoke.

Liquid Gas CO2 gas dissolved in water (aerated drinks).

Liquid Liquid Mixture of miscible liquids, e.g., alcohol in water.

Liquid Solid Salt in water, sugar in water.

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 Solid Gas Adsorption of gases over metals; hydrogen over palladium.

Solid Liquid Mercury in zinc, mercury in gold, CuSO4.5H2O.

Solid Solid Homogeneous mixture of two or more metals (alloys), e.g., copper in gold,
zinc in copper.

Among these solutions the most significant type of solutions are those which are in liquid phase and
may be categorized as: (i) Solid in liquid solutions, (ii) Liquid in liquid solutions and (iii) Gas in liquid
solutions.

(i) Solid in liquid solutions: For the solid in liquid solutions the solid is referred to as solute. The amount
of solute that is dissolved in 100 g of a solvent, to form a saturated solution at a particular temperature
is called solubility. The solubility of a solid solute in liquid depends upon

(a) Nature of solute and solvent

(b) Temperature: Usually the solubility of the solute increases with increase in temperature

(e.g., KI, KNO 3 , NH 4 Br ) but in some cases increase in solubility is negligible (e.g. NaCl ) and in cases of
some salts (e.g., NaOH , Na 2 SO 4 , CeSO 4 ) solubility decreases with increase in temperature.
Cause of miscibility of solids in liquids : The basic cause of solubility of solid solute in liquid solvent can
be summed up in one line, i.e., “Similia similibus solvanter” meaning like dissolves like which implies that
polar solvents dissolve polar solutes and non-polar solvents dissolve non-polar solutes.
For ionic solutes, the solubility, in general, is related to the magnitude of hydration (or salvation) energy
and lattice energy. In general if the magnitude of hydration energy is greater than lattice energy, the
solute is soluble otherwise it is insoluble.

(ii) Liquid in liquid solutions: When two liquids are mixed, the mixture may be of the following types:

(a) The two components may be almost immiscible: In this case, one of the liquids is polar while the
other is of non-polar nature. For example, benzene and water.

(b) The miscibility of the component may be partial: If the intermolecular attraction of one liquid is
different from intramolecular attraction of the other, there may be a partial miscibility of the two liquids.
For example, ether and water.

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(c) The two components may be completely miscible: In this case, the two liquids are of the same
nature, i.e., they are either polar (like alcohol and water) or non-polar (like benzene and hexane).

Cause of Miscibility of Liquids

(a) Chemically alike liquids dissolve in one another more freely as compared to others, for example,
alkanes are miscible in all proportions with one another. Alkanes are however, not miscible with water
because they cannot form H-bonds with water molecules.

(b) Dipole-Dipole interactions also play an important role in forming liquid solutions.

(c) Molecular sizes of liquids which are mutually soluble, are also approximately same.

(iii) Gas in Liquid solutions: Most of the gases are soluble in water to some extent. The solubility of gas
in water generally depends upon the following factors

(a) Nature of the gas: In general the gases which are easily liquefiable are more soluble in water.
(b) Temperature: The dissolution of gas in water is exothermic process. Hence, the solubility of gas
decreases with rise in temperature.
(c) Pressure: Effect of pressure on the solubility of gas is explained by “Henry’s law”. According to
Henry’s law “mass of gas dissolved in a given volume of solvent, at a constant temperature, is
proportional to the pressure of the gas with which it is in equilibrium.”
Solubility  Pressure; S  KP where K is Henry’s constant.
Higher the value of K at given pressure, the lower is the solubility of the gas in the liquid. Value of K
increases with increase in temperature while solubility of gas decreases. It is due to this reason that
aquatic species are more comfortable in cold water rather than hot water.

Applications of Henry's law: Henry's law finds several applications in industry and explains some
biological phenomena. Notable among these are:
(i) To increase the solubility of CO 2 in soft drinks and soda water, the bottle is sealed under high
pressure.
(ii) To minimize the painful effects accompanying the decompression of deep sea divers, oxygen diluted
with less soluble helium gas is used as breathing gas.
(iii) In lungs, where oxygen is present in air with high partial pressure of oxygen to form
oxohaemoglobin. In tissues where partial pressure of oxygen is low. Oxohaemoglobin releases oxygen
for utilization in cellular activities.
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3. Methods of expressing concentration of solution.

Concentration of solution is the amount of solute dissolved in a known amount of the solvent or
solution. The concentration of solution can be expressed in various ways as discussed below.

