1

C-02:- Solutions

1. INTRODUCTION
A solution may be defined as a homogeneous mixture of two or more non-reacting substance whose composition can be varied
within caertain fixed limit.
In a homogeneous mixture the particles are of molecular size i.e., up to 109 to 107 m.
The dissolved substance in solution is called as solute and the medium in which it is dissolved is known as the solvent. Conventionally
the substance present in larger quantity is called the solvent and the one present in smaller quantity is called solute.
When a solution is composed of two, three of four components then it is called binary, ternary or quanternary solution respectively.
2. TYPE OF SOLUTIONS
A solution can exist in all the thre states of matter i.e., in the solid, liquid and gaseous states. Depending upon the physical states of the
components there can be nine different types of solutions as tabulated below in the table

Sr. No. Solute Solvent Examples

i) Solid Solid Alloys such as brass
ii) Solid Liquid Sugar or NaCl in water
iii) Solid Gas Iodine or computer vapour in air
iv) Liquid Liquid Ethanol in water
v) Liquid Solid Hg in Zn, i,e zinc
vi) Liquid Gas Humidity in air
vii) Gas Gas Air, mixture of gases
viii) Gas Liquid Aerated drinks
ix) Gas Solid Adsorption of gases on metals
2.1 Solutions of liquids in liquids : When two liquids are mixed, the mixture maybe of the following types:
i) 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
examole, benzene and water, carbon tetrachloride and water, benzene and alcohol.
ii) The miscibility of the component may be partial. If the intermolecular attraction of one liquid is different from intermolecular
attraction of the other, there may be a partial miscibility of the two liquids. For example, ether and water, water and phenol; nicotine
and water.
iii) 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 n-hexane)
Solutions in water are caled aqueous solutions and the solutions in which water is not the solvent are called non-aqueous solutions.
2.1.1Cause of Miscibility of Liquids
i) Chemically alike liquids dissolv in one anothr more freely as compared to others, for examole, alkanes are, however, not miscible with
water because they cannot form H-Bonds with water molecules.
ii) Dipole-dipole interactions also play an important role in forming liquid solutions.
iii) Molecular sizes of liquids, which are mutually soluble, are also approximately same.
iv) Randomness or disorder of the system increases with increase in temperature. Hence the solubility increases with the increase in
temperature in most cases.
2.2 Solution of gases in Liquids: All gases are soluble in water as well as in other liquids to a greatr or lesser extent. The solubility of a
gas in liquids depends upon the following factors:
i) Nature of the gas
ii) Nature of the solvent
iii) Temperature and
iv) Pressure
2.2.1 Causes of Miscibility of gases in liquids: Generally, the gases which can be easily liquefied, are more soluble in water. For
example, CO2 is more soluble than hydrogen or oxygen in water. The gases which are capable of forming ions in aqueous solutions
are much more soluble in water (due to hydration of ions) than in other solvents. Gases like hydrogen chlorine and ammonia are
highly soluble in water but not in organic solvent in which they do not form ions. The solubility of most gases in liquids decreases
with increase of temperature. However, some gases are more soluble at higher temperature than at lower.
 2

The most important factor which influences the solubility of a gas in liquids is the pressure. The quantitative connection between the
solubility and the pressure is given by Henrys law. According to this law mass of gas dissolved by a given volume of a liquid, at
constant temperature, is proportional of the pressure of the gas. It has been found that most gases obey Henrys law provided.
i) The pressure is not too high.
ii) The temperature is not too low
iii) The gas is not highly soluble and does not enter into chemical combination with the solvent.
iv) The gas does not dissociate.
2.3 Solution of solids in liquids: For the solid in liquid solutions the solid is reffered to as solute. The amount of solute that is dissolved
in 100g 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
i) Temperature
ii) Nature of solute and solvent
2.3.1 Cause of miscibility of solids in liquids
Th basic cause attributable to th solubility of solid solute in liquid solvent can be summed up in one line, i.e., like dissolves like
which implies that polar solvent 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 solvation) 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.
Heat of solution (Hmix). Is the algebric sum of lattice energy and hydration energy of the solute.
Thus, heat of solution = lattice energy + hydration energy.
3. METHODS OR MODES OF EXPRESSING CONCENTRATION OF A SOLUTION
The term concentration means the exact quantity of the solute present in exact amount of solvent of that of solution. A solution of
known concentration is referred to as standard solution. The following are some of the different modes of expressing the concentration
of solutions.
3.1 Molarity (M): It is the most common unit of expressing the concentration of a solution. The molarity of a solution is the number of
moles of the solute dissolved per litre of the solution. It is denoted as M.
A solution which contains 1 mole of the solute dissolved in one litre of the solution is called a molar solution. The molarity of a
solution can be calculated from the following expression:
Strength in gram/litre wt.of the solute grams 1
Molarit (M) = =
molecular mass of solute Mol.wt.of the solute Vol.of the solution in litres
For preparing 0.1 M NaOH solution, we will dissolve (40(Mol. Wt.) 0.1 = 4g per litre of the solution.
3.2 Molarity (m): The molality of a solution is the number of moles of solute dissolved per 1000g (1 kg) of the solvent. It is denoted
asm. A solution haivng one mole of the solute dissolved in 1 kg of the solvent is called a molal solution. Mathematically,
No.of moles of the solute wt.of the solute grams 1000
m= 1000 =
Wt.of the solvent in grams Mol.wt of the solute wt.of the solvent in grams
For preparing 0.1 m Na2CO3 solution, we will dissolve (mol.wt., 106) 0.1 = 10.6 g per kg. of water.
Similarly one kg of water containing 4g of NaOH is 0.1 molal solution.
3.3 Normality (N): The normality of a solution is the number of gram equivalents of the solute dissolved per litre of the solution. It is
denoted as N
A solution having one gram equivalent of the solute per litre of the solution is calle a normal solution.
Normality of a solution is given by relation:
strength in grams/litre strength in grams 1
Normality(N) = =
Eg.wt.of the solute eg.wt.of the solute Vol.of solution in litres
or Normality Eq. Wt. of the solute = strength of the solution (g/|)
3.3.1 Relationship between Normality and Molarity
As, normality Eq. wt. = strength of the solution (g/|)
Similarly, molarity Mol. wt. = strength of the solution (g/|)
Hence normality Eq. Wt. = Molarity mol. wt
Normally Molwt.
Or = =n
Molarity Eq.Wt
So normality = n molarity
Normality
Or molarity =
n
Solutions are expressed as 1N, 2N, N/2, N/10, N/100, N/1000, etc.
1N = normal = one gram equivalent of the solute per litre of solution (normality is 1)
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N/2 = seminormal = 0.5 g equivalent of the solute per litre of solution (Normality is 0.5)
N/10 = decinomal = 1/10 g equivalent of the solute per litre of solution (Normality is 0.1)
N/100 = centinormal = 1/100g equivalent of the solute per litre of solution (Normality is 0.01)
N/1000 = Millinormal = 1/1000g equivalent of the solute per litre of solution (Normality is 0.001)
For preparing 100 ml o 1.0 N Na2CO3 solution, we will dissolve:
(Equivalent wt. 53) 1.0 100/1000 = 5.3 g per litre of the solution.
3.4 Formality(F). This term is used for ionic solids which dissolve in a polar solvent to give cations and atoms. It may be defined as the
number of gram formula mass o the solute dissolved in one litre of the solution. Thus a solution is said to be one formal when one
gram formula mass of it is dissolved in one litre of the solution. It is denoted by F. In general:
Formality =
Amount of solute in grams per litre of solution
. It is almost the same as molarity. For ionic solids the term molecular mass is replaced
Gram formula mass of the solute
by formula mass.
3.5 Mole fraction (x) : Mole fraction of a component is the ratio of number of moles of the component to be total number
of the moles of all the components of solution. It is denoted be X. For a binary solution consisting of two components,
the mole fraction of component 1 is denoted as X1 and that of component 2 is denoted as X2. Therefore, by definition:
n n
X1 = 1 and X2 = 2 where, n1 and n2 , are the number of moles of component 1 and component 2, respectively.
n1 +n2 n1 +2
For a solution, consisting of more than two components, we can write:
n1 n2 n3
X1 = X2 = ; X3 =
n1 +n2 +n3 n1 +n2 +n3 .. 1 +n2 +n3 .
It is evident from above that sum of the mole fraction of all the components is always unity i.e., X1 + X2 + X3 + . .1 and for a
binary solution: X1 + X2 = 1.
It is of interest to note that the units molality and mole fraction are based upon the weights of solvents. These units are preferred to
molarity, normality, formality which are based on volumes because it is easier to determine the weights of solvents accurately than the
volumes. Also these concentration units are independent of temperatures. With increase in temperature mole fraction, mass fraction,
mass fraction, mass percentage etc. do not show any change. But molarity, normality, formality, percentage by volume decrease with
the increase in temperature as these concentration terms are volume based and volume increases with increase in temperature .
3.6 Mole percent: Mole percent is the number of moles of a component in 100 moles o the solutes and the solvent. It may also be
expressed as:
Mole percent = mole fraction 100
For a solution containing 0.8 moles of ammonia and 1.2 mole of H 2O
0.8 8
Mole fracation o ammonia X NH3 = =
1.2+0.8 20
8
Mole percent of NH3 = 100 = 40 mole %
20
3.7 Mass fraction and mass percentage: (percentage by weight w/W): The mass fraction of a component in solution is the mass of the
component per unit mass o the solution. If A and B represent the masses of component A and B in a solution, their mass fractions
are represented as:
A B
Mass fraction A (WA ) = ; Mass fraction of B(WB ) =
A +B A +B
Mass percentage, i.e., percentage by weight is the weight of the component present in 100 parts by weight of the solution. In a solution
containiong 5g of sugar in 45g of water, the mass percentage or is expressed as:

Mass percentage of sugar = 100 = 10%
+
3.8 Parts per million (ppm): This is generally employed or those solutions in which a substance is present in a very small quanitity. It
is the number of grams of a solute per million grams of solution or the grams of a solute per million grams of solution or the number
of cm3 of solute per million cm3 of the solution.
Mass of one component
Mathematically, ppm = 106
Total mass
(g,mg or cm3 )of solute
in general, ppm = (g,mg 106
or cm2 )or solution
For instance, a sample of hard water containing 7mg of CaSO 4 per kg of solution i.e., 106 mg of water has
7mg
ppm = 106 = 7
106 mg
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3.9 Percent by volume: In case of a solid or liquid dissolved in a liquid. It is expressed as w/V or v/V. (a) Percentage weight by volume
(w/V) means wt. of the solute in grams dissolved 100cm3 of the solution (b) percentage volume by volume (v/V) means the volume of
the component in 100 parts by volume of the solution. In a solution containing 10cm3 of alcohol is
10100
90cm3 of water, the volume percentage of alcohol is = 10%. When nothing is mentioned, it stands for w/W.
10+90
4. VAPOUR PRESSURE OF SOLUTIONS
The pressure of the vapour above the liquid at equilibrum in a closed container refers to as the vapour pressure of the iquid. It will
have a characterstic value at a particular temperature and will increase with temperature. The vapour pressure of a liquid at a given
temperature may thus be defined as the pressure of the vapour in equilibrium with the liquid at that temperature in an enclosed space.
The magnitude of the equilibrium vapour pressure depends on (i) the nature of the liqui (ii) temperature.
5. RAOULTS LAW
5.1 For a solution of volatile liquids. Raoults law states that, for a solution of volatile liquids, the partial vapour pressure of any
volatile component at a given temperature is equal to product of the vapour pressure of the component in pure state and mole fraction
of the component in solution.
For a soluton of two volatile liquids A and B, let XA and XB be their mole fractions and PA and PB be their partial pressure respectively
then,
PA = X PA0 are the vapour pressures of A and B in their pure states.
For an ideal solution, a graph plot between pA and pB against XA and XB is always a straight line in the following graph. Suppose the
component B is more volatile than component A and PA0 and PB0 represent their vapour pressure in the pure state.
From the graph, it is clear that vapour pressure of the solution P at any composition is equal to the sum of vapour pressure of each
component. The vapour above the solution must obey Daltons law of partial pressures, so that
P = pA + pB
OrP = XA PA0 + XB PB0

5.2 For a solution of a non-volatile soute. In case of solution of a non-volatile solute in a volatile solvent, there is hardly any
contribution of solute to the total vapour pressure of the solution. So, the vapour pressure of the solution is infact due to that of solvent
only. In such a case, the above equation becomes:
P = PA = XA PA0 .(i)
As XA = 1XB
Puring this value P = (1 XB )PA0 or P = PA0 PA.0 X B .(ii)
From th equation (ii), it is clear that greatr the mole fraction (conc.) of the soute, lowr will be the vapour pressure of the solution
P0
A P nB
Therefore from (ii) XB P0 = PA0 P or = XB =
P0
A nA +nB
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P0
A P
Where PA0 P is the lowering of vapour pressure, is the relative lowering of vapour pressure, nA and nB are the number of moles
P0
A
of solvent and solute respectively. Hence Raoults law may also be stated as, the relative lowering of vapour pressure of solution is
equal to the mole fraction of the solute when solvent alone is volatile.
6. IDEAL AND NON-IDEAL SOLUTIONS
6.1 Ideal solution: An ideal soution may be defined as that solution which obeys Raoults law and in which the average strength of the
intermolecular forces of attraction between the soute and the solvent is equal to the avrage strength of the forces of attraction between
pure solute molecules and between pure solvent molecules.
It means that in an ideal solution of two liquids A and B, the force of attraction between molecules of A and B (AB) will be same as
those for AA and BB molecular attraction. This is because the molecules of the two mixing components(A and B) having
similarity in shape, size and polarity.
A solution is said to be ideal if it fulfills the following conditions:
i) It obeys Raoults law over the entire range of concentration (PA = XA PA0 )
ii) There should be no volume change on mixing the components, i.e. Vmix = zero.
iii) There should be no heat change on diluting the solution, i.e., Hdil = 0. We have only a concept of ideal solutions but no solution is
exactly idal. i.e., they tend to approach ideal behaviour. For example, a mixture of n-hexane and n-heptane, ethyl bromide and ethyl
iodide, benzene and toluene, chloro benzene and bromo benzene are almost ideal solution. The componnts of an ideal solution can be
separated into their pure forms by fractional distillation. The boiling points of such mixtures are intermediate between those of the
pure liquids. It may be noted that as the concentration of the solute approaches zero, all solutions tend to behave ideally. In other
words, all dilute solutions are almost ideal.
6.2 Non-ideal solutions: A solution is said to be non-ideal, it does not fulfil the required conditions for an ideal solution and does not
obey Raoults Law. Most of the solutions are nonoideal solutions and they show considerable deviations from ideal behaviour. Non-
ideal solutions are of the following two types:
6.2.1 Non ideal solution showing positive deviations.
i) In these solutions, the partial vapour pressure of a component A in the solution obtained by mixing B and A is more than what it
should be according to Raoults law. Similarly the partial vapour pressure of B in the solution obtained by mixing A with B is more
than that calculated from Raoults law. The total vapour pressure of the solution is more than that of an ideal solution of the same
composition. In the graph shown, the dotted lines represent ideal behaviour, whereas full line curves represent non-ideal behaviour.
The molecular interaction between A
and B (AB) are weaker than A A and
B B. In such a case, both A and B find
easier to escape from the solution. Thus
their partial pressure and their total
pressure is higher than expected. In
case of solution showing positive
deviation Vmix and H are always
positive. Ethyl alcohol-chloroform, propyl
alcohol-water. Ethyl alcohol-n-heptane
and acetone-water are some examples
of this type of solution.
ii) Azeotropic mixture : At some composition of the component of such a solution, the vapour pressure is highest and its boiling point
is the lowest. At this temperature, the mixture solution distils over withour any change in composition. A liquid mixture which distils
without change in composition is called constant boiling mixture or azeotropic mixture or azeotropic mixture or azeotropes. Such
solution are minimum boiling points azeotropes. This azotropic mixture boils at a lower temperature than either of thw tow liquid
components.
6.2.2 Non ideal solutions which show negative deviations
i) In some cases, the vapour pressure of a component A in a solution obtained by mixing B with it is less than that calculated from
Raoults Law. Similarly the vapour pressure of a components B and also that of the solution is to be less than the calculated value. The
molecular interacation between A and B (A B) are stronger than A A and BB. in such a case, the escaping tendency (vapour
pressure) of A and B becomes les and total pressure is lower than expected. Vmix and Hmix for such solution will have negative
value. Water-sulphuric acid, acetone-chloroform are some common example showing negative deviation.
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ii) Azeotropic mixture. At some composition of such a solution the vapour pressure of solution is lowest and its boiling point is the
higehest. Solutions of this composition which boil at a constant temperature and distills over without any change in composition are
called azeotropes. Such solutions are called maximum boiling point azeotropes. This azeotropic mixture boils at a higher temperature
than either of the two liquid components.
6.2.3 Factors responisble for Deviations
The deviations from ideal behaviour in solutions are due to change in the magnitude of intermolecular forces on mixing the
components.
i) Positive deviations. A soution of ethanol and cyclohexane shows positive deviations from Raoults Law. In pure ethanol, the
molecules are hydrogen bonded. On mixing, the molecules of cyclohexane get in between the molecules of ethanol. Thus hydrogen
bonds are broken and weak vander waals bonds are formed between the molecules of ethanol and cyclohexane. Therefore enthalpy of
the soution increases. It leads to a slight increase in volume and absorption of heat. In other words, Hmix are positive.
ii)Nagative deviation. A solution of chloroform and acetone shows negative deviation from Raoults law. On mixing the components,
the hydrogen bonds are developed between the molecules of the two components. This increases the inter-molecular forces which
leads to slight decrease in volume and evolution of heat. In other words, both Vmix and Hmix are negative.

