ELEMENTS OF +2 CHEMISTRY SOLUTIONS

solutions

INTRODUCTION: A solution is a homogeneous mixture of two or more non-reacting substances

whose composition can be varied within certain limits. The substances making up the solution are
known as components. The solution which is made up of two components is known as binary
solution while the solution with three components is known as ternary solution.
SOLUTE AND SOLVENT: The component which has the same state as that of the solution is
known as the solvent and the other component is known as the solute. The solvent, in general, is
present in larger amount by weight while the solute is present in smaller amount by weight. In
solution, the size of solute particles is less than 10−7 cm (or 10−9 cm) and the different components
of the solution cannot be separated by any of the physical method such as filtration, centrifugation
etc.
The solution with water as solvent is known as aqueous solution and those with solvent other than
water are known as non-aqueous solutions.
TYPES OF SOLUTION:
There are nine types of solutions:
S.No. SOLUTE E SOLVENT EXAMPLE
1. Solid Solid Alloys
2. Solid Liquid NaCl in H2O
3. Solid Gas Iodine or Camphor Vapour in air
4. Liquid Solid Hg in Zinc
5. Liquid Liquid C2H5OH in H2O
6. Liquid Gas Moisture in air
7. Gas Solid Dissolved gases in minerals or H2 in Pd
8. Gas Liquid Air in H2O or CO2 in H2O
9. Gas Gas Air

Out of various types of solutions given, the most common types of solutions are those which exist in
liquid state. These may be saturated or unsaturated depending upon the ability of the solution to
contain more of the solute.

(a) SATURATED SOLUTIONS: In which more of the solute cannot be dissolved at the given
temperature.

(b) UNSATURATED SOLUTIONS: In which more of the solute can be dissolved at the given
temperature.

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ELEMENTS OF +2 CHEMISTRY SOLUTIONS

(c) SUPERSATURATED SOLUTIONS: It contains more of the solute than in the saturated
solution at the temperature of the saturated solution. It is an unstable state and by slight
disturbance the extra solute separate out giving a saturated solution.

SOLUBILITY: Solubility is the amount of solute present in 100 g of saturated solution at a given
temperature. Factors affecting solubility are:
1. Nature of solute
2. Nature of solvent
3. Temperature
4. Pressure (in case of gases)
CONCENTRATION OF SOLUTION:
It is the amount of solute present in the given quantity of the solution. There are several ways
for expressing the concentration of solution a given follows:
1. MASS FRACTION: It is the ratio of the mass of one component to the total mass of the

solution. For example: If WA is the mass of the component ‘A’ and WB is the mass of the
component ‘B’, then
WA
Mass fraction of the component ‘A’ =
WA + WB
WB
Mass fraction of the component ‘B’ =
WA + WB
The product of mass fraction and 100 gives mass percentage
WA
i.e. Mass percentage of ‘A’ =  100
WA + WB
When a liquid is dissolved in liquid, the concentration is expressed in volume percentage.
VA
Volume percentage of A =  100
VA + VB
where VA and VB are the two volumes of the components A and B of solution respectively.
Example: If 40 cm3 of C2H5OH id dissolved in 60 cm3 of water, then

40
Volume percentage of C2H5OH =  100 = 20% by volume
40 + 160
2. MOLE FRACTION: It is the ratio of number of moles of one component to the total number
of moles present in the solution. If NA and NB are the number of moles A and B respectively, then
NA
mole fraction of the component A (XA) =
NA + NB
NB
Mole fraction of the component B (XB) =
NA + NB

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ELEMENTS OF +2 CHEMISTRY SOLUTIONS

The sum of the mole fraction of all the components in a solution is 1 (Unity).
i.e. XA + XB = 1 or XA = 1 − XB Also XB = 1 − XA
Numerical: If 20 g of ethanol (C2H5OH) is dissolved in 40 g of water then find out mole fraction of
ethanol and H2O.
20 / 46
Sol. Mole fraction of ethanol i.e. X C2H5OH =
90 / 18 + 20 / 46
20 / 46 20 / 46
= = = 0.0798
(90  20) + (20  90) 3600 / 828
828
90 / 18 5
Mole fraction of H2O i.e. X H2O = = = 0.920
90 / 18 + 20 / 46 5.434
From these two; sum of mole fraction
0.434 5 5.434
i.e. X C2H5OH + X H2O = + = =1 Hence Proved
5.434 5.434 5,434
3. MOLARITY: It is the number of moles of solute dissolved per litre of the solution. It is
denoted by M.
No. of moles of solute n
Molarity of M = = B
Volume of solution in litre V
WB
But nB = , where WB = mass of the solute and MB = molecular mass of the solute
MB
WB
Therefore, M=
MB  V
Example: The molarity of a solution changes with change in temperature. It is because the
molarity depends upon volume of the solution and volume changes with change in temperature.
4. MOLALITY: It is defined as the number of moles of a solute dissolved per kilogram (1000
g) of the solution. It is denoted by ‘m’
Mathematically: If ‘NB’ is the number of moles of the solute dissolved in W grams of solution. Then,
NB Mass (WB )
Molality, m =  1000 g Since, NB =
Wg Molecilar mass (MB )
WB 1000
Molality,m = 
MB W grams
Example: If 20 g of K2CO3 is dissolved in water to make 1500 g of solution, then