(1) Percentage: It refers to the amount of the solute per 100 parts of the solution. It can also be called
as parts per hundred (pph). It can be expressed by any of following four methods:
Wt.of solute
(i) Weight to weight percent (% w/w)   100
Wt.of solution
e.g., 10% Na 2 CO 3 solution w/w means 10 g of Na 2 CO 3 is dissolved in 100 g of the solution. (It means
10 g Na 2 CO 3 is dissolved in 90 g of H 2 O )
Wt.of solute
(ii) Weight to volume percent (% w/v)   100
Volume of solution
e.g., 10% Na 2 CO 3 (w/v) means 10 g Na 2 CO 3 is dissolved in 100 cc of solution.
Vol. of solute
(iii) Volume to volume percent (% v/v)   100
Vol. of solution
e.g., 10% ethanol (v/v) means 10 cc of ethanol dissolved in 100 cc of solution.
Vol. of solute
(iv) Volume to weight percent (% v/w)   100
Wt.of solution
e.g., 10% ethanol (v/w) means 10 cc of ethanol dissolved in 100 g of solution.

(2) Parts per million (ppm) and parts per billion (ppb): When a solute is present in trace quantities, it
is convenient to express the concentration in parts per million and parts per billion. It is the number of
parts of solute per million (10 6 ) or per billion (10 9 ) parts of the solution. It is independent of the
temperature.
mass of solute component mass of solute component
ppm   10 6 ; ppb   10 9
Total mass of solution Total mass of solution

(3) Strength: The strength of solution is defined as the amount of solute in grams present in one litre
(or dm 3 ) of the solution. It is expressed in g/litre or (g / dm 3 ) .
Mass of solute in grams
Strength 
Volume of solution in litres

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(4) Normality (N): It is defined as the number of gram equivalents (equivalent weight in grams) of a
solute present per litre of the solution. Unit of normality is gram equivalents litre–1. Normality changes
with temperature since it involves volume. When a solution is diluted x times, its normality also
decreases by x times. Solutions in term of normality generally expressed as,
N  Normal solution; 5 N  Penta normal, 10 N  Deca normal; N / 2  semi normal
N / 10  Deci normal; N / 5  Penti normal
N / 100 or 0.01 N  centinormal, N / 1000 or 0.001= millinormal
Mathematically normality can be calculated by following formulas,
Number of g.eq. of solute Weight of solute in g.
(i) Normality ( N )  
Volume of solution (l) g. eq. weight of solute  Volume of solution (l)
Wt.of solute per litre of solution
(ii) N ,
g eq. wt. of solute
Wt.of solute 1000
(iii) N  
g.eq. wt. of solute Vol. of solution in ml
Percent of solute  10
(iv) N ,
g eq. wt. of solute
Strength in g l-1 of solution
(v) N 
g eq. wt. of solute
Wt% density  10
(vi) N
Eq. wt.
(vii) If volume V1 and normality N 1 is so changed that new normality and volume N 2 and V2 then,
N 1 V1  N 2 V2 (Normality equation)
(viii) When two solutions of the same solute are mixed then normality of mixture (N ) is
N 1 V1  N 2 V2
N
V1  V2
(ix) Vol. of water to be added i.e., (V2  V1 ) to get a solution of normality N 2 from V1 ml of normality
N1
 N  N2 
V2  V1   1  V1
 N2 
(x) If Wg of an acid is completely neutralized by V ml of base of normality N
Wt.of acid VN Wt.of base Vol. of acid  N of acid
 ; Similarly, 
g eq. wt. of acid 1000 g eq. wt. of base 1000

(xi) When Va ml of acid of normality N a is mixed with Vb ml of base of normality N b

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(a) If Va N a  Vb N b (Solution neutral)
(b) If Va N a  Vb N b (Solution is acidic)
(c) If Vb N b  Va N a (Solution is basic)
Va N a  Vb N b
(xii) Normality of the acidic mixture 
(Va  Vb )
Vb N b  Va N a
(xiii) Normality of the basic mixture 
(Va  Vb )
No. of meq * of solute
(xiv) N  (* 1 equivalent = 1000 milliequivalents or meq.)
Vol. of solution in ml

(4) Molarity (M): Molarity of a solution is the number of moles of the solute per litre of solution (or
number of millimoles per ml. of solution). Unit of molarity is mol/litre or mol/dm3 For example, a
molar (1 M ) solution of sugar means a solution containing 1 mole of sugar (i.e., 342 g or 6.02  10 23
molecules of it) per litre of the solution. Solutions in term of molarity generally expressed as,
M
1 M = Molar solution, 2 M = Molarity is two, or 0.5 M = Semimolar solution,
2
M M
or 0.1 M = Decimolar solution, or 0.01 M = Centimolar solution
10 100
M
or 0.001 M = Millimolar solution
1000

 Molarity is most common way of representing the concentration of solution.