(Hydrogen bonding between chloroform and acetone)

Besides hydrogen bonding, there may be some other factors which are responsible for changing magnitude of intermolecular
attraction.
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7. COMPARISON OF LIQUID AND VAPOUR (KONOWALOFFS RULE)

Consider a two component solution (A and B). Let A be more volatile than B. the composition of the vapour in equilibrium with this
solution can be calculatd by applying Daltons Law o partial pressure. In case of an ideal solution, the vapour phase is richer in the
more volatile component, i.e., the one having relatively greater vapour pressure. This is Knowalofs rule and serves as a principle or
fractional distillation for the liquid mixtures.
8. LIMITATION OF RAOULTS LAW
Raoults law does not hold good in the following cases:
i) When the solution is not dilute, there are strong interactions between solute and solvent molecules. This leads to +ve or vedeviations.
ii) If the solute molecules undergo dissociation in solution, the number of particles increases in the solution and Raoults law is not
obeyed.
iii) If the solute molecules associate in the solution, there are less particles in the solution and again Raoults law is not obeyed.
9. COLLIGATIVE PROPERTIES O DILUTE SOLUTIONS
There are certain properties of solutions which depend only on the number of particles (molecules or ions) of solute in the definite
amount of solvent but are independent of nature of solute. Such properties of solutions which depends only on the relative
concentration (or no. of molecules) of the solute and solvent regardless of the nature of the solute are called colligative properties or
democratic properties.
Some of these propertis are:
p0 P
i) Relative lowering of vapour pressure ( )
p0
ii) Elevation of boiling point (Tb )
iii) Depression of freezing point (Tf )
iv) Osmotic pressure (P or )
It may be noted that these properties are independent on the nature of the solute, but are considerably influenced by the nature of
solvent. For a particular solvent, they depend upon the concentration of solute and not upon the nature of solute. Thus greater the
number of solute prticles (conc.) higher will be colligative property.
10. LOWERING OF VAPOUR PRESSURE
When any non-volatile substance is dissolved in the liquid, the vapour pressure of the solution is lowered. This is caleld lowering of
vapour pressur. The lowering in vapour pressure can be explained on the basis of the escaping tendency of the energetic molecules
form the surface. Each volatile component in a solution has certain vapour pressure, which is less than the vapour pressure of the pure
substance at the same temperature. This is due to the fact that the other component occupies a part of the surface and thus decareases
the chances of the molecule of the first component to escape in the vapour state and exert vapour pressure. When a non-volatile solute
is dissolved in a volatile liquid solvent, the number of molecules of the solvent on the surface of solution becomes less than that of the
pure solvent. The chances of the escape of solvent molecules in the vapour phase are reduced in case of solution and the vapour
pressure is lowered. Thus greater the amount of the solute lesser will be escaping tendency of the molecules of the solvent and hence
lower will the vapour pressure of the solution.
Suppost P0 is the vapour pressure of pure liquid component and P is the vapour pressure of the solution when some non-volatile solute
is dissolved in it. (P 0 P) is called the lowring of vapour pressure. This factor has a different value at different tempratrue for a
P0 P
particular solution. But the factor ( ), which is called relative lowering of vapour pressure. Relative lowering of vapour pressure is
P0
equal to mole fraction of the solute and does not depend upon the solvent at given concentration of solute. Relative lowering of vapour
pressure is a colligative property. According to Raoults Law, the relative lwering of vapour pressure is equal to the mole fraction of
the solute.
P0 P nB
= XB =
P0 nA +n
Where n anf nB are number of moles of solvent and solute respectively.
For a very diute solution nA nB
P0 P nB
nB may be neglecte from demoninator. =
P0 nA
For a given volume of solvent nA is constant
P0 P
nB
P0
Thus, relative powering of vapour pressure depends upon the number of moels of solute. Hence relative lowering of valour pressure is
a colligative property.
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10.1 Determination of Molecular masses of non-volatile solute.

According to Raoults Law, the reltive lowering of vapour pressure of a solution is equal to the
P0 P nB
Mole fraction of the soute. = XB =
P0 nA +nB
Where nA and nB represent to number of moles of solvent a and the solute B, respectively. Suppose WB g of the solute B of a
molecular mass MB is dissolved in WA of the solvent having molecular mass, MA .
WB
P0 P nB MB
= = WB WA
P0 nA +nB +
MB MA
WB
For a dilute solution, the number of moles of the solute may be neglected in the denominator.
MB
WB
P0 P MB WB MA
= WA =
P0 MB WA
MA
P0 P
For the above equation it clear that relative lowering of vapour pressure ( ) is inversely proportional to the molecular mass of th
P0
solute (MB).
Knowing the lowering of vapour pressure (P) and the vapour pressure of the pure solvent (P 0) and the molecular weight of the
solvent (MA), we can calculate the molecular weight of solute.
11. ELEVATION IN BOILING POINT
The boiling point of a liquid is the temperature at which the vapour pressure of the liquid becomes equal to the atmosphere pressure.
As a consequence of this, the boiling points of pure solvent like water decrease at high altitudes due to decrease in the external
pressure and increase when the external pressure ( as in pressure cookers) increases. It has been observed that boiling point of a
solution is always higher than that of the pure solvent. Since the vapour pressure over the surface of solution is lower than that of pure
solvent, the solution shall have to be heated to a higher temperature so that vapour pressure over its surface becomes equal to the
atmosphere pressure. The difference between the boiling point of a solution and that of a pure solvent is called elevation in boiling
point. It is denoted by Tb and is given by
Tb = Tb Tb0 , where Tb is the boiling point of solution and T ob is the boiling point of pure solvent.
The effect of a non-volatile solute on the boiling point of
a pure solvent is illustrated in fig. The vapour pressure of
a pure solvent and a solutions have been plotted against temperature. These are AB and CD.
It is clear that vapour pressure of solution is less than
that of pure solvent at any temperature. The vapour
pressure of pure solvent becomes equal to the
atmospheric pressures at temperature T 0b, which is
boiling point of the solvent. Similarly T b represents the boiling points of the solution. The elevation in boiling points for solution is
T = Tb T o b
11.1 Expression for the elevation in boiling point. It is also clear that elevation of boiling point is proportional to the lowering of
vapour pressure, which in turn is proportional to the mole fraction of the solute.
Tb P
P XB
Or Tb XB
Tb = kXB ..(i)
Where k is proportionally constant and XB is the mole fraction of solute.
For dilute solutions,
nB nB MA
X = = WA = nB ..(ii)
nA WA
M