20 1000 20
Molality, m =  = = 0.09 m
138 1500 40

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 ELEMENTS OF +2 CHEMISTRY SOLUTIONS

Difference between Molarity and Molality

• In molarity, the volume of the solution is considered while in molality, the mass of the solvent is
taken into account
• The volume of the solution changes with the temperature while the mass of the solvent does not
change. This means that molarity of a solution changes with temperature whereas molality does
not.
• Molality of a solution is considered better for expressing the concentration of the solution as
compared to molarity.
5. NORMALITY: It is defined as the number of gram equivalent of solute dissolved in 1 litre
of a solution. It is denoted by ‘N’
Mathematically, Normality
Wt. of solute dissolved per litre of solution
N=
Equivalent Wt. of the solute
Let ‘x’ be the No. of gram equivalent of solute dissolved in V cm3 of the solution, then
x WB 1000
Normality N =  1000 or N = 
V E V
where : WB is the mass of solute and
WB
E is the equivalent weight of solute  x=
E
If 4 gram of NaOH is dissolved in 50 cm3 of solvent, then
4 1000
Normality N =  = 0 .2 N
40 500
Numerical: Calculate the normality of solution in which 20 g of Na2CO3 is dissolved in 10 litre of
the solution.
Molecular weight 106
Sol. Mass of Na2CO3 = = = 53
Positive weight 20
20 1000
 Normality N =  = 0.05 N
53 10,000
NOTE: The normality of a solution also changes with the change in temperature.

6. FORMALITY: It is the number of gram formula mass of the solute dissolved per litre of the
solution. It is denoted by F.
No. of gram formula of the solute
Formality (F) =
Volume of solution in litre
Mass of solute
But No. of gram formula mass of Solute =
Formula mass
Mass of solute
 Formality (F) =
Formula mass  Vol. of Sol. in litre

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ELEMENTS OF +2 CHEMISTRY SOLUTIONS

EXAMPLE: The formality of solution containing 29.25 g of NaCl (Formula mass = 58.5) in 1 litre
solution is 0.5 F.
29.25
i.e. F= = 0 .5 F
58.5  1
Parts per million parts (ppm): This expression is used for very very dilute solution. It is the
number of parts of solute dissolved per million parts of the solution.
Mass of solute
ppm of solute =  10 6
Mass of solution
EXAMPLE: A sample of hard water containing 7 mg of CaSO4 per kg (106 mg) of water has ppm
of 7.
7 mg
i.e. ppm of CaSO4 = 6
 10 6 = 7
10 mg

PERCENTAGE BY VOLUME: It is the volume of the component in 100 parts by volume of the
solution.
volume of component
Percentage volume =  100
volume of solution
EXAMPLE: In a solution containing 10 cm3 of alcohol in 20 cm3 of water
10
Volume percentage of alcohol is  100 = 10%
10 + 20
Tools
Mass Percent
Volume Percent
Parts per million (ppm)
Molarity (M)
Molality (m)
Relation between Molarity and molality
Molality (m)
Normality (N)
Mole fraction
Mass fraction
Relation between molarity and density
Molarity (M)
Relation between normality and density
Normality (N)
Relation between Molarity and Mole traction
Molarity (M)

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 ELEMENTS OF +2 CHEMISTRY SOLUTIONS

Normality of Acid = Molarity x Basicity

Normality of Base = Molarity x Acidic
Molarity on mixing solution: M1V1 + M2V2 = M3 (V1 + V2)
Normality on mixing solution: N1V1 + N2V2 = N3 (V1 + V2)
Problems for Practice
1. A solution has been prepared by dissolving 5 g of urea in 95 g of water. What is the percent of urea
in the solution?
2. Calculate the masses of cane sugar and water required to prepare 250 g of 25% solution of cane
sugar.
3. Calculate the molarity of a solution containing 5 g of NaOH dissolved in 450 mL of the solution.
4. Calculate the molality of 2.5 g of ethanoic acid (CH3COOH) in 75 g of benzene.
5. Calculate the mole fraction of ethylene glycol (C2H6O2) in a solution containing 20% of ethylene
glycol by mass
6. Find the molarity and molality of a 15% solution w/w of H2SO4 (density of H2SO4 = 1.02 g cm-3).
SOLUBILITY OF SOLIDS AND LIQUIDS:
When a small amount of solid (solute) is added to a large but fixed quantity of solvent at
room temperature, the solute gets dissolved in the solvent to form a solution. This process is
known as dissolution. The process of dissolution continues until the concentration of solute
acquires a constant value. If more of the solute is added to the solvent, it remains undissolved.
Such a solution is known as saturated solution. A solution which has less concentration of solute
than the saturated solution is known as unsaturated solution. In a saturated solution it seems that
no activity is taking place. However, two opposing processes are taking place simultaneously. At
constant temperature, some of the molecules of solute pass into the solution thereby, leading to
an increase in concentration of solution. On the other hand, the dissolved sugar molecules move
into the solid state thereby leading a decrease in the concentration. When the two opposing
processes balance each other, the amount of solute dissolved per unit volume of solution remains
constant and the stage is known as equilibrium stage. Hence, the solubility of a solid in a liquid at
a given temperature
may be defined as,
“The maximum amount of solute which can be dissolved in 100 g of solvent to form a
saturated solution at a given temperature.”
e.g. The solubility of NaCl in water is 28 i.e. 28 g of NaCl can be dissolved in 100 g of water at
room temperature and the resulting solution is known as Brine.
FACTORS AFFECTING SOLUBILTIY OF A SOLID IN A LIQUID:

1. Nature of Solvent and Solute: In a solid, the atoms, molecules or ions are arranged as very
regular pattern and the attractive forces are very strong. Hence for dissolution the solute-solvent
forces of attraction must be sufficient to overcome the attractive forces that hold the solid
together. In general, polar solvent (water, ammonia, HCl etc.) dissolve polar solutes (ionic
compounds) and non-polar solutes (covalent compounds) dissolve in non-polar solvents e.g. CCl4,
Benzene (C6H6), Ether etc. This is based on the theory ‘like dissolve like’ e.g. NaCl is more soluble
in water than sugar. Their solubility in water are 5.3 moles per litre and 3.8 moles per litre
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ELEMENTS OF +2 CHEMISTRY SOLUTIONS

respectively. However, reverse is the case with organic solvents. Similarly, iodine (covalent
compound) is more soluble in alcohol than in water. This can be explained as under:
In case of ionic compounds dissolved in polar solvents, a strong electrostatic force of attraction
exists between the ions of the crystal and the polar solvent molecule. The negative ions are
attracted by the positive poles of solvent and the positive ions by the negative poles.
Consequently, the ions of the crystal break apart leading to dissolution of crystal. Moreover, the
ions of the crystal get surrounded by the solvent (water) and prevent their recombination. This
process is known as salvation or hydration. The energy supplied by the solvent for breaking an
ionic compound into its ions is known as Solvation energy or Hydration energy or Lattice energy.
A substance dissolves if there is a net lowering of energy i.e. the reaction is exothermic.
2. Effect of Temperature: Temperature has a significant effect on the solubility of solute in
particular solvent. The effect of temperature on the solubility of a solid in a liquid solvent depend
upon heat of solution (enthalpy of solution). On the basis of heat of solution, the effect of
temperature can be studied as under:
(a) Endothermic Processes: Solids like NaCl, KCl, KBr, KNO3, NH4Cl, NH4NO3 etc. when dissolved in
water involve absorption of heat.
Solvent(1) + Solute(s) Saturated Solution; H = +ve
Since the forward process is endothermic therefore, according to Le-Chatelier’s Principle
should be followed at high temperature, i.e., when the temperature is raised, more of the solute
will dissolve in solvent.
(b) Exothermic Processes: Salts like Li2CO3, Na2CO3, CaO, CaCO3, Na2SO4 etc when dissolved in
water involve evolution of heat i.e.,
Solvent(1) + Solute(s) Saturated Solution; H = −ve
Since the forward reaction is exothermic, therefore, it will be favoured by low temperature.
Therefore, when the temperature is decreased, the solubility increases. There are certain
substance which on heating change from one polymorphic form to another, one hydrated form to
another or from hydrated form to anhydrous form. Such substances do not show a continuous
increase or decrease in solubility with the change in temperature. For example, Glauber’s salt,
Na2SO4 shows an increase in solubility upto 32.4oC and then shows a decrease in solubility. This is
because upto 32.4oC the salt remains hydrated and the process of dissolution is endothermic. Above
this temperature this changes to anhydrous form and the process is exothermic. This temperature
at which a substance changes from one form to another is known as transition temperature.
Because of this reason solubility of the salt initially increases and then decreases.
SOLUBILITY OF GASES IN LIQUIDS : Gases dissolve in liquids to form true solutions. The
solubility of a gas in a solvent is usually determined by measuring the volume rather than the mass
of gas that dissolves in the solvent and is expressed in terms of absorption coefficient () ⎯
introduced by Bunsen, which may be defined as,

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ELEMENTS OF +2 CHEMISTRY SOLUTIONS

The volume of a gas at STP dissolved by unit volume of a solvent at a given temperature and
under a partial pressure of one atmosphere. If Vo is the volume of the gas that dissolves in a liquid
having a volume V and partial pressure P, then
Vo
Absorption coefficient () =
Vp