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 Molarity is depend on temperature as, Molarity
T emperature

 When a solution is diluted (x times), its molarity also decreases (by x times)

Mathematically molarity can be calculated by following formulas,

No. of moles of solute (n)

(i) M ,
Vol. of solution in litres

Wt.of solute (in gm) per litre of solution

(ii) M
Mol. wt. of solute

Wt.of solute (in gm) 1000

(iii) M 
Mol. wt. of solute Vol. of solution in ml.

No. of millimoles of solute

(iv) M
Vol. of solution in ml
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 Percent of solute  10
(v) M
Mol. wt. of solute

Strength in gl-1 of solution

(vi) M
Mol. wt. of solute

10  Sp. gr. of the solution  Wt.% of the solute

(vii) M
Mol. wt. of the solute

(viii) If molarity and volume of solution are changed from M 1 , V1 to M 2 , V2 . Then,

M 1 V1  M 2 V2 (Molarity equation)

(ix) In balanced chemical equation, if n1 moles of reactant one react with n 2 moles of reactant
two. Then,

M 1 V1 M 2 V2

n1 n2

(x) If two solutions of the same solute are mixed then molarity (M) of resulting solution.

M 1 V1  M 2 V2
M
(V1  V2 )

(xi) Volume of water added to get a solution of molarity M 2 from V1 ml of molarity M 1 is

 M  M2 
V2  V1   1  V1
 M2 

Relation between molarity and normality

Molecular mass
Normality of solution = molarity 
Equivalent mass

Normality  equivalent mass = molarity  molecular mass

Molecular mass
For an acid, = basicity
Equivalent mass

So, Normality of acid = molarity  basicity.

Molecular mass
For a base, = Acidity
Equivalent mass

So, Normality of base = Molarity  Acidity.

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(6) Formality (F): Formality of a solution may be defined as the number of gram formula masses of the
ionic solute dissolved per litre of the solution. It is represented by F . Commonly, the term formality is
used to express the concentration of the ionic solids which do not exist as molecules but exist as
network of ions. A solution containing one gram formula mass of solute per litre of the solution has
formality equal to one and is called formal solution. It may be mentioned here that the formality of a
solution changes with change in temperature.
Number of gram formula masses of solute
Formality (F) = =
Volume of solution in litres
Mass of ionic solute (g)
(gm. formula mass of solute)  (Volume of solution (l))
W B (g) WB (g)  1000
Thus, F or
GFM  V (l) GFM  V (ml)

(7) Mole fraction (X): Mole fraction may be defined as the ratio of number of moles of one component
to the total number of moles of all the components (solvent and solute) present in the solution. It is
denoted by the letter X . It may be noted that the mole fraction is independent of the temperature.
Mole fraction is dimensionless. Let us suppose that a solution contains the components A and B and
suppose that W A g of A and WB g of B are present in it.
WA W
Number of moles of A is given by, n A  and the number of moles of B is given by, n B  B
MA MB
Where M A and M B are molecular masses of A and B respectively.
Total number of moles of A and B  n A  n B
nA nB
Mole fraction of A , X A  ; Mole fraction of B , X B 
nA  nB nA  nB
The sum of mole fractions of all the components in the solution is always one.
nA nB
XA  XB   1.
n A  nB n A  nB

Thus, if we know the mole fraction of one component of a binary solution, the mole fraction of the
other can be calculated.

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Relation between molality of solution (m) and mole fraction of the solute (XA).

m
XA 
55 .5  m

(8) Mass fraction: Mass fraction of a component in a solution is the mass of that component divided by
the total mass of the solution. For a solution containing w A gm of A and w B gm of B
wA wB
Mass fraction of A  ; Mass fraction of B 
wA  wB wA  wB
Note: It may be noted that molality, mole fraction, mass fraction etc. are preferred to molarity, normality, etc.
because the former involve the weights of the solute and solvent whereas later involve volumes of solutions.
Temperature has no effect on weights but it has significant effect on volumes.

(9) Demal unit (D): The concentrations are also expressed in “Demal unit”. One Demal unit represents
one mole of solute present in one litre of solution at 0 o C .