Molality (m) of a solute is written as

nB mWA
m= 1000 or nB =
WA 1000
Putting the value of nB in eqn. (ii)
WA MA mMA
XB = m = .(iii)
1000 WA 1000
Putting the value of XB in eqn (i)
kmMA
Tb = = Kb m .(iv)
1000
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Where Kb a new proportionally constant is called the molal elevation constant or ebulioscopic constant of the solvent and it is the ratio
of the elevation in boiing point to the molality. If m = 1, Tb = K b 1 = K b
Thus molal elevation constant (Kb) may be defined as the elevation in boiling point when molality of the solution is unity i.e.. when
one mole of the solute is dissolved in 1000g of the solvent. The value of k b is different for different solvents e.g., Kb values for water,
ethyl alcohol and benzene are 0.52, 1.22 and 2.53 respectively. Thus Tb depends upon the number of moles of solute and not upon
the nature of the solute. It also depends upon Kb, which depends upon nature of the solvent. So elevation of boiling point is colligativ
property. Thus higher the concentration (the number of particles) of the solute, higher will be the lowering of vapour pressure and
hence higher will be the boiing point of the solution.
11.2 Beckmann Thermometer. As Tb is very small i.e., of the order of 103 , only extremly sensitive thermometer should be used to
register this small change. Generally Beckmann thermometer (which is differential thermometer) is used. It measures small changes in
temperature and not the temperature itself.
11.3 Calculate of Molecular masses. Suppose WB g of solut of molecular mass MB are dissolved in WA g of solvent. The number of
WB
moles of the solute present in the solution is equal to moles. The molality of (m) of the solution, i.e., the number of moles of the
MB
WB 1000
solute dissolved in 1000 g of solvent
MB WA
Substituting value of molality in the formula, Tb = K b m
WB 1000
Tb = K b
MB WA
From the above equation it is clear that elevation it is clear that elevation in boiling point is inversely proportiona to the molecular
K W 1000
mass of or MB = = g mol1
Tb WA
Where MB is the molecular weight of sout and can b calculated.
By knowing elevation in b.p. it is possible to determine the molecular mass of the dissolved solute.
Solvent b.p.(K) Kb(K/m)
Water 373 0.52
Benzene 353.3 2.53
CCl4 350 5.05
CS2 319.4 2.34
Chloroform 334.4 3.63
Thyl alcohol 351.5 1.20
Ther 307.8 2.02
Acetic acid 391.3 3.07
12. DEPRESSION IN FREEZING POINT
Freezing point of anyliquid is that temperature at which the vapour pressure of the liquid and the solid become equal. In othr words, it
is that temperature at which the solid and the liquid form of the substance co-exist.
We know that the vapour pressure of a solutionof a non-volatile substance is ower than that of the pure solvent at any given
temperature. It means that vapour pressure of the solution would become equal to the vapour pressure of the solid solvent at a lower
temperature as compared to that of a lower temperature as compard to that of a pure solvent. Obviously, th freezing point of a pur
solvent and the freezing point of a solution is calld the depression in freezing point. It is denoted by Tf and is given by Tf = T f =
Tf where T 0 f and Tf are the freezing points of a pure solvent and solution respectively.
The effect of a non-volatile solute on the
Freezing point of a pure solvent is illustrated in
the graph. The vapour pressure of a pure
solvent and a solution has been plotted against
temperature in the graph.
It is clear from the graph that the vapour pressure
of the pure substance in the liquid state becomes
equal to that of the solid state at the point A; which
represents the freezing point of the pure solvent
(Tof). At the point A. the vapour pressures curve
of the liquid and solid phases meet. Similarly T f
represents the freezing pointsof the solution. The
depression in freezing point in case of solution is
Tf = T 0 fTf .
 10

12.1 Expression for the depression in freezing point: It is also clear that depressions in freezing point is proportional to the mole
fracation of the solute.
Tf P
and X
= .(i)
Where k is the proportionally constant and XB is the mole fraction of the solute.
mMA
For dilute solutions, XB = (By definition)
1000
Where m is the molality of the solute, M A is the molcular mass of the solvent. Putting the value of XB in eqn. (i)
MA
Tf = k m = Kf m .(ii)
1000
Where Kf is called the molal depression constant or cryoscopic constant of the solvent. If m = 1, Tf = K f . Thus the molal
depression constant may be defined as the dpression in freezing point when the moality of the soluton is unity i.e., when one mole of
the solute is dissolved in 1000g of the solvent. The value of K f is different for different solvents, e.g., Kf values for water, ethyl
alcohol and benzene are 1.86, 1.99 and 5.1 respectively. Thus Tf depends upon the number of moles of the solute and not upon the
nature of the solute. It means larger the concentration of the solute lower will be the freezing of the solution and higher will be the
lowering of vapour pressure and hence higher will be Tf . It also depends upon KF which depends upon nature of the solvent. Thus
depression in freezing point is a coligative property.
(Depression in freezing point is also measurd with the help of Beckmann thermometer).
12.2 Calculation of molecular masses
If WB g of solute of molecular mass MB are dissolved in WA g of solvent.
WB
Thus number of moels of the solute present in the solution is equal to
MB
The molality (m) of the solution, i.e., the number of moles of the solute dissolved in 1000g of solvent.
WB 1000
=
M WA
Substituting the value of molality in the formula, T = K f m
WB 1000
Tf = K f .
MB WA
From by above equation it is clear that depression in freezing point is inversely proportional to the molecular mass of the solute.
Kf WB 1000
MB = = g mol1
Tf WA
Thus by knowing the dprssion in freezing point, it is possible to determine the molecular mass of the dissoved solute.
Thus by knowing the depression in freezing point, it is possible to determine the moecular mass of the dissolved solute.

Solvent F.P. (K)

( )

Acetic acid 289.7 3.90
Benzene 278.6 5.12
Camphor 452.0 39.7
CS2 164.2 3.83
CCl4 250.5 31.8
Chloroform 209.6 4.70
Ether 156.9 1.79
Ethyl alcohol 155.7 1.99
Naphthalene 353.3 6.80
Water 273.0 1.86
13. SEMIPERMEABL MEMBRANE
A membrane, which allows the passage of solvent molecules through it but not that of solute when a solution is separated from the
solvent by it, is known as a semi permeable membrane.
The semi permeable memebranes are of two types.
i) Natural: Vegetable membranes and animal memebranes, which are just found under the outer skin of plants and animals. The pigs
bladder is the most common animal membrane.
ii) Artificial: These are parchment paper, cellophane, collodion and certain freshly precipitated inorganic substance e.g., copper
ferrocyanide, calcium phosphate, silicate of iron, cobalt or nickel etc.
 11