FACTORS AFFECTING SOLUBILITY OF A GAS IN A LIQUID:

1. Nature of Gas and Solvent: Natural gases like oxygen, hydrogen, nitrogen etc. are sparingly
(less) soluble in water while gasses like HCl, CO2, SO2, NH3 etc. are more soluble. In general,
gases that can be easily liquefied are more soluble while the gases that are difficult to liquefy
are less soluble e.g. hydrogen gas has an absorption coefficient of 0.017 while ammonia has 71
and HCl has 442. Moreover, nitrogen, hydrogen, oxygen are more soluble in alcohol than in
water under similar conditions of temperature and pressure, but HCl, CO2, SO2, NH3 etc. are
more soluble in water than in alcohol. The gases which form ions in aqueous solution are readily
soluble in water while gases which fail to form ions are less soluble in water but more soluble in
organic solvents.
2. Effect of Temperature: The solubility of a gas decreases with the increase in temperature.
This is because dissolution of a gas in a liquid is an exothermic process. Hence according to Le-
Chatelier’s Principle, the rise in temperature will decrease the solubility of gas. For this reason
the beverages containing dissolved CO2 are stored under cold conditions because CO2 is more
soluble at lower temperatures.
3. Effect of Pressure: The solubility of gases increases with the increase in pressure. On the
basis of experimental evidences William Henry in 1803 gave a quantitative relationship between
the solubility of a gas in a liquid and its pressure at a given temperature. The law is known as
Henry’s Law and states that
“At a given temperature, the mass of a gas dissolved in a given liquid is directly proportional
to the pressure of the gas”
i.e. m  P
or m = kP
or kH = m/P
where kH is a constant of proportionality and is
characteristic of the nature of gas, solvent and
temperature. According to Eq. 1 when the solubility of the
gas is plotted against equilibrium pressure at a given
temperature, straight lines as shown in Fig.1 are obtained.
Henry’s law can be explained on the basis of Le-Chatelier’s

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ELEMENTS OF +2 CHEMISTRY SOLUTIONS

Principle. According to this an increase in pressure will shift the equilibrium in a direction in which
there is a decrease of pressure. Hence on increasing the pressure more gas will dissolve in liquid to
decrease the pressure.
Dalton expressed the solubility of a gas in a liquid in terms of its mole fraction as:
Partial pressure of the Gas (P)  Mole fraction of gas in the solution
= k  Mole fraction of gas in the solution
Partial pressure of the gas
 kH =
Mole fraction of the gas in the solution

where kH is known as Henry’s Constant.

Limitations of Henry’s Law
Henry’s law holds good if the following conditions are fulfilled:
(i) The present is not too high,
(ii) The temperature is not very low.
(iii) The gas does not chemically combine with the solvent. The gas molecules do not either
dissociate or associate in the solvent. In case the dissolved gas reacts with the solvent, higher
solubilities can result. The solubility of ammonia in water is much higher than expected
because of the following recation:
NH3 + H2O = NH4OH
Carbon dioxide also reacts with water.
CO2 + H2O H2CO3

Application of Henry’s Law

1. Soft drink bottles are sealed at high pressure, to increase the solubility of CO2 in the soft drink
2. At high altitude, partial pressure of oxygen is low it leads to low concentration of oxygen in
blood of people living there. Low concentration of oxygen develops anoxia, i.e., unable to think
and act properly.
3. When scuba divers go deep in the sea, solubility of atmospheric gases increases in blood. When
the divers come up, there is release of dissolved gases and it leads to the formation of bubbles
of nitrogen in our blood capillaries and hence there is painful sensation called bends. To avoid
bends the tanks of scuba diversare filled with 11.7% He, 56.2% N2 and 32.1% oxygen.
Azeotropes or Azeotropic mixtures: Many non-ideal binary solutions at definite
compositions behave like pure liquids because their vapours have same composition of the
two components as in solution. Such solutions are called azeotropes or azeotropic
mixtures. Thus, azeotropes are the mixtures of liquids which boil at constant temperature
like a pure liquid without undergoing any change in the composition. Azeotropes are also
called constant boiling mixtures. These mixture cannot be separated into individual pure
components by fractional distillation. Azeotropes are of two types.
(i) Minimum boiling azeotropes: These are formed by those liquid pairs which show a positive
deviation from ideal behaviour. Such azeotropes have boiling points lower than either of the
components.
(ii) Maximum boiling azeotropes: These are formed by those liquid pairs which show a negative
deviation from ideal behaviour. Such azeotropes have boiling points higher than either of the
components.

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ELEMENTS OF +2 CHEMISTRY SOLUTIONS

PROPERTIES OF SOLUTION: (VAPOUR PRESSURE AND RAOULT’S LAW)

Vapour Pressure of Liquid/Solution: In order to explain vapour pressure take the liquid/solution
in a closed container which is attached with
manometer and in order to keep the temperature
constant, it is covered with thermostat. The
molecules of the liquid/solution will escape from
the surface to form vapours which move in the
empty space over the surface. In the beginning the
pressure of vapours will go increasing and ultimately
it will become constant which can be observed with
the help of pressure in mano-meter. This is due to the reason that at this stage the rate of
evaporation and the rate of condensation of vapours are equal and known as equilibrium stage.