4. Colligative properties.

Certain properties of dilute solutions containing non-volatile solute do not depend upon the nature of
the solute dissolved but depend only upon the concentration i.e., the number of particles of the solute
present in the solution. Such properties are called colligative properties. The four well known examples
of the colligative properties are

(1) Lowering of vapor pressure of the solvent.

(2) Osmotic pressure of the solution.
(3) Elevation in boiling point of the solvent.
(4) Depression in freezing point of the solvent.

Since colligative properties depend upon the number of solute particles present in the solution, the
simple case will be that when the solute is a non-electrolyte. In case the solute is an electrolyte, it may
split to a number of ions each of which acts as a particle and thus will affect the value of the colligative
property.

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Each colligative property is exactly related to any other and thus if one property is measured, the other
can be calculated. The study of colligative properties is very useful in the calculation of molecular
weights of the solutes.

5. Lowering of vapor pressure.

The pressure exerted by the vapors above the liquid surface in equilibrium with the liquid at a given
temperature is called vapor pressure of the liquid. The vapor pressure of a liquid depends on
(1) Nature of liquid: Liquids, which have weak intermolecular forces, are volatile and have greater vapor
pressure. For example, dimethyl ether has greater vapor pressure than ethyl alcohol.

(2) Temperature: Vapor pressure increases with increase in temperature. This is due to the reason that
with increase in temperature more molecules of the liquid can go into vapor phase.

(3) Purity of liquid: Pure liquid always has a vapor pressure greater than its solution.

Raoult’s law: When a non-volatile substance is dissolved in a liquid, the vapor pressure of the liquid
(solvent) is lowered. According to Raoult’s law (1887), at any given temperature the partial vapor
pressure (pA) of any component of a solution is equal to its mole fraction (XA) multiplied by the vapor
pressure of this component in the pure state ( p 0A ) . That is, p A  p 0A  X A

The vapor pressure of the solution (Ptotal ) is the sum of the partial pressures of the components, i.e., for
the solution of two volatile liquids with vapor pressures p A and p B .

Ptotal  p A  p B  (p 0A  X A )  (p B0  X B )

Alternatively, Raoult’s law may be stated as “the relative lowering of vapor pressure of a solution
containing a non-volatile solute is equal to the mole fraction of the solute in the solution.”
Relative lowering of vapor pressure is defined as the ratio of lowering of vapor pressure to the vapor
pressure of the pure solvent. It is determined by Ostwald-Walker method.
Mole fraction of the solute is defined as the ratio of the number of moles of solute to the total number
of moles in solution.
Thus according to Raoult’s law,

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 w
p0  p n m
 
p0 nN w W

m M
Where, p  Vapor pressure of the solution; p 0  Vapor pressure of the pure solvent
n  Number of moles of the solute; N  Number of moles of the solvent
w and m  weight and mol. wt. of solute; W and M  weight and mol. wt. of the solvent.

Limitations of Raoult’s law

 Raoult’s law is applicable only to very dilute solutions.
 Raoult’s law is applicable to solutions containing non-volatile solute only.
 Raoult’s law is not applicable to solutes which dissociate or associate in the particular solution.

6. Ideal and Non-Ideal solution.

(1) Ideal solution: An ideal solution may be defined as the solution which obeys Raoult’s law over the
entire range of concentration and temperature and during the formation of which no change in
enthalpy and no change in volume takes place. So for ideal solutions the conditions are,
(i) It should obey Raoult’s law, i.e., PA  PA0 X A and PB  PB0 X B .
(ii) H mixing  0

(iii) Vmixing  0

The solutions in which solvent-solvent and solute-solute interactions are almost of the same type as
solvent-solute interactions, behave nearly as ideal solutions.
This type of solutions are possible if molecules of solute and solvent are almost of same size and have
identical polarity. For example, solutions of following pairs almost behave as ideal solutions,
n-Heptane and n-hexane.; Chlorobenzene and bromobenzene.
Benzene and toluene; Ethyl bromide and ethyl iodide.
Ethylene bromide and ethylene chloride; Carbon tetrachloride and silicon tetrachloride.
For such solutions the vapor pressure of the solution is always intermediate between the vapor
pressures of pure components A and B, i.e., PA0 and PB0 .

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(2) Non-Ideal solution: The solutions which do not obey Raoult’s law and are accompanied by change
in enthalpy and change in volume during their formation are called non-ideal solutions. So, for non-
ideal solutions the conditions are:
(i) It does not obey Raoult's law. PA  PA0 X A ; PB  PB0 X B
(ii) H mixing  0

(iii) Vmixing  0

Either component of non-ideal binary solution do not follow Raoult's law. The non-ideal solutions are
further divided into two types:
(a) Solutions showing positive deviations. (b) Solutions showing negative deviations.