13.1 Preparation of semi-permeable membrane. Copper ferrocyanide membrane is regarded to be the best and convenient. The
copper ferrocyanide membrane is prepared on the walls of a porous pot by electrical method.
A copper sulphate solution is placd inside the cleaned porous pot and potassium ferrocyanide solution outside the pot in a container. A
copper electrode is dipped in copper sulphate solution and a platinum electrode in potassium ferrocyanide move towards platinum
electrode and [Fe(CN)6 ]4 each towards copper electrode. Both the ions meet each other in the pores of the pot and deposit the
precipitate of copper ferrocyanide there:- 2Cu++ + [Fe(CN)6 ]4 Cu2 [Fe(CN)6 ]
14. DIFFUSION
If the two solutions of different concentrations are kept in contact, the molecules of the solute and solvent both move from region of
higher concentration to lowr concentration till a uniform concentration is obtained. The spontaneous mixing of the particles of solute
and solvent to form a homogeneous mixture is caleld diffusion in solutions.
15. OSMOSIS
A different phenomenon has been observed whenever a
Solution and a pure solvent or two solutions of different
Concentration are kept in contact through a semi-permeable
membrane. In this case only the solvent molecules
penetrate through the membrane while the solute particles
are held back. The solvent molecules pass through the semipermeable
membrane from the solvent to the solution side or from less concentrated to
more concentrated solution till an equilibrium is attained.
This process of flow of the solvent molecules from the solvent to the
solution or from less concentrated to a more concentrated solution through a
semi-permeable membrane is called osmosis.
15.1 Difference between osmosis and diffusion. The main points of difference are
i) Osmosis can be carried out only with the help of semi-permeable memebrane, but no such external egency is required for diffusion to
take place.
ii) In diffusion the movement of the molecules is from both sides. The solute molecules move in one direction whereeas solvent
molecules in the other. But in osmosis the movement of molecules is one sided.
iii) In diffusion the molecules of solute move from solution of higher concentration tow lower concentration giving a homogenous
mixture, whereas in osmosis the solvent molecules move from solution of lower concentration to that of higher concentration or
molecules of solvent from pure solvent to the solution making it dilute.
iv) Osmosis occur in biological systems.
v) Osmosis can be stopped by applying pressure to the solution but diffusion cannot be stopped.
15.2 Osmotic pressure (P or ). The equilibrium hydrostatic pressure developed on the solution due to the net flow of the solvent
molecules through a semipermeable membrane is called the osmotic pressure.
The term osmotic pressure of a solution is, however,
not strictly correct: A solution does not, in itself, have
any osmotic pressure. Osmotic pressure is the
hydrostatic pressure developed by osmosis. Thus we
see that it osmosis that develops osmosis. Osmotic
pressure is a measure of the force, which produces
osmosis.
The flow of solvent into solution may also be stronger
by the application or sufficient pressure. This extra
pressure which must be applied to a solution in order
to stop the flow of the solvent into it through a
semipermeable membrane separating the two is a
measure of osmotic pressrue of the solution.
15.3 Determination of osmotic pressure Berkley and Hartleys method. The measurement of osmotic pressure inovolves essentially
the determination of the excess pressure that has to be applied upon the solvent to produce a state of equilibrium in the system (i.e., to
stop osmosis). The method commonly employed for the determinaton of osmotic pressure is due to Berkley and Hartley (1904). In this
method th osmotic pressure is balanced by a counter pressrue, which prevents the passage of the solvent into the solution. The
apparatus employed, consist of a fine uniformly texured porcelain tube A, within the pores of which the semipermeable membrane o
 12

copper ferrocyanide is deposited electrolytically towards its outer surface. This porcelain tube A is fitted into a fun metal jacket B,
which liquid tight joint. The outer vessel is provided with an air-tight piston. One end of the porcelain tube is completely filled with
water while the outer vessel B is filled with the semipermeable memebrane in the solution. External pressure, which is measured by a
pressure gauge, is applied on the solution by working the piston C so as to prevent the entrance of water into the solution, which is
indicated when the level of water in the capillary tube T remains stationary. This pressue measures the osmotic pressure of the
solution.

So long as the hydraulic pressure is less than the osmotic pressure, the level of the solvent in the capillary tube will fall. When the
hydraulic pressure becomes equal the osmotic pressure, the liquid in the capilary tube remains constant, indicating that the two
opposing pressures balance each other.
i) The equilibrium is established very quickly and so it gives the result in very short time.
ii) Since the external pressure applied balances the osmotic pressure, there is a little strain on the semipermeable membrane.
iii) The concentration of the solution does change during the determination of osmotic pressure.
15.4 Cause of Osmosis. There exists difference in the vapour pressure of the solvent and solution (or between the two solutions). Now
in solution, the escaping tendency of the solvent is less as compared to that in a pure solvent, thereore the vapour pressure of solution
is less than that of pure solvent. This difference in vapour pressure, permits the transfer of solvent molecules from pure solvent into
solution through semipermeable membrane.
16. VANT HOFF THEORY OF DILUTE SOLUTIONS
Vant Hoff proposed that an analogy exists between gases and solutions provided osmotic pressure of solution is used in place of
ordinary gas pressrue. He showed that for dilute solutions of non-electrolytes the following three law hold good.
i) Boyle-Vant Hoff law. The osmotic pressure (P, the symbol (pi) is also used in place of P) of a solution is directly proportional to its
concentration (C) when the temperatrue is kept constant.
n
Where C is molar concentration of the solute i.e. C = (n is the number of moles of the solute and V is the volume of the solution)
V
Thus P C
n
P
V
or PV = constant
ii) Pressure temperature Law for solutions (Gay-Lusac-Vant Hoff Law): Concentration remaining same, the osmotic pressure of a
dilute solution is directly proportional to its absolute temperatrue (t), i.e., P T
P
Or = constant
T
Combing the two laws, i.e., when concentration and temperature both are changing the osmotic pressure will be given by;
P cT or P = cRT
n n
Or P = RT (since C = )
V V
Or PV = nRT (R is called as solution constant)
The value of R comes out to 0.082 L atm K 1 mol1 which is in agreement with the value of R, the molar gas constant. For one mole
of the solute dissolved in V litres of the solution, the equation becomes PV=RT.
iii) Equimolecular solutions of different solutes exert equal osmotic pressure under identical conditions of temperature.
 13

Such solutions which have the same osmotic pressure are termed isotonic or iso-osmotic. Thus for the solution to be isotonic then
w1 w w
= 2 = 3 where w1 , w2 , w3 are the masses and m1 , m2 . m3 are the molecular masses of the solutes 1,2,3 respectively.
m1 m2 m3
Hence 6gL of urea; 34.2 gL1 sucrose and 18gL1 of glucose solutions are isotonic. When two isotonic solutions are separated by a
1

semipermeable membrane, no flow of solvent molecules is observed in either side. The law is similar to Avogadro law. It can be
stated as., Equal volumes of dilute solutions of different solutes, having the same temperatrue and osmotic pressure, contain equal
number of molecules.
Because these laws of the dilute solutions are similar to the gas laws, this led Vant Hoff to suffest that a solute in the solution,
behaves as a gas and the osmotic pressure of the solution is equal to the pressure which the solute would exert if it were a gas at the
same temperatrue and occupying the same volume as that of the solution. This statement is known as Vants Hoff theory of dilute
solutions.

17. OSMOTIC PRESSURE IS A COLLIGATIVE PROPERTY

It has been observed that behaviour of non-electrolyte substances in dilute solutions are very much similar to the behaviour or gases.
Vant Hoff equation for dilute solution is given below.
PV = nRT
Where P is the osmotic pressure of the solution at temperature T containing n moles of the solute dissolved in V litres of the solution
R is a constant called soluton constant. The value of the constant R is the same as for the gas constant.
From above equations, we have
n
P = RT
V
n
means number of moles per litre of the solutions, which may be taken as the molar concentration (C) of the solutions. It is clear that
V
osmotic pressrue (P) is proportional to the concentration of the solute and not upon the nature of the solute. So osmotic pressure is a
colligative property.
17.1 Calculation of molecular masses from osmotic pressrue. According to Vant Hoff equation for dilut solutions, we have PV =
nRT
If Wb of the solute is dissolved in V litres of the solution and M b is the molecular mass of the solute than
WB
n=
M
WB
Substitude the value of n in the above equation PV = RT
MB
WB RT
MB =
PV
Thus measuring the osmotic pressure (P) of the solution of known concentration at a given temperature (T), the molecular mass (MB)
of the solute can be calculated. The value of R is taken as 0.0821 litre atm/degree/mole or 8.314 JK 1mol1
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 subsances are measurable.
17.2 Biological importance of osmosis. The growth of plants and animals depends largely on the phenomenon of osmosis. Plants and
animals bodies are composed of a very large number of microscopic units called cells. Cell contains a fluid (cell sap) and its wall is
composed of a living cytoplasmic membrane, which is semipermeable and is responsible for the phenomenon of osmosis in living
organisms. If such a cell comes in contact with water or some dilute solution, the osmotic pressrure of which is less than that of cell
sap present in the cell, there will be a tendency of water to enter into the cell through the cell wall. The pressure developed inside the
cell due to the inflow of water into it is caleld turgor. On the other hand, it the cel comes in contact with a solution of higher osmotic
pressure, the cell would shrink due to going out of water from the cell through the cell wall. This shrinking of the cell is caleld
plasmolysis.
17.3 Brusting of red blood cells when placed in water is due to osmosis. It is interesting to note the following:
i) A 0.91% solution of pure NaCl is isotonic with human red blood corpuscles (RBC). Hence in this solution RBC neither swel nor
undergo plasmolysis.
ii) A pure NaCl solution with concentration less than 0.91% is called hypotonic solution. On placing RBC in this solution, they will
swell and even burst.
iii) A pure NaCl with concentration more than 0.91% is caled hypertonic solution. On placing RBc in this solution, they shrink due to
plasmolysis.
 14

