152 Solution and Colligative properties

Chapter

4
Solution & Colligative properties

“A solution is a mixture in which substances are Liquid Solid Salt in water, sugar in water.
intermixed so intimately that they can not be observed Solid Gas Adsorption of gases over metals;
as separate components”. The dispersed phase or the hydrogen over palladium.
substance which is to be dissolved is called solute, Solid Liquid Mercury in zinc, mercury in gold,
CuSO4.5H2O.
while the dispersion medium in which the solute is
Solid Solid Homogeneous mixture of two or more
dispersed to get a homogenous mixture is called the metals (alloys), e.g., copper in gold,
solvent. zinc in copper.
Solubility Among these solutions the most significant type of
solutions are those which are in liquid phase and may
“Solubility of a substance may be defined as the be categorised as, (1) Solid in liquid solutions, (2)
amount of solute dissolved in 100gms of a solvent to Liquid in liquid solutions and (3) Gas in liquid
form a saturated solution at a given temperature”. A solutions.
saturated solution is a solution which contains at a
Methods of expressing concentration of solution
given temperature as much solute as it can hold in
presence of dissolveding solvent. Any solution may Concentration of solution is the amount of solute
contain less solute than would be necessary to saturate dissolved in a known amount of the solvent or solution.
it. Such a solution is known as unsaturated solution. The concentration of solution can be expressed in
When the solution contains more solute than would be various ways as discussed below,
necessary to saturate it then it is termed as (1) Percentage : It refers to the amount of the
supersaturated solution. solute per 100 parts of the solution. It can also be called
as parts per hundred (pph). It can be expressed by any
Kinds of solutions of following four methods,
All the three states of matter (gas, liquid or (i) Weight to weight percent
solid) may behave either as solvent or solute. Wt.of solute
% w/w   100
Depending on the state of solute or solvent, Wt.of solution
mainly there may be following nine types of binary Example : 10% Na2CO 3 solution w/w means
solutions.
10g of Na2CO 3 is dissolved in 100g of the
Solven Solute Example
t solution. (It means 10g Na2CO 3 is dissolved in
Gas Gas Mixture of gases, air. 90g of H 2O )
Gas Liquid Water vapours in air, mist.
Gas Solid Sublimation of a solid into a gas, (ii) Weight to volume percent
smoke. Wt.of solute
Liquid Gas CO2 gas dissolved in water (aerated % w/v   100
drinks).
Volumeof solution
Liquid Liquid Mixture of miscible liquids, e.g., alcohol
in water.
 153 Solution and Colligative properties

Example : 10% Na2CO3 (w/v) means 10g (i)

Na2CO 3 is dissolved in 100cc of solution. Numberof g.eq.of solute
(N) 
Normality
(iii) Volume to volume percent
Volumeof solution (l)
Vol. of solute (ii) N
% v/v   100
Vol. of solution Weightof solutein g.

Example : 10% ethanol (v/v) means 10cc of  Volumeof solution
g.eq.weightof solute (l)
ethanol dissolved in 100cc of solution.
Wt.of soluteperlitreof solution
(iv) Volume to weight percent (iii) N 
g eq.wt.of solute
Vol. of solute
% v/w   100 (iv)
Wt.of solution
Wt.of solute 1000
Example : 10% ethanol (v/w) means 10cc of N  
g.eq.wt.of solute Vol. of solutionin ml
ethanol dissolved in 100g of solution.
(2) Parts per million (ppm) and parts per Percentof solute 10
(v) N  ,
billion (ppb) : When a solute is present in trace g eq.wt.of solute
quantities, it is convenient to express the concentration
in parts per million and parts per billion. It is the number Strengthin g l-1 of solution
(vi) N 
6
of parts of solute per million (10 ) or per billion g eq.wt.of solute