(a) Solutions showing positive deviation: In this type of deviations, the partial vapor pressure of each
component (say A and B) of solution is greater than the vapor pressure as expected according to
Raoult’s law. This type of deviations are shown by the solutions in which solvent-solvent and solute-
solute interactions are stronger than solvent-solute interactions.
P=PA+PB
For the non-ideal solutions exhibiting positive deviation.

Vapor Pressure
PA  PA0 X A , PB  PB0 X B ; H mixing   ve ; Vmixing   ve PB

E.g. of solutions showing positive deviations PA

(CH 3 )2 CO  CS 2 ; (CH 3 )2 CO  C 2 H 5 OH
Mole Fraction
C6 H 6  (CH 3 )2 CO ; CCl 4  C6 H 6
Partial and total vapor
CCl 4  CHCl 3 ; CCl 4  C6 H 5 CH 3 pressure curves for solutions
that show positive deviations
H 2 O  CH 3 OH ; H 2 O  C 2 H 5 OH

CH 3 CHO  CS 2 ; CHCl 3  C 2 H 5 OH

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(b) Solutions showing negative deviation: In this type of deviations the partial vapor pressure of each
component of solution is less than the vapor pressure as expected according to Raoult’s law. This type
of deviations are shown by the solutions in which solvent-solvent and solute-solute interactions are
weaker than solvent-solute interactions.
For non-ideal solution showing negative deviation.

Vapor Pressure
P=PA+PB
PA  PA0 X A , PB  PB0 X B ; H mixing   ve ; Vmixing   ve
PB
E.g. of solutions showing negative deviations
PA
CH 3 COOH  C 5 H 5 N (pyridine)
Mole Fraction
CHCl 3  (CH 3 )2 CO ; CHCl 3  C 6 H 6

CHCl 3  (C 2 H 5 )2 O ; H 2 O  HCl A vapor pressure curve

showing negative deviation
H 2 O  HNO 3 ; (CH 3 )2 CO  C 6 H 5 NH 2 (solid lines) from ideal

Differences between ideal and non-ideal solutions

Ideal solutions Solutions with positive Solutions with negative

deviations deviations
A……B interactions are similar to A……B interactions are smaller A……B interactions are greater
A……A and B……B interactions than A……A and B……B than A……A and B……B
interactions interactions
PA  PA0 X A ; PB  PB0 X B PA  PA0 X A ; PB  PB0 X B PA  PA0 X A ; PB  PB0 X B

H sol.  0 H sol.  0 H sol.  0

Vmix  0 Vmix  0 Vmix  0

Do not form azeotrope Exhibit minimum boiling point Exhibit maximum boiling
azeotropy azeotropy

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7. Azeotropic mixture.

Azeotropes are defined as the mixtures of liquids which boil at constant temperature like a pure liquid
and possess same composition of components in liquid as well as in vapor phase. Azeotropes are also
called constant boiling mixtures because whole of the azeotropes changes into vapor state at constant
temperature and their components cannot be separated by fractional distillation. Azeotropes are of two
types as described below:

(1) Minimum boiling azeotrope: For the solutions with positive deviation there is an intermediate
composition for which the vapor pressure of the solution is maximum and hence, boiling point is
minimum. At this composition the solution distills at constant temperature without change in
composition. This type of solutions are called minimum boiling azeotrope. e.g.

Components Mass % of B Boiling points (K)

A B A B Azeotrope
H 2O C 2 H 5 OH 95.57 373 351.3 351.1
H 2O C 2 H 5 CH 2 OH 71.69 373 370 350.72
CHCl 3 C 2 H 5 OH 67 334 351.3 332.3
(CH 3 )2 CO CS 2 6.8 329.25 320 312.2

(2) Maximum boiling azeotrope: For the solutions with negative deviations there is an intermediate
composition for which the vapor pressure of the solution is minimum and hence, boiling point is
maximum. At this composition the solution distills at constant temperature without the change in
composition. This type of solutions are called maximum boiling azeotrope. e.g.