17.4 Swelling and shrinking of an egg. When the outer shel of an egg is removed (by dissolving it in dil HCl) and it is placed in water
or very diute solution it sells but if it is placed in concentrated sodium choride solution it shrinks. It is due to osmosis as the membrane
beneath the outer shell of an egg acts as a semipermeabl membrane. Similar is a case with a mango.
17.5 Some other important biological phenomena due to osmosis
i) Plants absorb water from the soil through their roots due to osmosis because concentration of cell sap inside root cel is higher than that
of the water present in the soil.
ii) water assimilated by the plants moves into body of the plants and reaches even to the top of a tal tree due to osmosis.
iii) in animals, water moves into different parts of body under the effect of the process of osmosis.
iv) Stretching of leaves, flowers etc. is also controlled by osmosis.
v) Osmosis helps in rapid growth of the plants and germination of seeds.
vi) Different movements of plants such as opening and closing of fowers etc. are controlled by osmosis.
18. NON-ELECTROLYTIC, ELECTROLYTIC SOLUTION
i) Non-electrolytic solution: Glucose, urea sucrose, fructose etc. neither associated nor dissociate in dilute solutions. So their number of
particles remain unchanged indilute soution. Such solution show normal colligative properties and their molecular masses remain
same in such solutions.
ii) Electroytic soutions in which the dissolved substance i.e., solute is an electrolyte are caled electrolytic solutions. Since the electrolyte
dissociates into charged particles caleld ions in solution, these conduct electric current.
For instance, solutions of NaCl, KNO3, HCl etc. in water are al electrolytic in nature. In these solutions of strong electrolytes, the
solute electrolyte is fully dissociated. When the solute is a weak electrolyte such as NH 4OH, H3C COOH etc. it is partially ionised in
solution. Due to ionisation of the solute (electrolyte) in solution, the number of particles in solution increases and such solutions show
higher values of colligative properties than that of non electrolytes. The molecular mass of an electrolyte determined on the basis of
colligative properties have been found to be abnormal as explained in the next article.
19. ABNORMAL MOLECULAR MASSES
We know that colligative properties depend upon the molar concentration of the soute in soution. These properties depend upon the
number and not upon the natrue of the solute particles in solution. Therefore, in many cases where the solute associate or dissociate in
solution, certain abnormal values of colligative properties are obtained. The values of molecular masses calculated on the basis o
colligative properties in such cases wil also be abnormal.
19.1 Association: If a solute associates in the solution, the number of particles present in the solution wil be less than the actual number
dissolved and hence the value of osmotic pressure and other consequently the molecular mass indicated will be higher than the true
molecular mass. For example, carboxylic acids such as acetic acid and benxoic acid associate in benzene to form cyclic dimers due to
hydrogen bonding and therfore the number of particles decrease and colligative properties also decrease and thus their molecular
masses become almost double in non-polar solvents.

19.2 Dissociation: If a solute dissociates in the solution, the number of particles in the solution will be more than actually in the value of
colligative properties will be higher and hence the molecular masses observed with be smaller than the true molecular mass. For
example, electrolytes like NaCl dissociates in solution and exist as Na+ and Cl ions.
water
NaCl(s) Na+ (aq) + Cl (aq)
Thus larger the number of ions given by an electrolyte higher will be its colligative property.
 15

20. VANT HOFFS FACTOR (i)

The account or the abnormal results, Vant Hof introduced a factor (i) known after this name. it is given by the expresson.
observed value of the colligative property
i=
Calculated or normal value assuming no dissociation or association
For example, the osmotic pressure observed in the case o electrolysis is such greater than what could come out from the equation PV =
nRT. Vant Hoff explained this abnormally by modiying the equation by putting factor (i), thus
Pobs V = inRT
Now the equation in case of calculated osmotic pressure is
Pcal. V = nRT
Dividing (1) by (2)
Pobs
= i osmotic pressure of the solution is proportional to the lowering of vapour pressure (P), elevation in boiling point (T b) and
Pcal.
depression in freezing point (T f). For substances undergoing association or dissociation in the solution, the various expressions for
the colligative properties are modified as follows:
Elevation in boiling point, T b = iKbm
Depressing in freezing point, T f = i Kfm
P0
A P
Relative lowering of vapour pressure, = iXB
P0
A
Pobs. Pobs Tb obs Tf .obs
i= = = =
Pcal. Pcal. Tb cal. Tf .cal.
Each colligative property is inversely proportional to the molecular mass of the solute. Therfore,
Observed colligative property
i=
Normal or calculated colligative property
Since a colligative property is directly proportional to the number of moles and inversely proportional to the molar of the solute, Vant
Hoff factor (i) may also be expressed as:
Number of particles after dissociation or dissociation
i=
Normal number of prticles
In case of dissociation, i is more than unity while it is less than unity it case of association. But in case of ideal solution its value is 1.
Vant Hoffs factor for non-electrolutes like glucose, fructose, urea, sucrose in their dilute solutions in unity while that for an
electrolytes is greater than 1.
Then no. of ions given by an electrolyte and the value of its Vant Hoff factor i' in dilute solution.

Electrolytes No. of ions furnished by the electrolyte The approximate value of (i) factor
NaCl, KNO3 , AgNO3 , MgSO4 , C6 H5 NH3 Cl, CuSO4 2 2
CaCl2 , Ca(NO3 )2 , Na 2SO4 , BaCl2 , K 2 SO4 3 3
K 3 [Fe(CN)6 ], AlCl3, (NH4 )3 PO4 , La(NO3 )3 4 4
K 4 [Fe(CN)6 ], Al2 (SO4 )3 5 5
For equimolar solutions, the electrolyte that gives largest no ions will show largest colligativ property.
21. DEGREE OF DISSOCIATION
Let a molecule on an electrolyte when dissolved in a solvent given n ions and is the degree of dissociaiton.

Number of moles before dissociaiton = 1 mole

Number of moles after dissociation = 1 + = 1 + ( 1)
1+(n1)a 11
Therefore i = or =a
1 n1
Thus a can be calculated.
 16

22. DEGREE OF ASSOCIATION

Let n molecules A associate to form one molecule and a is the degree of association.