(109 ) parts of the solution. It is independent of the Wt% density 10

(vii) N 
temperature. Eq. wt.
massof solutecomponent 6 (viii) If volume V1 and normality N1 is so
ppm  10
Total massof solution
changed that new normality and volume N 2 and V2
massof solutecomponent 9 then,
ppb  10
Total massof solution N1V1  N 2V2 (Normality equation)
(3) Strength : The strength of solution is defined (ix) When two solutions of the same solute are
as the amount of solute in grams present in one litre (or
mixed then normality of mixture (N) is
dm3 ) of the solution. It is expressed in g/litre or
N1V1  N 2V2
(g / dm3 ) . N
V1  V2
Massof solutein grams
Strength (x) Vol. of water to be added i.e., (V2  V1 ) to
Volumeof solutionin litres
get a solution of normality N 2 from V1 ml of
(4) Normality (N) : It is defined as the number of
gram equivalents (equivalent weight in grams) of a normality N1
solute present per litre of the solution. Unit of normality
 N  N2 
is gram equivalents litre–1. Normality changes with V2  V1   1  V1

temperature since it involves volume. When a solution  N2 
is diluted x times, its normality also decreases by x (xi) If Wg of an acid is completely neutralised by
times. Solutions in term of normality generally
expressed as, V ml of base of normality N
Wt.of acid VN
N  Normal solution; 5N  Penta normal, 
g eq.wt.of acid 1000
10N  Deca normal; N / 2  semi normal
Similarly,
N / 10  Deci normal; N / 5  Penti normal Wt.of base Vol. of acid N of acid

N / 100 or 0.01 N  centinormal, g eq.wt.of base 1000

N / 1000 or 0.001= millinormal (xii) When Va ml of acid of normality N a is

Mathematically normality can be calculated by mixed with Vb ml of base of normality N b
following formulas,
(a) If Va N a  Vb N b (Solution neutral)

(b) If Va N a  Vb N b (Solution is acidic)

 Solution and Colligative properties 154
(c) If Vb N b  Va N a (Solution is basic) Percentof solute 10
(v) M 
(xiii) Normality of the acidic mixture Mol. wt.of solute
Va N a  Vb N b (vi) M 
Strengthin gl-1of solution

(Va  Vb ) Mol.wt.of solute
(vii)
(xiv) Normality of the basic mixture
10 Sp.gr.of thesolution Wt.% of thesolute
V N  Va N a M 
 b b Mol. wt.of thesolute
(Va  Vb ) (viii) If molarity and volume of solution are
No. of meq * of solute changed from M 1 ,V1 to M 2 , V2 . Then,
(xv) N 
Vol. of solutionin ml M 1V1  M 2V2 (Molarity equation)
(* 1 equivalent = 1000 milliequivalent or
meq.) (ix) In balanced chemical equation, if n1 moles of
(5) Molarity (M) : Molarity of a solution is the reactant one react with n2 moles of reactant two.
number of moles of the solute per litre of solution (or Then,
number of millimoles per ml. of solution). Unit of
molarity is mol/litre or mol/dm3 For example, a molar M 1V1 M V
 2 2
(1M ) solution of sugar means a solution containing 1 n1 n2
mole of sugar (i.e., 342 g or 6.02 1023 molecules of (x) If two solutions of the same solute are
it) per litre of the solution. Solutions in term of molarity mixed then molarity (M) of resulting solution.
generally expressed as, M 1V1  M 2V2
1M = Molar solution, 2M = Molarity is two,
M
(V1  V2 )
M (xi) Volume of water added to get a solution of
or 0.5 M = Semimolar solution,
2
molarity M 2 from V1 ml of molarity M 1 is
M
10
or 0.1 M = Decimolar solution,  M  M2 
V2  V1   1  V1
M  M 2 
or 0.01 M = Centimolar solution
100 Relation between molarity and normality
M Normality of solution = molarity
or 0.001 M = Millimolar solution
1000 Molecularmass