Components Mass % of B Boiling points (K)

A B A B Azeotrope
H 2O HCl 20.3 373 188 383
H 2O HNO 3 58.0 373 359 393.5
H 2O HClO4 71.6 373 383 476

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8. Osmosis and Osmotic pressure of the solution.
The flow of solvent from pure solvent or from solution of lower concentration into solution of higher
concentration through a semi-permeable membrane is called Osmosis. Osmosis may be divided in
following types,
(1) Exo-Osmosis: The outward osmotic flow of water from a cell containing an aqueous solution
through a semi-permeable membrane is called as Exo-osmosis. For example, egg (after removing hard
shell) placed in conc. NaCl solutions, will shrink due to Exo-osmosis.

(2) Endo-osmosis: The inward flow of water into the cell containing an aqueous solution through a
semi-permeable membrane is called as endo-osmosis. e.g., an egg placed in water swells up due to
endo-osmosis.

(3) Reverse osmosis: If a pressure higher than osmotic pressure is applied on the solution, the solvent
will flow from the solution into the pure solvent through the semi-permeable membrane. Since here the
flow of solvent is in the reverse direction to that observed in the usual osmosis, the process is called
reverse osmosis.

Differences between osmosis and diffusion

Osmosis Diffusion
In osmosis movement of molecules takes place In diffusion there is no role of semi-permeable
through a semi-permeable membrane. membrane.
It involves movement of only solvent molecules It involves passage of solvent as well as solute
from one side to the other. molecules from one region to the other.
Osmosis is limited to solutions only. Diffusion can take place in liquids, gases and
solutions.
Osmosis can be stopped or reversed by applying Diffusion can neither be stopped nor reversed
additional pressure on the solution side.

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Osmotic pressure (): Osmotic pressure may be defined in following ways,
The osmotic pressure of a solution at a particular temperature may be defined as the excess hydrostatic
pressure that builds up when the solution is separated from the solvent by a semi-permeable
membrane. It is denoted by.
Or
Osmotic pressure may be defined as the excess pressure which must be applied to a solution in order
to prevent flow of solvent into the solution through the semi-permeable membrane.
Or
Osmotic pressure is the excess pressure which must be applied to a given solution in order to increase
its vapor pressure until it becomes equal to that of the solution.
Or
Osmotic pressure is the negative pressure which must be applied to (i.e. the pressure which must be
withdrawn from) the pure solvent in order to decrease its vapor pressure until it becomes equal to that
of the solution.

Measurements of osmotic pressure: Following methods are used for the measurement of osmotic
pressure: (i) Pfeffer’s method, (ii) Morse and Frazer’s method, (iii) Berkeley and Hartley’s method, (iv)
Townsend’s negative pressure method, (v) De Vries plasmolytic method.

Determination of molecular mass of non-volatile solute from osmotic pressure ():

According to Van’t Hoff equation,
nB W RT
  RT ; M B  B Where, WB  known mass of solute in gm
V V

This method is especially suitable for the determination of molecular masses of macromolecules such as
proteins and polymers. This is due to the reason that for these substances the values of other colligative
properties such as elevation in boiling point or depression in freezing point are too small to be
measured. On the other hand, osmotic pressure of such substances are measurable. Conditions for
getting accurate value of molecular mass are,

(i) The solute must be non-volatile.

(ii) The solution must be dilute.
(iii) The solute should not undergo dissociation or association in the solution.

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Van’t Hoff’s solution equation:

The osmotic pressure is a colligative property. For a given solvent the osmotic pressure depends only
upon the molar concentration of solute but does not depend upon its nature. Osmotic pressure is
related to the number of moles of the solute by the following relation:
n
V  nRT or   RT    CRT ; here, C = concentration of solution in moles per litre
V
R = gas constant; T = temperature; n = number of moles of solute; V = volume of solution
Above eq. is called Van’t Hoff’s solution equation

Relation of osmotic pressure with different colligative properties: Osmotic pressure is related to
relative lowering of vapor pressure, elevation of boiling point and depression of freezing point
according to the following relations.
 Po  P  dRT dRT dRT
(1)    A o A 
 M (2)   Tb  (3)   T f 
 PA  B 1000  K b 1000  K f

In the above relations,  = Osmotic pressure; d = Density of solution at temperature T; R = Universal

gas constant; M B = Mol. Mass of solute; K b = Molal elevation constant of solvent; K f = Molal
depression constant of solvent

Isotonic, Hypertonic and Hypotonic solutions

Isotonic or iso-osmotic solutions: Two solutions of different substances having same osmotic
pressure at same temperature are known as isotonic solutions.
For isotonic solutions,  1   2 Primary Condition …..(i)
Also, C1  C 2
n1 n
or  2
V1 V2 Secondary
w1 w2
or  …..(ii)
Conditions
m 1 V1 m 2 V2
Eq. (ii) holds good only for those solutes which neither possess the tendency to get associate nor
dissociate in solution, e.g.,
(a) Urea and glucose are isotonic then,  1   2 and C1  C 2
(b) Urea and NaCl are isotonic then,  1   2 but C1  C 2
(dissociate)