The pressure at the stage of equilibrium (i.e. when the rate of evaporation and the rate of
condensation are equal) at particular temperature is known as vapour pressure.

Effect of Non-Volatile Solute on the vapour pressure of Solution:

Whenever non-volatile solute is added to the volatile solvent to make the solution, the
vapour pressure of solution is less than vapour pressure of the pure solvent. This is due to reason
that in the solution the evaporation takes place from reduced surface. As part of the surface is
occupied by the molecules of non-volatile solute which do not change into vapours. Therefore, the
vapour pressure of solution of non-volatile solute is always less than pure solvent and known as
lowering in vapour pressure.

Mathematically, If PAo is the vapour pressure of pure solvent and PA is the vapour pressure of
solution of non-volatile solute, then

Lowering in vapour pressure = PAo − PA

RAOULT’S LAW: Raoult studied the vapour pressure of a large number of binary solutions of
miscible liquid and gave a generalization named as Raoult’s law, which is as under:

(A) For Solution of Volatile Liquids:

“The partial vapour pressure of each component of a solution is directly proportional to its
mole fraction.”

Let us consider a binary solution of two miscible liquids A

and B. Let PA and PB be the vapour pressure of A and B and XA
and XB be their mole fractions respectively. Then according to
Raoult’s law

PA  XA and PB  XB
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ELEMENTS OF +2 CHEMISTRY SOLUTIONS

or PA = PAo  X A andPB = PBo  X B

where PAo and PBo are constant of proportionality and are known as vapour pressure of pure
component A and B respectively.

It follows from Raoult’s law that a graph plotted between PA and XA or PB and XB should give a
straight line that should pass through the points PAo and PBo when XA and XB become unity.

The total pressure (P) of the solution is the sum of the partial pressure of A and B at any
composition.

P = PA + PB = PAo  X A + PBo  X B

(B) For a Solution of non-volatile solute: Consider a solution formed by dissolving a non-volatile
solute in water. In such a solution, there is no contribution of the solute of the total vapour
pressure of the solution so that vapour pressure of the solution is only due to that of solvent. The
vapour pressure of the solution will be lowered when mole fraction of solvent in the solution
decreases.

Thus total pressure (P) of the solution is given by

P = PA or PA = PAo  X A -------- (i)

Here PAo = vapour pressure of pure solvent

XA = Mole fraction of solvent A.

For a binary solution XA + XB = 1 or XA = 1 − XB

Substituting the value of XA in equation (i), we get

PA
PA = PAo  (1− X B ) or = (1− X B ) …….. (ii)
PAo

Rearranging the equation (ii), we have

P PAo − PA
1− Ao = X B or = XB …….. (iii)
PA PAo

PAo − PA
In Eq. (iii) P − PA is the lowering of the vapour pressure while the quantity
o
A represents
PAo
the relative lowering of vapour pressure.

On adding a non-volatile solute to a solvent, Raoult’s law may, therefore, be stated as under:

“Relative lowering of vapour pressure of a solution is equal to the mole fraction of solute
in the solution.”

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 ELEMENTS OF +2 CHEMISTRY SOLUTIONS

IDEAL SOLUTIONS: A solution is said to be ideal when it obeys Raoult’s law over entire range
of concentration, in an ideal solution like and unlike molecular interaction are the same. An ideal
solution satisfies the following conditions:

1. Raoult’s law is obeyed.

2. There is no change in volume when two components are mixed to form an ideal solution
(i.e. V(mixing) = 0).

3. There is no change in enthalpy on mixing the two components (i.e. H(mixing) = 0).

4. There should be no enthalpy change on diluting the solution (H(dil) = 0).

In fact, no solution is exactly ideal. However, the solutions approach ideal behaviour at
sufficient dilution. When the concentration of solute approaches almost zero, all solutions tends to
become ideally. In other words, all dilute solutions are nearly ideal. Examples of solutions showing
nearly ideal behaviour are:

(a) Benzene − Toluene

(b) n-Haxane − n-Heptane

(c) ChloroBenzene − BromoBenzene

(d) Ethly Bomide − Ethly Iodide

NON-IDEAL SOLUTIONS: A solution is said to be non-ideal when it does not obey Raoult’s law
and whose formation is accompanied by change in volume or enthalpy of both. Most of the
solutions are non-ideal and these show a large deviation from ideal behaviour. There are two types
of non-ideal solutions:

(I) SOLUTIONS SHOWING POSITIVE DEVIATIONS:

This type of deviation is observed in those solutions in which A-B interactions are weaker than
A-A or B-B interactions. In these solutions, the observed vapour pressure of each component A or B
and the total vapour pressure is greater than that predicted by Raoult’s law, i.e.