 Molarity is most common way of representing the Equivalent
mass
concentration of solution. Normality  equivalent mass = molarity 
1 molecular mass
 Molarity is depend on temperature as, M 
T Molecular
mass
For an acid, = Basicity
 When a solution is diluted (x times), its molarity Equivalent
mass
also decreases (by x
times) So, Normality of acid = molarity  basicity.
Mathematically molarity can be calculated by Molecular
mass
following formulas, For a base, = Acidity
Equivalent
mass
No. of molesof solute(n)
(i) M  , So, Normality of base = Molarity  Acidity.
Vol. of solutionin litres
(6) Molality (m) : It is the number of moles or
(ii) gram molecules of the solute per 1000 g of the solvent.
Wt.of solute(ingm)perlitreof solution Unit of molality is mol/ kg . For example, a 0.2 molal
M 
Mol. wt.of solute (0.2m) solution of glucose means a solution obtained
(iii) by dissolving 0.2 mole of glucose in 1000gm of water.
Wt.of solute(ingm) 1000 Molality (m) does not depend on temperature since it
M   involves measurement of weight of liquids. Molal
Mol. wt.of solute Vol. of solution
in ml.
solutions are less concentrated than molar solution.
No. of millimolesof solute
(iv) M  Mathematically molality can be calculated by
Vol. of solutionin ml following formulas,
 155 Solution and Colligative properties