Where n = factor of association

a
Total no. of moles after association = 1 a +
n

1+

Therefore, i =
1

n
Or = 1 i
1
EXAMPLE :1- At 300 K, the vapour pressure of an ideal solution containing one mole A and 3 moles of B is 550 mm of Hg. At
the same temperature, if one mole of B is added to this solution, the vapour pressure of the solution increases by 10 mm of Hg.
Calculate the vapour pressure of A and B in their pure state.
EXAMPLE:2- The molar volume of liquid benzene (density = . ) increases by a factor of 2750 as it vaporises at 20 0C
and that of liquid toluene (density = 0.867 g ml 1 ) increases by a factor of 7720 at 200C. A solution of benzene and toluene at
200C has a vapour pressure of 46.0 torr. Find the mole fraction of benxene in vapour above the solution.
EXAMPLE:3- Find the molality of a solution containing a non-volatile solute if the vapour pressure is 2% below the vapour
pressure of pure water.
EXAMPLE:4- A very small amount of non-volatile solute (that does not dissociate) is dissolved in 56.8 cm3 of benzene (density
0.889 g cm-3). At room temperature, vapour pressure of this solution is 98.88 mm Hg while that of benzene is 100 mm Hg. Find
the molality of this solution. If the freezing temperature of this solution is 0.73 degree lower than that of benzene, what is the
value of molal freezing point depression constant of benzene?
EXAMPLE:5- A solution contains 7.31 g urea in 50 g of water. When air was bubbld through this solution and thn successively
through water and concentrated sulphuric acid, the bulb containing pure water lost 0.087 g while a gain in weight of 2.036 g
was noted for the sulphuric acid bulb. What is the mass of one mol of urea?
EXAMPLE :6- Calculate the amount of ice that will separate out on cooling a soution containing 50 g of ethylene glycol in 200 g
water to . . ( = . ).
EXAMPLE:7- A solution of a non-volatile solute in watr freezes at . . The vapour pressure of pure water at 298 K is
23.51 mm Hg and Kf for water is 1.86 degree molal1. Calculate the vapour pressure of this solution at 298 K.
EXAMPLE:8- A decimolar solution of potassium ferrocyanide is 50% dissociated at 300 K. Calculate the osmotic pressure of the
solution. (R=8.314 JK1 mol1 )
EXAMPLE:9- A 1.7% solution (W/V) of siliver nitrate is isotonic with 3.4 solution of glucose. Calculate the degree of ionisation
of silver nitrate solutions?
EXAMPLE:10- The freezing point of a solution containing 0.2 g of acetic acid in 20.0 g benzene is lowered by 0.450C. calculate
the degree of association of acetic acid in benzene. Assume acetic acid dimerises in benzene. K f for benzene = 5.12 K mol1 kg.
EXAMPLE:11- The so- caleld ozone layer in the earths stratosphere has an average total pressure of 10 mm with partial
pressure of ozone in the lyer . . what is the concentration of ozone (in ppm) assuming that the average mass of
air is 29g/mol?
EXAMPLE :12- What is vant Hoff factor in each of the following cases?
A. . [() which is 20% ionised
B. which is 50 dissociated
C. Benzoic acid which forms dimer to the extent of 50 in benzene
D. Glucose solution
EXAMPLE:13. Latent heat of vaporization of water is 9.72 kcal mol 1 at 373.15 K. Calculate molal boiling point elevation
constant of water and also b.p of 0.1 molal sucrose soution.
EXAMPLE:14. A 0.10 M solution of HgCl2 in water freezes at . whereas a 0.10 M solution of ( ) freezes at
. . Deduce the structural states of these two compounds. The freezing point depression constant for water is 1.86 kg
mol1K and assume molality = molarity
 17

EXAMPLE:15. Cellobiose is a sugar obtained by degradation of cellulose. If 200.0 mL of aqueous solution containing 1.500 g of
celloboise at 25.00C. gives rise to an osmotic pressure of 407.2 mmHg what is the molecular weight of celloboise?
EXAMPLE:16. What is normality of 0.30 M H3 PO4 (a tribasic acid) in the following reaction?
+ +
A. 0.30 N B. 0.60 N
C. 0.90 N D. 0.15 N
EXAMPLE:17. pH of a 0.1 M monobasic acid is found to be 2. Hence, its osmotic pressure at a given temperature T K is:
A. 0.1 RT B. 0.11 RT
C. 1.1 RT D. 0.01 RT
EXAMPLE:18. The most likely of the following mixture to ba an ideal solution is:
A. B.
C. () D.
EXAMPLE:19. Relative decreases in V.P. of an aqueous glucose dilute solution is found to be 0.018. Hence, elevation in boiling
points is: (it is given 1mol aq. urea solution boils at 100.54 0 C at 1 atm pressure):
A. 0.0180 B. 0.180
C. 0.540 D. 0.030
EXAMPLE:20. Relative decrease in vapour pressure of an aqueous solution containing 2 mol [( ) ] is
0.50. On reaction with AgNO3, this solution will form:
A. 1 mol AgCl B. 0.25 mol AgCl
C. 2 mol AgCl D. 0.40 mol AgCl
EXAMPLE:21. Mixture of volatile components A and B has total vapour pressure (in Torr) =
Where is mole fracation of A in mixture. Hence and are in (Torr)
A. 254, 119 B. 119, 254
C. 135, 254 D. 154, 119
EXAMPLE:22. Consider following solution:
I) 1M aq. glucose
II) 1 M aq. sodium chloride
III) 1 M benzoic acid in benzene
IV) 1 M ammonium phosphate
Select incorrect statements(s):
A. All are isotonic solutions B. III is hypotonic of I, II, IV
C. I, II, IV are hypertonic of III D. IV is hypertonic of I, II, III
EXAMPLE:23. The mineral atacamit (A) is [ . () ]. . . were required to react completely
with 1.6320 g of A. Hence, x is (mol. Wt of A = 427):
A. 2 B. 3
C. 4 D. 1
EXAMPLE:24. At a given temperature, the vapour pressures of pure A and B is 108 and 36 Torr respectively. What will be the
mole fraction of B in the vapour phase which is equillibrium with a solution containing equimole fraction of A and B, under
ideal behaviour conditions?
A. 0.25 B. 0.33
C. 0.50 D. 0.60
EXAMPLE:25. At 1000C and 1 atm, of the density of liquid water is . and that of water vapour is 0.006 g cm3, then
the volume occupied by water molecules in 1L of steam at that temperatur is:
A. 6 cm3 B. 60 cm3
3
C. 0.6 cm D. 0.06 cm3
EXAMPLE:26. Select correct statements:
A. gases which have high value of van der waals constant a are easily iquefied
B. easily liquefied gasses are water soluble
C. ions forming gases in a solvent are soluble in that solvent.
D. All are correct statements
EXAMPLE:27. Select incorrect statement:
A. higher the value of kH (Henrys law constant) at a given pressure, the lower is the solubility of the gas in the liquid
 18

B. solubility of a gas in a liquid decreases with increases in temperatrue and pressure

C. to minimise the painful effects accompanying the decompositions of deep sea divers, O 2 diluted with less soluble He gas is used
as breathing gas
D. the solubility of a gas in a liquid is governed by Henrys law
EXAMPLE:28. 25 ml of a solution of barium hydroxide on titration with a 0.1 molar solution of hydrochloric acid gave a litre
value of 35 ml. The molarity of barium hydroxide solution was
A. 0.14 B. 0.28
C. 0.35 D. 0.07
EXAMPLE:29. In a 0.2 molal aqueous solution of a week acid HX, the degree of ionizatio is 0.3. Taking K f for water as 1.85 , the
freezing point of the solutions will be nearest to
A. . B. .

C. +. D. .
EXAMPLE:30. A 0.001 molal solution of [( ) ] in water had a freezing point depression of . . if Kf for water is
1.80, the correct formulaton of the above molecule is
A. [( ) ] B. [( ) ]
C. [( ) ] D. [( ) ]
EXAMPLE:31. The molarity of in the solution after 2 litres of 3 M AgNO3 is mixed with 3 litres of 1 M BaCl2 is
A. 1.2 M B. 1.8 M
C. 0.5 M D. 0.4 M
EXAMPLE:32. For a dilute solution containing a nonvolatile solute, which of the following expressions correctly represents the
molar mass of solute?

A. = B. =
( / ) ( / (/ )

C. = D. = ( ) (/ )
( / )(/

EXAMPLE:33. The degree of dissociation () of a weak electrolyte AxBy is related to vant Hoff factor (i) by the expression

A. = B. =
(+) ++
+ ++
C. = D. =

EXAMPLE:34. The percentage composition by weight of an aqueous solution of a solute (molecular mass 150 ) which boils at
373.26 is (Kb=0.52)
A. 5 B. 15
C. 7 D. none of the above
EXAMPLE:35. How many grams o sucrose (M.wt.=342) should be dissolved in 100 g water in order to produce a solution with a
105.00C diference between the freezing point and the boiling temperature? (K f = 1.86 C/m, Kb = 0.510C/m)
A. 34.2 g B. 72 g
C. 342 g D. 460 g
EXAMPLE:36. Water and chlorobenzene are immisible liquids. Their mixture boils at 900C under a reduced pressure of
. . The vapour pressure of pure water at 900C is . and molecular weight of chlorobenzene is 112.5
On what percent basis, chlorobenzene in the distillate is equal to
A. 50 B. 60
C. 70 D. 80
EXAMPLE:37. A solution X contains 30 mole percent of A and is in equilibrium with its vapour that contains 40 mole percent of
B. The ratio of vapour pressure of pure A and B will be
A. 2:7 B. 7:2
C. 3:4 D. 4:3


EXAMPLE:38. = . : = . . Calculate the ratio of , . ., the ratio of mole fractions of O2 to N2

dissolved in water at 250C from air,

A. 0.62 B. 0.92
C. 0.421 D. 0.52
EXAMPLE:39. Two liquids X and Y form an ideal solution. The mode fraction o X in vapour phase is 0.2 while in liquid phase is
0.8. if the total pressure is 800 torr then what are the original vapour pressures o X and Y?
 19