PA > PAo  X A ; PB > PBo  X B Also P > PA + PB.

When such a solution is formed there is change in volume (i.e. V(mixing)  0) and also change in
enthalpy (i.e. H(mixing)  0). This positive deviation of solutions shows that the energy required to
separate the molecules in the pure state is greater than the energy liberated in the association of
unlike molecules.

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ELEMENTS OF +2 CHEMISTRY SOLUTIONS

Explaination of Positive Deviation:

Consider a solution of ethyl alcohol and cyclohexane.

There is association of ethyl alcohol molecules by H-bonds.
When cyclohexane is added, its molecules tends to adjust
themselves between ethyl alcohol molecules thereby
weakens H-bonds. Absorption of energy takes place and
volume increases i.e. H  0 and V  0. Due to weakening of H-bonds also there is slight
increase in vapour pressure.

EXAMPLES:

1. Benzene (C6H6) − Carbontetrachloride (CCl4)

2. CCl4 − CHCl3 (Chloroform)

3. Ethyl alcohol − Cyclohexane

4. C2H5OH and H2O

(II) SOLUTIONS SHOWING NEGATIVE DEVIATIONS:

This type of deviation is observed in such solution in

which A-B interactions are stronger than A-A or B-B
interactions. In these solutions the observed vapour
pressure of each component A or B and the total vapour
pressure is less than that predicted by Raoult’s law

i.e. PA < PAo  X A ; PB < PBo  X B

Also P < PA + PB.

When such a solution is formed there is change in volume (i.e. V(mixing)  0) and also change in
enthalpy (i.e. H(mixing)  0).

The negative deviation show that the energy required to separate molecules in the pure state is
less than the energy liberated in the association of unlike molecules.

Explaination of Negative Deviation:

Consider a solution of chloroform and acetone. When two

are mixed H-bond are formed between acetone and
chloroform molecules. The attractive forces become
stronger and escaping tendency of each liquid from the
solution decreases. Thus the volume decreases (V(mixing) is negative) and energy is liberated.
Vapour pressure of the solution also decreases due to formation of H-bonds.

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ELEMENTS OF +2 CHEMISTRY SOLUTIONS

EXAMPLES:

1. Acetone and Chloroform

2. H2SO4 and H2O

3. CHCl3 − C6H6

4. HNO3 − H2O

FACTORS RESPONSIBLE FOR DEVIATION FROM RAOULT’S LAW:

1. Intermolecular Interactions: The solutions show non-ideal behaviour when like and unlike
molecular interactions are different.

2. Association or Dissociation of Solute Particles in Solution: Association or dissociation of

solute particles in solution make the solution non-ideal.

3. Low Temperature: Low temperature favours deviation from ideal behaviour as at low
temperature, intermolecular forces are strong.

4. High Pressure: At high pressure, solutions shows deviation from ideal behaviour as at high
pressure intermolecular attraction increases while intermolecular separation decreases.

5. High Concentration: At higher concentration solution shows deviation from Raoult’s law as at
high concentration solute-solvent interactions are quite prominent.

LIMITATIONS OF RAOULT’S LAW:

1. Raoult’s law does not hold good for concentrated solutions.

2. Raoult’s law is not applicable for solutions in which the solute particles undergo

association or dissociation.

COLLIGATIVE PROPERTIES OF DILUTE SOLUTIONS:

It is defined as “the certain properties of dilute solution of non-volatile solute into volatile
solvent which are directly proportional to mole fraction of solution in a definite quantity of
solvent and do not depend upon the nature of solute.” They may be called as democratic
properties of dilute solution. The important colligative properties of dilute solutions are:

1. Relative lowering of vapour pressure.

2. Osmotic pressure.

3. Elevation in boiling point of the solutions.

4. Depression in the freezing point of solutions.

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ELEMENTS OF +2 CHEMISTRY SOLUTIONS

A. RELATIVE LOWERING OF VAPOUR PRESSURE:

When a non-volatile solute is dissociated in a liquid solvent, the vapour pressure of the solution is
only due to solvent as the contribution of the solute particles to the total vapour pressure is zero.
Let us consider a solution in which ‘A’ is the solvent and ‘B’ is the solute. Let X A and XB be the mole
fractions of A and B respectively. Let PAo is the vapour pressure of the pure solvent ‘A’ and ‘P’ is
the vapour pressure of solution. Since vapour pressure contribution due to solute is zero, vapour
pressure of the solution will be equal to the vapour pressure of the solvent i.e. P = PA.

But according to Raoult’s law

PA = PAo  X A …….. (i)

or P = PA = PAo  X A

For a binary solution XA + XB = 1 or XA = 1 − XB ……..(ii)

Therefore, substituting value of XA in (i), we get

PA
PA = PAo (1− X B ) or = 1− X B …….. (iii)
PAo

Rearranging Eq. (iii), we get

P PAo − PA
1− Ao = X B or = XB
PA PAo

PAo − PA
Here ( P − PA ) is called lowering of vapour pressure while
o
A is called Relative lowering of
PAo
vapour pressure.