(i) WB (g) WB (g)  1000

Number of moles
of the Thus, F 
solute or
m GFM  V(l)
 1000 GFM  V(ml)
Weight
of thesolventin grams
(8) Mole fraction (X) : Mole fraction may be
Strengthper1000gramsof solvent defined as the ratio of number of moles of one
(ii) m 
Molecularmassof solute component to the total number of moles of all the
components (solvent and solute) present in the solution.
No. of gmmolesof solute It is denoted by the letter X . It may be noted that the
(iii) m 
Wt.of solvent
in kg mole fraction is independent of the temperature. Mole
(iv) fraction is dimensionless. Let us suppose that a solution
contains the components A and B and suppose that
Wt.of solute 1000
m  WA g of A and WB g of B are present in it.
Mol. wt.of solute Wt.of solvent
in g
No. of millimoles
of solute WA
(v) m  Number of moles of A is given by, nA 
Wt.of solventin g MA
and
10 solubility
(vi) m  WB
Mol. wt.of solute the number of moles of B is given by, nB 
MB
1000 wt.% of solute(x)
(vii) m  where M A and M B are molecular masses of
(100 x)  mol.wt.of solute
A and B respectively.
(viii) Total number of moles of A and B  nA  nB
1000 Molarity nA
m
(1000 sp.gravity)  Mol. wt.of solute)Mole fraction of A , X A 
 (Molarity
nA  nB
Relation between molarity (M) and molality
nB
(m) Mole fraction of B , XB 
nA  nB
Molality (m) =
The sum of mole fractions of all the components in
Molarity the solution is always one.
Molarity molecular
mass nA nB
Density X A  XB    1.
1000 nA  nB nA  nB
Molality density Thus, if we know the mole fraction of one
 component of a binary solution, the mole fraction of the
Molarity (M) Molality molecular
mass
1 other can be calculated.
1000 Relation between molality of solution (m)
and mole fraction of the solute (XA).
(7) Formality (F) : Formality of a solution may be
defined as the number of gram formula masses of the m
XA 
ionic solute dissolved per litre of the solution. It is 55.5  m
represented by F . Commonly, the term formality is (9) Mass fraction : Mass fraction of a component
used to express the concentration of the ionic solids in a solution is the mass of that component divided by
which do not exist as molecules but exist as network of the total mass of the solution. For a solution containing
ions. A solution containing one gram formula mass of wA gm of A and wB gm of B
solute per litre of the solution has formality equal to one
wA
and is called formal solution. It may be mentioned here Mass fraction of A ; Mas fraction of
that the formality of a solution changes with change in wA  wB
temperature. wB
Formality (F)= B
wA  wB
Numberof gramformulamasses of solute It may be noted that molality, mole fraction, mass
Volumeof solutionin litres fraction etc. are preferred to molarity, normality, etc.
because the former involve the weights of the solute
=
and solvent where as later involve volumes of solutions.
Massof ionicsolute(g) Temperature has no effect on weights but it has
significant effect on volumes.
 (Volumeof solution
(gm. formulamassof solute) (l))
 Solution and Colligative properties 156
(10) Demal unit (D) : The concentrations are also Ptotal  pA  pB  (p0A  X A )  (pB
0
 XB )
expressed in “Demal unit”. One demal unit represents
one mole of solute present in one litre of solution at Alternatively, Raoult’s law may be stated as “the
0o C . relative lowering of vapour pressure of a solution
containing a non-volatile solute is equal to the mole
Colligative properties fraction of the solute in the solution.”
Certain properties of dilute solutions containing Relative lowering of vapour pressure is defined as
non-volatile solute do not depend upon the nature of the ratio of lowering of vapour pressure to the vapour
the solute dissolved but depend only upon the pressure of the pure solvent. It is determined by
concentration i.e., the number of particles of the solute Ostwald-Walker method.
present in the solution. Such properties are called
Thus according to Raoult’s law,
colligative properties. The four well known examples of
the colligative properties are, w
(1) Lowering of vapour pressure of the solvent. p0  p n
(2) Osmotic pressure of the solution.   m
p0 n N w  W
(3) Elevation in boiling point of the solvent.
(4) Depression in freezing point of the solvent.
m M
Since colligative properties depend upon the where, p  Vapour pressure of the solution
number of solute particles present in the solution, the
p0  Vapour pressure of the pure solvent
simple case will be that when the solute is a non-
electrolyte. In case the solute is an electrolyte, it may n Number of moles of the solute
split to a number of ions each of which acts as a particle
and thus will affect the value of the colligative property. N  Number of moles of the solvent
Each colligative property is exactly related to w and m weight and mol. wt. of solute
other, Relative lowering of vapour pressure, elevation in
boiling point and depression in freezing point are
W and M  weight and mol. wt. of the solvent.
directly proportional to osmotic pressure. Limitations of Raoult’s law
Lowering of vapour pressure  Raoult’s law is applicable only to very dilute
solutions.
The pressure exerted by the vapours above the
liquid surface in equilibrium with the liquid at a given  Raoult’s law is applicable to solutions containing
temperature is called vapour pressure of the liquid. The non-volatile solute only.
vapour pressure of a liquid depends on,  Raoult’s law is not applicable to solutes which
(1) Nature of liquid : Liquids, which have weak dissociate or associate in the particular solution.
intermolecular forces, are volatile and have greater
vapour pressure. For example, dimethyl ether has
greater vapour pressure than ethyl alcohol.
(2) Temperature : Vapour 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 vapour phase.
(3) Purity of liquid : Pure liquid always has a
vapour pressure greater than its solution.
Raoult’s law : When a non-volatile substance
is dissolved in a liquid, the vapour pressure of the
liquid (solvent) is lowered. According to Raoult’s law
(1887), at any given temperature the partial vapour
pressure (pA) of any component of a solution is equal
to its mole fraction (XA) multiplied by the vapour
pressure of this component in the pure state (p0
A) .

That is, pA  p0A  X A

The vapour 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 vapour pressures
pA and pB .
 157 Solution and Colligative properties