(c) Urea and Benzoic acid are isotonic then,  1   2 but C1  C 2

(associate)

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Hypertonic and Hypotonic Solution: The solution which has more osmotic pressure than the other
solution is called as hypertonic solution and the solution which has lesser osmotic pressure than the
other is called as hypotonic solution.
The flow of solvent is always from lower osmotic pressure to higher osmotic pressure i.e. from
hypotonic to hypertonic solution.

9. Elevation in boiling point of the solvent (Ebullioscopy).

Boiling point of a liquid may be defined as the temperature at which its vapor pressure becomes equal
to atmospheric pressure, i.e., 760 mm. Since the addition of a non-volatile solute lowers the vapor
pressure of the solvent, solution always has lower vapor pressure than the solvent and hence it must be
heated to a higher temperature to make its vapor pressure equal to atmospheric pressure with the
result the solution boils at a higher temperature than the pure solvent. Thus sea water boils at a higher
temperature than distilled water. If Tb is the boiling point of the solvent and T is the boiling point of the
solution, the difference in the boiling point (T or  Tb) is called the elevation of boiling point.
T  Tb  Tb or T

Elevation in boiling point is determined by Landsberger’s method and Cottrell’s method. Study of
elevation in boiling point of a liquid in which a non-volatile solute is dissolved is called as ebullioscopy.

Important relations concerning elevation in boiling point

(i) The elevation of boiling point is directly proportional to the lowering of vapor pressure, i.e.,
Tb  p 0  p

(ii) Tb  K b  m

Where K b  molal elevation constant or ebullioscopic constant of the solvent; m  Molality of the
solution, i.e., number of moles of solute per 1000 g of the solvent; Tb  Elevation in boiling point
1000  K b  w 1000  K b  w
(iii) Tb  or m 
m W Tb  W

Where, K b is molal elevation constant and defined as the elevation in B.P. produced when 1 mole of
the solute is dissolved in 1 kg of the solvent. Sometimes the value of K b is given per 0 .1kg ( 100 g ), in
such case the expression becomes

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 100  K b  w
m
Tb  W

Where w and W are the weights of solute and solvent and m is the molecular weight of the solute.
0 .002(T0 )2
(iv) K b 
lV

Where T0  Normal boiling point of the pure solvent; l V  Latent heat of evaporation in cal / g of pure
solvent; K b for water is 0.52 deg  kg mol 1

10. Depression in freezing point of the solvent (Cryoscopy).

Freezing point is the temperature at which the liquid and the solid states of a substance are in
equilibrium with each other or it may be defined as the temperature at which the liquid and the solid
states of a substance have the same vapor pressure. It is observed that the freezing point of a solution
is always less than the freezing point of the pure solvent. Thus the freezing point of sea water is low
than that of pure water. The depression in freezing point (T or T f ) of a solvent is the difference in
the freezing point of the pure solvent (Ts ) and the solution (Tsol . ) .

Ts  Tsol  T f or T

NaCl or CaCl 2 (anhydrous) are used to clear snow on roads. They depress the freezing point of water
and thus reduce the temperature of the formation of ice.

Depression in freezing point is determined by Beckmann’s method and Rast’s camphor method. Study
of depression in freezing point of a liquid in which a non-volatile solute is dissolved in it is called as
cryoscopy.

Important relations concerning depression in freezing point.

(i) Depression in freezing point is directly proportional to the lowering of vapor pressure.
T f  p 0  p

(ii) T f  K f  m

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Where K f  molal depression constant or cryoscopic constant; m  Molality of the solution (i.e., no.
of moles of solute per 1000 g of the solvent); T f  Depression in freezing point

1000  K f  w 1000  K f  w
(iii) T f  or m 
m W T f  W

Where K f is molal depression constant and defined as the depression in freezing point produced when
1 mole of the solute is dissolved in 1kg of the solvent. Sometimes the value of K f is given per
0.1kg (100 g) , in such case the expression becomes

100  K f  w
m
T f  W

Where w and W are the weights of solute and solvent and m is the molecular weight of the solute.