EXAMPLE:40. Solubility of NaCl in D2O is less than H2O, although dielectric constant of H2O is more because
A. Lower viscosity is responsibe or ow solubility of NaCl
B. Higher viscosity is responsible for low solubiity o NaCl
C. There is no relation between solubility and viscosity of NaCl
D. None of these
EXAMPLE:41. Which of the following is false?
A. Sodium thiosulphate can form super saturated solution
B. Red blood cells on keeping in hypotonic solution will swell up
C. Water boils at lower boiling point is pressure cooker
D. During osmosis solvent moecules move from higher vapour pressure to lower vapour pressure
EXAMPLE:42. Which of the following statement is false?
A. 0.01 M solution of the following has osmotic pressure
B. = where c is molarity
C. = according to Raoults law
D. Two sucrose solutions of same molarity prepared in different solvents will have same frezing point depression
EXAMPLE:43. Which of the following solutions is not isotonic?
A. 4% NaOH (wt/volume) and 6% urea (wt/volume)
B. 17.4 % K2SO4 (wt/volume) ( = %) and 4% NaOH (wt/volume) ( = %)
C. 1 molal glucose and 1 molal urea
D. 0.745 g of KCl in 100 ml of watr and 0.585 g of NaCl in 100 ml of water.
EXAMPLE:44. A needle can float on clear water but sinks when some detergent is added to it, because
A. detergent increases the surace tension of water
B. detergent decreases the surface the tension of water
C. detergent increases the vapour pressure of water
D. detergent decreases the vapour pressure of water
III. MULTIPLE CHOICE QUESTIONS (with more than one correct choice)
EXAMPLE:45. Which of the following is/are true?
A. Sodium thiosuphate can form super saturated solution
B. Red blood cells on keeping in hypotonic solution will swell up
C. Water boils at lower boiing point in pressure cooker
D. During osmosis solvent molecules move from higher vapour pressure, to lower vapour pressure, to lower vapour pressure
EXAMPLE:46.

From the diagram it is clear that

A. When = . = . then a charcteristic colouration would be formed on x-side
B. When = . = . then a characteristic colouration would be observed on side y
C. when the = . =0.5 M then a characteristic colour would be observed at side y
D. when a pressure of 20 atm is kept at side x and = . = . then a charactristic colour would be observd at
side x
EXAMPLE:47. Which of the following is/are correct statements(s) about the Raoults law applied to soluton of non-volatile
solute?
A. Vapour pressure of solution is proportional to mole fraction of solute
B. V.P o solution is proportional to the mole fraction of solvent
C. Relative lowering o V.P. = mole fraction of solute
D. Lowering of vapour pressure is proportional to the mole fraction of solute
EXAMPLE:48. In a binary and ideal liquid mixture
A. Partial vapour pressure of each component varies directy with respective mole fracation in the solution
 20

B. = +
C. = +
D. = +
EXAMPLE:49. Solid is gradually added to KI solution, which of the following statements is/are correct?
A. Freezing point increases and then becoms constant
B. Freezing point decreases constantly
C. Boiling point decreases and then becomes constant
D. Vapour pressur increases to a constant vale
EXAMPLE :50. The diagram given aside depicts the
boiling point as the function of
composition of the mixtur of CCl4
and SiCl4. Which of the following statements
about the diagram is false?

A. The point a represents the composition of solution and that point b that of the vapour in equilibrium
B. The proportional of CCl4 in the solution is smaller than that in the vapour in equilibrium
C. ba represents the sondensation of the vapours
D. The point c represents the composition of soluton and the point b that of the vapour at equilibrium
EXAMPLE:51. Assertion (A): Relative lowering of vapour pressur is equal to mole fraction of the solvent.
Reason (R): Relative lowering of vapour pressure is a colligative property.
A. A B. B
C. C D. D
EXAMPLE:52 Assertion: Cooking time is reduced in pressure cooker.
Reason : Boiling point of water inside the pressure cooker is elevated.
A. A B. B
C. C D. D
EXAMPLE:53. Assertion: When mercuric iodide is added to the aquous solution of KI, the freezing point is raised.
Reason: reacts with KI forming complex ion [ ]
A. A B. B
C. C D. D
EXAMPLE:54. Assertion: One molar aqueous solution has always highr concentration than one molal solution
Reason : The molality of a solution depends upon the density of the solution whereas molarity does not.
A. A B. B
C. C D. D
EXAMPLE:55. Assertion: NaCl in water and organic acids in benzene show abnormal molecular mass
Reason: Abnormal molecular mass is obtaind when the substance in the solution undergos dissociation or association.
A. A B. B
C. C D. D
COLUMN MATCHING
EXAMPLE 56 Match the following:
Column I Column II
A. CH3 COOH in H2 O P) Neither association nor dissociation
B. CH3 COOH in benzene Q) When a non-volatile solut is added
C. Polymer in water R) Molecular mass observed grater than molecular mass actual
D. Vapour pressure of a liquid (S) Tb(obs) > Tb(calc.) decreases
EXAMPLE:57. Match the following:
Column I Column II
A) Steel P) Minimum boiling azeotrope
B) Brass Q) V = +ve, H = +ve
C) C2 H5 OH + Benzene R) Molecular mass observed greater than actual molecular mass
 21

D) CHCl3 + CH3 COOCH3 S) Substitutional solid solution

T) H = ve, V = ve
U) Maximum boiling azeotrope
EXAMPLE:58. H = Molar heat of fusion of ice; Lf = Latent heat of fusion of ice (g 1 )
Hv = Molar heat of vaporisation of water; Lv = Latent hat of vaporisation of water (g 1 ) Match the following appropriately:
Column I Column II
18373373
A. Molal depression constant of water P)
1000Hf
373373R
B. Molal elevation constant of water Q)
1000L
18273273R
C. Tf of solution containing 9.0 g of R)
1000 Hf
glucose in 50 g of water
273273R
S) Tb of solution containing 3.0 g of S)
1000 Lf
urea in 50 g of water

VII. TRUE/FALSE
EXAMPLE:64. The vapour pressure of the solution is always more than that of a pure solvent.
EXAMPLE:65. In the procss of osmosis, solvent molecules move from the dilute solution towards the solution of higher concentration.
EXAMPLE:66. Osmotic pressure is the excess pressure which is applied on the solution side to check osmosis.
EXAMPLE:67. Addition of sodium chorid lowers the boiling and freezing point of water.
EXAMPLE:68. The value of observed osmotic pressure is always more than that of the actual value of the solute which undergoes
dissociation in solution.
EXAMPLE:69. The value of observed molecular weight is always less than its normal value of the solute which undergos dissociation
in the solvent.
EXAMPLE:70. The relative lowering of vapour pressure of a solvent by a solute is proportional to the molarity of the solution.
EXAMPLE:71. The molarity of a solution depends on the temperature whereas the mole fraction of a solution does not change with
temperature.
EXAMPLE:72. A mixture of ideal gases is cooled upto liquid helium temperature (4.22 K) to form an ideal solution.
EXAMPLE:73. Freezing point of a solution is directly proportonal to its molality.
VIII. FILL IN THE BLANKS
EXAMPLE:74. When a solute is dissolved in a solvent, the vapour pressure of the solution.
EXAMPLE:75. A colligativ property is one which depends upon theand not on the .
EXAMPLE:76. The osmotic pressure () of a solution = cR x
EXAMPLE:77. Given that Tf is th depression in f.pt. of the solvent in a solution of a non-volatile solute of molality, m, then
lim Tf
[ ] =
m0 m
EXAMPLE:78. The sum total of the mole fractions of th components of the solution is equal to..
EXAMPLE:79. A solution obtained by dissolveing 342 g of sugar (C12 H22 O11 ) in 1000g water is .molal.
EXAMPLE:80. An ideal solution is a solution for which H mixing and .mixing are zero,
EXAMPLE:81. Vant Hoff factor, I for KCl is
EXAMPLE:82. Every solution behaves as ideal solution..
EXAMPLE:83. Thein boiling point of a solvent is directly proportional to thesolution.