Ideal and Non-Ideal solution

Table: 4.1 Ideal and non-ideal solutions
Non-ideal solutions
Ideal solutions Positive deviation from Raoult's Negative deviation from
law Raoult's law
1. Obey Raoult's law at every 1. Do not obey Raoult's law. 1. Do not obey Raoult's law.
range of concentration.
2. H mix  0; neither heat is 2. H mix  0. Endothermic 2. H mix  0. Exothermic
evolved nor absorbed dissolution; heat is absorbed. dissolution; heat is evolved.
during dissolution.
3. Vmix  0; total volume of 3. Vmix  0. Volume is increased 3. Vmix  0. Volume is
solution is equal to sum of after dissolution. decreased during dissolution.
volumes of the components.
4. P  pA  pB  p0A X A  pB
0
XB i. 4. pA  p0A X A ; pB  pB
0
XB 4. pA  p0A X A ; pB  pB
0
XB
e.,
 pA  pB  p0A X A  pB0 X B  pA  pB  p0A X A  pB0 X B
pA  p0A X A : pB  0
pB XB
5. A  A, A  B, B  B 5. A  B attractive force should 5. A  B attractive force should
interactions should be same, i.e., be weaker than A  A and be greater than A  A and
'A' and 'B' are identical in shape,
B  B attractive forces. 'A' and B  B attractive forces. 'A' and
size and character.
'B' have different shape, size 'B' have different shape, size
and character. and character.
6. Escaping tendency of 'A' and 'B' 6. 'A' and 'B' escape easily 6. Escaping tendency of both
should be same in pure liquids showing higher vapour pressure components 'A' and 'B' is
and in the solution. than the expected value. lowered showing lower vapour
pressure than expected ideally.
Examples: Examples: Examples:
Dilute solutions; Acetone +ethanol Acetone + aniline;
benzene + toluene: acetone + CS2 : acetone + chloroform;
n-hexane + n-heptane; CH 3OH  CH 3COOH ;
water + methanol;
chlorobenzene +
water + ethanol; H 2O  HNO3
bromobenzene;
CCl4  toluene; chloroform + diethyl ether;
ethyl bromide + ethyl iodide;
n-butyl chloride + n-butyl CCl 4  CHCl 3 ; water + HCl;
bromide acetic acid + pyridine;
acetone + benzene;
chloroform + benzene
CCl4  CH 3OH ;
cyclohexane + ethanol

Graphical representation of ideal and non-ideal solutions

Vapour pressure

Vapour pressure

Vapour pressure

Ideal solution Positive deviation Negative deviation

Total vapour
p°A P=pA + pB p°A pressure p°A Total vapour
pressure
PA=p0A XA p°B p°B p°B

PB=p0B XB
Ideal
Ideal

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

XB = 0 XB = 1 XB = 0 XA= 0 XB = 0 XB = 1
 Solution and Colligative properties 158

Azeotropic mixture through a semi-permeable membrane.