Thus relative lowering of vapour pressure is the ratio of the lowering of vapour pressure of pure
solvent. The relative lowering of vapour pressure depends upon the molar concentration of solute
and is independent of nature of solute in the solution. It is, therefore, a colligative property.

CALCULATION OF MOLECULAR MASS OF SOLUTE FROM RELATIVE LOWERING OF

VAPOUR PRESSURE:

PAo − PA
We know that = XB
PAo

nB
But X B = , where nA and nB are the number of mole of solvent and solute
n A + nB
respectively.

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ELEMENTS OF +2 CHEMISTRY SOLUTIONS

PAo − PA nB
Therefore, =
PAo
n A + nB

WA WB Here, WA = Mass of the solvent

But n A = and nB =
MA MB MA = Molecular mass of solvent

PAo − PA WB / MB WB = Mass of the solute

 o
= MB = Molecular mass of solute
PA WA WB
+
M A MB

For a very dilute solution, the concentration of solute is very small. Therefore, neglecting WB/MB in the
denominator, we get

PAo − PA WB MA
= 
PAo MB WA

WB  M A
or MB =
 PAo − PA 
 
 P o   WA
 A 

B. OSMOTIC PRESSURE:

OSMOSIS: In 1748, Abbe Noilet studied for first time the phenomenon in which solvent and solution
are separated from each other by a semipermeable membrane.

Semipermeable Membrane: It is a membrane having very small pores through which one
component of the solution (i.e. solvent) can easily pas but not the other component
(solute). Cellophane is very common semipermeable membrane.

One of the best semipermeable membrane is Copper Ferrocyanide.

PHENOMENON: When a solution is separated from its pure solvent through a semi-permeable
membrane, the solvent molecules begin to flow into the solution through the pores of the semi-
permeable membrane. When a semi-permeable membrane separates two solutions of different
concentrations, the solvent begins to flow from higher concentration of solvent to the lower
concentration of the solvent (i.e. from dilute solution to the concentrated solution).

The spontaneous flow of the solvent to the lower concentration of solvent through the pores
of the semi-permeable membrane is called Osmosis.

CAUSE OF OSMOSIS: The phenomenon of Osmosis takes place due to reason that when solvent
and solution of non-volatile solute are separated from each other, the vapour pressure exerted at
the surface of solvent will be more than vapour pressure exerted at the surface of solution. Due to
lowering in vapour pressure. Thus due to extra pressure on solvent surface, the molecules of

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ELEMENTS OF +2 CHEMISTRY SOLUTIONS

solvent flow towards the solution. Similar is the reason for flow of solvent molecules from dilute
solution towards concentration solution.

OSMOTIC PRESSURE: It is defined as , “measure of extra pressure exerting on the solvent or

dilute solution when they are separated from concentrated solution by a semi-permeable
membrane, due to which Osmosis takes place.”

OR

Osmotic pressure can also be defined as, “the excess pressure which must be applied to a
solution of non-volatile solute in order to stop the flow of solvent into the solution through
semi-permeable membrane.”

DETERMINATION OF OSMOTIC PRESSURE:

BERKELEY-HARTLEY’S METHOD: It is the simplest and most accurate method for determining
the osmotic pressure of dilute solution.

THEORY: In this method, a gradually increasing pressure is applied to the solution which is
separated from its pure solvent through a semi-permeable membrane and the pressure which just
stops the osmosis is noted. This pressure is the measure of the osmotic pressure of the solution.

METHOD: The arrangement is shown in the Fig. The apparatus consists of a porous pot fitted with
copper ferrocyanide semi-permeable membrane in its walls. It is fitted with a capillary tube of very
fine bore at one end and a water reservoir at the other end.

The porous pot is filled with water till it stands at a

definite mark in the capillary tube which is noted. The
porous pot is surrounded by a brass or a copper jacket
which is filed with solution whose osmotic pressure is
to be determined. The brass jacket is fitted with a
piston to apply the pressure and pressure gauge to
note down the pressure. Osmosis takes place and
water begins to flow into the solution through the wall of the porous pot.

As a result water meniscus in the capillary tube moves downward. Pressure is now applied to the
solution with the help of the piston till the water meniscus in the capillary tube remains constant.
The pressure applied to stop osmosis is read from the pressure gauge and is equal to the osmotic
pressure of solution.

CONDITION FOR GETTING ACCURATE RESULT:

1. The solute should be non-volatile.

2. The solution must be dilute.

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ELEMENTS OF +2 CHEMISTRY SOLUTIONS

3. There should be no association or dissociation of the solute in the solution.

DETERMINATION OF MOLECULAR MASS OF THE SOLUTE FROM OSMOTIC PRESURE

MEASUREMENT:

Osmotic pressure () of a solution is found to be directly proportional to the concentration (C) of
the solution and its temperature (T).