R(T0 )2 0 .002(T0 )2
(iv) K f  
l f 1000 lf

Where T0  Normal freezing point of the solvent; l f  Latent heat of fusion/g of solvent; K f for water is
1.86 deg  kg mol 1

Relative lowering of vapor pressure, elevation in boiling point and depression in freezing point are
directly proportional to osmotic pressure.

11. Colligative properties of electrolytes.

The colligative properties of solutions, viz. lowering of vapor pressure, osmotic pressure, elevation in
b.p. and depression in freezing point, depend solely on the total number of solute particles present in
solution. Since the electrolytes ionize and give more than one particle per formula unit in solution, the
colligative effect of an electrolyte solution is always greater than that of a non-electrolyte of the same
molar concentration. All colligative properties are used for calculating molecular masses of non-volatile
solutes. However osmotic pressure is the best colligative property for determining molecular mass of a
non-volatile substance.

Points to remember
(i) Colligative properties  Number of particles
 Number of molecules (in case of non-electrolytes)
 Number of ions (In case of electrolytes)
 Number of moles of solute
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 Mole fraction of solute
(ii) For different solutes of same molar concentration, the magnitude of the colligative properties is
more for that solution which gives more number of particles on ionization.
(iii) For different solutions of same molar concentration of different non-electrolyte solutes, the
magnitude of the colligative properties will be same for all.
(iv) For different molar concentrations of the same solute, the magnitude of colligative properties is
more for the more concentrated solution.
(v) For solutions of different solutes but of same percent strength, the magnitude of colligative property
is more for the solute with least molecular weight.
(vi) For solutions of different solutes of the same percent strength, the magnitude of colligative
property is more for that solute which gives more number of particles, which can be known by the
knowledge of molecular weight and its ionization behavior.

12. Abnormal molecular masses.

Molecular masses can be calculated by measuring any of the colligative properties. The relation
between colligative properties and molecular mass of the solute is based on following assumptions.
(1) The solution is dilute, so that Raoult’s law is obeyed.
(2) The solute neither undergoes dissociation nor association in solution.

In case of solutions where above assumptions are not valid we find discrepancies between observed
and calculated values of colligative properties. These anomalies are primarily due to
(i) Association of solute molecules.
(ii) Dissociation of solute molecules.

(i) Association of solute molecules: Certain solutes in solution are found to associate. This eventually
leads to a decrease in the number of molecular particles in the solutions. Thus, it results in a decrease in
the values of colligative properties. As already discussed, the colligative properties are inversely related
to the molecular mass,
1
Colligative property  , therefore, higher values are obtained for molecular
molecular mass of solute
masses than normal values for unassociated molecules.

22
(ii) Dissociation of solute molecules: A number of electrolytes dissociate in solution to give two or
more particles (ions). Therefore, the number of solute particles, in solutions of such substances, is more
than the expected value. Accordingly, such solutions exhibit higher values of colligative properties.
Since colligative properties are inversely proportional to molecular masses, therefore, molecular masses
of such substances as calculated from colligative properties will be less than their normal values.

Van’t Hoff’s factor (i): In 1886, Van’t Hoff introduced a factor ‘i’ called Van’t Hoff’s factor, to express
the extent of association or dissociation of solutes in solution. It is ratio of the normal and observed
molecular masses of the solute, i.e.
Normal molecular mass
i
Observed molecular mass

In case of association, observed molecular mass being more than the normal, the factor i has a value
less than 1. But in case of dissociation, the Van’t Hoff’s factor is more than 1 because the observed
molecular mass has a lesser value than the normal molecular mass. In case there is no dissociation the
value of ‘i’ becomes equal to one.

Since colligative properties are inversely proportional to molecular masses, the Van’t Hoff’s factor may
also be written as:
Observed value of colligative property
i
Calculated value of colligative property assuming no associatio n or dissociati on
No. of particles after associatio n or dissociati on
i
No. of particles before associatio n or dissociati on

Introduction of the Van’t Hoff factor modifies the equations for the colligative properties as follows:
PAo  PA
Relative lowering of vapor pressure   iXB
PAo
Elevation of boiling point, Tb  ik b m
Depression in freezing point, T f  ik f m

inRT
Osmotic pressure,   ;   iCRT
V

From the value of “i”, it is possible to calculate degree of dissociation or degree of association of
substance.

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Degree of dissociation (): It is defined as the fraction of total molecules which dissociate into simpler
molecules or ions.
i1
 ; m= number of particles in solution
m 1

Degree of association (): It is defined as the fraction of the total number of molecules which
associate or combine together resulting in the formation of a bigger molecules.
i1
 ; m = number of particles in solution
1/m 1

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