membrane.
Azeotropes are defined as the mixtures of liquids
which boil at constant temperature like a pure liquid and It involves movement of only It involves passage of
possess same composition of components in liquid as solvent molecules from one solvent as well as solute
side to the other. molecules from one region
well as in vapour phase. Azeotropes are also called
to the other.
constant boiling mixtures because whole of the
azeotropes changes into vapour state at constant Osmosis is limited to Diffusion can take place in
temperature and their components can not be solutions only. liquids, gases and solutions.
separated by fractional distillation. Azeotropes are of Osmosis can be stopped or Diffusion can neither be
two types as described below, reversed by applying stopped nor reversed
(1) Minimum boiling azeotrope : For the additional pressure on the
solutions with positive deviation there is an solution side.
intermediate composition for which the vapour pressure (2) Osmotic pressure ()
of the solution is maximum and hence, boiling point is
minimum. At this composition the solution distills at The osmotic pressure of a solution at a particular
constant temperature without change in composition. temperature may be defined as the excess hydrostatic
This type of solutions are called minimum boiling pressure that builds up when the solution is separated
azeotrope. e.g., from the solvent by a semi-permeable membrane. It is
denoted by .
H 2O  C2H 5OH, H 2O  C2H 5CH 2OH
or
CHCl 3  C 2H 5OH , (CH 3 )2 CO  CS2 Osmotic pressure may be defined as the excess
(2) Maximum boiling azeotrope : For the pressure which must be applied to a solution in order to
solutions with negative deviations there is an prevent flow of solvent into the solution through the
intermediate composition for which the vapour pressure semi-permeable membrane.
of the solution is minimum and hence, boiling point is or
maximum. At this composition the solution distill`s at Osmotic pressure is the excess pressure which
constant temperature without the change in must be applied to a given solution in order to increase
composition. This type of solutions are called maximum its vapour pressure until it becomes equal to that of the
boiling azeotrope. e.g., solution.
H 2O  HCl, H 2O  HNO3, H 2O  HClO4 (i) Measurements of osmotic pressure :
Following methods are used for the measurement of
Osmosis and Osmotic pressure of the solution osmotic pressure,
(1) Osmosis : The flow of solvent from pure (a) Pfeffer’s method, (b) Morse and Frazer’s
solvent or from solution of lower concentration into method, (c) Berkeley and Hartley’s method, (d)
solution of higher concentration through a semi- Townsend’s negative pressure method, (e) De Vries
permeable membrane is called Osmosis. Osmosis may plasmolytic method.
be divided in following types, (ii) Determination of molecular mass of non-
(i) Exo-Osmosis : The outward osmotic flow of volatile solute from osmotic pressure () : The
water from a cell containing an aqueous solution osmotic pressure is a colligative property. For a given
through a semi-permeable membrane is called as Exo- solvent the osmotic pressure depends only upon the
osmosis. For example, egg (after removing hard shell) molar concentration of solute but does not depend upon
placed in conc. NaCl solutions, will shrink due to exo- its nature. The following relation relates osmotic
osmosis. pressure to the number of moles of the solute,
(ii) Endo-osmosis : The inward flow of water into According to Boyle Van't Hoff law (at conc. temp.)
the cell containing an aqueous solution through a semi-
permeable membrane is called as endo-osmosis. e.g.,  C .....(i)
an egg placed in water swells up due to endo-osmosis. According to Gaylussac Van't Hoff law (at conc.
(iii) Reverse osmosis : If a pressure higher than temp.)
osmotic pressure is applied on the solution, the solvent  T .....(ii)
will flow from the solution into the pure solvent through
the semi-permeable membrane. Since here the flow of From equation (i) and (ii)
solvent is in the reverse direction to that observed in   CT ,   CRT (Van't Hoff equation)
the usual osmosis, the process is called reverse
osmosis. n  n w RT
 RT  C   ;  
Differences between osmosis and diffusion V  V m V
Osmosis Diffusion  w
In osmosis movement of In diffusion there is no role  n  
 m
molecules takes place of semi-permeable
 159 Solution and Colligative properties

Here, C = concentration of solution in moles per NaCl are isotonic then,    but
litre Urea and (dissociat
e) 1 2

R = gas constant ; T = temperature C1  C2

n = number of moles of solute ; V = volume of
solution Urea and Benzoicacidare isotonic then,
(associate
)
m = molecular weight of solute ; w = weight of
solute  1   2 but C1  C2
(iii) Conditions for getting accurate value of
(b) Hypertonic and hypotonic solution : The
molecular mass are,
solution which has more osmotic pressure than the
(a) The solute must be non-volatile.
other solution is called as hypertonic solution and the
(b) The solution must be dilute. solution which has lesser osmotic pressure than the
(c) The solute should not undergo dissociation or other is called as hypotonic solution.
association in the solution.
The flow of solvent is always from lower osmotic
(iv) Relation of osmotic pressure with
pressure to higher osmotic pressure i.e. from hypotonic
different colligative properties : Osmotic pressure is
to hypertonic solution.
related to relative lowering of vapour pressure,
elevation of boiling point and depression of freezing Elevation in b.pt. of the solvent (Ebullioscopy)
point according to the following relations,
Boiling point of a liquid may be defined as the
 P o  P  dRT temperature at which its vapour pressure becomes
(a)    A o A   (b) equal to atmospheric pressure, i.e., 760 mm. Since the
 PA  M addition of a non-volatile solute lowers the vapour
dRT pressure of the solvent, solution always has lower
  Tb  vapour pressure than the solvent and hence it must be
1000 K b
heated to a higher temperature to make its vapour
dRT pressure equal to atmospheric pressure with the result
(c)   Tf  the solution boils at a higher temperature than the pure
1000 K f
solvent. Thus sea water boils at a higher temperature
In the above relations,  = Osmotic pressure; d = than distilled water. If Tb is the boiling point of the
Density of solution at temperature T; R = Universal gas solvent and T is the boiling point of the solution, the
constant; M = Mol. Mass of solute; K b = Molal difference in the boiling point (T or  Tb) is called the
K f = Molal elevation of boiling point.
elevation constant of solvent;
depression constant of solvent T  Tb  Tb or T
(v) Isotonic, Hypertonic and Hypotonic Elevation in boiling point is determined by
solutions Landsberger’s method and Cottrell’s method. Study of
(a) Isotonic or iso-osmotic solutions : Two solutions elevation in boiling point of a liquid in which a non-
of different substances having same osmotic pressure at volatile solute is dissolved is called as ebullioscopy.
same temperature are known as isotonic solutions.
Important relations concerning elevation in
For isotonic solutions,  1   2 Primary Condition boiling point
…..(i) (1) The elevation of boiling point is directly
C1  C2 proportional to the lowering of vapour pressure, i.e.,
Also,
Tb  p0  p
n1 n2
or  Secondary Conditions
V1 V2 (2) Tb  K b  m

w1 w2 where Kb  molal elevation constant or

or  ebullioscopic constant of the solvent; m  Molality of
m1V1 m2V2
the solution, i.e., number of moles of solute per
…..(ii)
1000g of the solvent; Tb  Elevation in boiling
Eq. (ii) holds good only for those solutes which
neither possess the tendency to get associate nor point
dissociate in solution, e.g., 1000 K b  w
(3) Tb  or
Urea and glucose are isotonic then,  1   2 and m W
C1  C2 1000 K b  w
m
Tb  W
 Solution and Colligative properties 160
where, Kb is molal elevation constant and where Kf is molal depression constant and
defined as the elevation in b.pt. produced when 1 mole defined as the depression in freezing point produced
of the solute is dissolved in 1 kg of the solvent. when 1 mole of the solute is dissolved in 1kg of the
w and W are the weights of solute and solvent solvent. w and W are the weights of solute and
and m is the molecular weight of the solute. solvent and m is the molecular weight of the solute.
0.002(T0)2 R(T0)2 0.002(T0)2
(4) Kb  (4) K f  
lV l f 1000 lf
where T0  Normal boiling point of the pure where T0  Normal freezing point of the solvent;
solvent; lV  Latent heat of evaporation in cal/ g of l f  Latent heat of fusion/g of solvent; K f for water is
pure solvent; K b for water is 0.52 deg kg mol1 . 1.86 deg kg mol1

Depression in f.pt. of the solvent (Cryoscopy) Colligative properties of electrolytes

Freezing point is the temperature at which the The colligative properties of solutions, viz.
liquid and the solid states of a substance are in lowering of vapour pressure, osmotic pressure,
equilibrium with each other or it may be defined as the elevation in b.p. and depression in freezing point,
temperature at which the liquid and the solid states of a depend on the total number of solute particles present
substance have the same vapour pressure. It is in solution. Since the electrolytes ionise and give more
observed that the freezing point of a solution is always than one particle per formula unit in solution, the
less than the freezing point of the pure solvent. Thus colligative effect of an electrolyte solution is always
the freezing point of sea water is low than that of pure greater than that of a non-electrolyte of the same molar
water. The depression in freezing point (T or concentration. All colligative properties are used for
calculating molecular masses of non-volatile solutes.
Tf ) of a solvent is the difference in the freezing
However osmotic pressure is the best colligative
point of the pure solvent (Ts) and the solution property for determining molecular mass of a non-
volatile substance.
(Tsol. ) .
Colligative properties are depending on following
Ts  Tsol  Tf or T factory

NaCl or CaCl2 (anhydrous) are used to clear (1) Colligative properties  Number of particles
snow on roads. They depress the freezing point of water  Number of molecules
and thus reduce the temperature of the formation of (in case of non-electrolytes)
ice.
Depression in freezing point is determined by
 Number of ions
Beckmann’s method and Rast’s camphor method. Study (In case of electrolytes)
of depression in freezing point of a liquid in which a non-  Number of moles of
volatile solute is dissolved in it is called as cryoscopy. solute
Important relations concerning depression in
freezing point.
 Mole fraction of solute

(1) Depression in freezing point is directly (2) For different solutes of same molar
proportional to the lowering of vapour pressure. concentration, the magnitude of the colligative
properties is more for that solution which gives more
Tf  p0  p
number of particles on ionisation.
(2) Tf  K f  m (3) For different solutions of same molar
Kf  concentration of different non-electrolyte solutes, the
where molal depression constant or
magnitude of the colligative properties will be same for
cryoscopic constant; m Molality of the solution (i.e., all.
no. of moles of solute per 1000g of the solvent); (4) For different molar concentrations of the same
Tf  Depression in freezing point solute, the magnitude of colligative properties is more
for the more concentrated solution.
1000 K f  w (5) For solutions of different solutes but of same
(3) Tf  or
m W percent strength, the magnitude of colligative property
is more for the solute with least molecular weight.
1000 K f  w
m (6) For solutions of different solutes of the same
Tf  W percent strength, the magnitude of colligative property
 161 Solution and Colligative properties

is more for that solute which gives more number of Since colligative properties are inversely
particles, which can be known by the knowledge of proportional to molecular masses, the Van’t Hoff’s factor
molecular weight and its ionisation behaviour. may also be written as,
Abnormal molecular masses Observedvalueof colligative property
Molecular masses can be calculated by measuring i
any of the colligative properties. The relation between Calculatedvalueof colligative property
colligative properties and molecular mass of the solute assumingnoassociation or dissociation
is based on following assumptions.
(1) The solution is dilute, so that Raoult’s law is
obeyed. No. of particl
esafterassociatio
n or dissociati
on
i
(2) The solute neither undergoes dissociation nor No. of particl
esbeforeassociatio
n or dissociati
on
association in solution.
Introduction of the Van’t Hoff factor modifies the
In case of solutions where above assumptions are equations for the colligative properties as follows,
not valid we find discrepencies between observed and
Relative lowering of vapour pressure
calculated values of colligative properties. These
anomalies are primarily due to PAo  PA
(i) Association of solute molecules.   iXB
PAo
(ii) Dissociation of solute molecules.
(i) Association of solute molecules : Certain Elevation of boiling point, Tb  ikbm
solutes in solution are found to associate. This
eventually leads to a decrease in the number of Depression in freezing point, Tf  ikf m
molecular particles in the solutions. Thus, it results in a inRT
decrease in the values of colligative properties. Osmotic pressure,   ;   iCRT
V
1
Colligative property  From the value of ‘i’, it is possible to calculate
molecular
massof solute degree of dissociation or degree of association of
therefore, higher values are obtained for substance.
molecular masses than normal values for unassociated Degree of dissociation ( ) : It is defined as the
molecules. fraction of total molecules which dissociate into simpler
(ii) Dissociation of solute molecules : A molecules or ions.
number of electrolytes dissociate in solution to give two i1
or more particles (ions). Therefore, the number of solute  ; m= number of particles in solution
particles, in solutions of such substances, is more than m 1
the expected value. Accordingly, such solutions exhibit Degree of association ( ) : It is defined as the
higher values of colligative properties. Since colligative fraction of the total number of molecules which
properties are inversely proportional to molecular associate or combine together resulting in the formation
masses, therefore, molecular masses of such of a bigger molecules.
substances as calculated from colligative properties will i 1
be less than their normal values.  ; m = number of particles in
1/ m  1
Van’t Hoff’s factor (i) : In 1886, Van’t Hoff
solution.
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.,
Normalmolecular
mass
i
Observed
molecularmass
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.