Mathematically,

nB
  CT or  = CRT But C =
V
Where nB = No. of molecules of the solute
nB V = volume of the solution in litre
Therefore,  =  RT
V

or V = nBRT

This equation may be called as VantHoff’s equation for dilute solutions.

WB Where WB = Mass of the solute

But nB =
MB MB = Mol. Mass of the solute

WB
Therefore, V =  RT
MB

WB RT WB RT
or =  or MB = 
MB V  V

C. ELEVATION IN BOILING POINT OF THE SOLUTION:

BOILING POINT: The boiling of the solution is that exact

temperature at which its vapour pressure becomes equal to the
atmospheric pressure. For example, pure water boils at 373 K as
this temperature its vapour pressure becomes equal to 1 atm (760
mm of Hg).

ELEVATION IN BOILING POINT OF SOLUTION: When a non-volatile solute is added to the

pure solvent to form the solution, the vapour pressure is lowered and the solution is required to be
heated at higher temperature to make its vapour pressure equal to the atmospheric pressure. The
difference in the boiling point of pure solvent and the solution is known as elevation in boiling
point of the solution.

Let the boiling point of pure solvent = T1 K

Boiling point of the solution = T2 K

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ELEMENTS OF +2 CHEMISTRY SOLUTIONS

Elevation in the boiling point of the solution

Tb = T2 K − T1 K = (T2 − T1) K

The vapour pressure curves of the pure solvent and solution at different temperatures are shown in
Fig. AB indicates the increase in vapour pressure of pure solvent with temperature while CD
indicates the increase in vapour pressure of solution with temperature. AB approaches the
atmospheric pressure at temperature T1 K which is the boiling point of pure solvent which CD
approaches atmospheric pressure at higher temperature T2 K which is the boiling point of the
solution. The difference in boiling point is called elevation in boiling point of the solution (Tb).

MOLAL ELEVATION CONSTANT:

Tb is directly proportional to the lowering of vapour pressure which in turn depends upon the
mole fraction of the solute in the solution. Therefore, (Tb  XB)

or Tb = K. XB, where K is known as proportionality constant ……. (i)

For dilute solutions

nB nB M
XB = = = nB  A …….. (ii)
n A (WA / MA ) WA

Molality (m) of the solution is given by

nB m  WA
m=  1000 or nB =
WA 1000

Putting the value of nB in Eq. (ii) we get

WA MA m  MA
XB = m   =
1000 WA 1000

Putting the value of XB in Eq. (i) we get

m  MA
Tb = K  = Kb  m (Here Kb = K.MA the product of constant terms)
1000

Tb
or K b =
m

the Kb is called molal Elevation constant or Ebullioscopic constant of the solvent.

If m = 1; Tb = Kb

Thus molal elevation constant (Kb) is defined as elevation in boiling point of the solution when one
mole of the solute is added in 1 kg or 1000 g of pure solvent (i.e. when molality of the solution is
1). The value of Kb is different for different solvents. For water, ethyl alcohol and Benzene, the
values of Kb are 0.52, 1.22 and 2.58 K/m respectively.
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ELEMENTS OF +2 CHEMISTRY SOLUTIONS

CALCULATION OF MOLECULAR MASS OF SOLUTE FROM TB :

We know that

1000  WB
Tb = Kb . m But m =
MB  WA

1000  WB 1000  K b WB
Therefore, Tb = K b  or MB = 
MB  WA Tb WA

This relation can be used to calculate the molecular mass (MB) of non-volatile solution.

D. DEPRESSION IN FREEZING POINT OF THE SOLUTION:

FREEZING POINT: The freezing of a liquid is that exact temperature at which the vapour
pressure of the liquid and solid phase becomes equal. At freezing point temperature, the liquid and
solid forms of substance co-exist. For example, the freezing point of pure water is 0oC or 273 K as
at this temperature, the vapour pressure of liquid and solid phase becomes equal.

DEPRESSION IN FREEZING POINT OF THE SOLUTION:

The addition of a non-volatile solute lowers the vapour

pressure of the solid phase of the solution. Therefore, the
solution is required to be cooled at a lower temperature to
make the vapour pressure of the liquid phase equal to the
solid phase. The difference in freezing points is called
depression in freezing point (Tf).

Let the freezing point if pure solvent = T1 K

Freezing point of the solution = T2 K

Depression in freezing point of the solution Tf = (T1 − T2) K

The vapour pressure of pure solvent and the solution is plotted against temperature. As in Fig. the
vapour pressure curve of pure solvent in liquid forms meets the vapour pressure curve of solid
solvent at point B, which corresponds to temperature T1, the freezing point of pure solvent.
Similarly, vapour pressure curve of solution meets the vapour pressure curve of solid solvent at
point A; which corresponds to temperature T2, the freezing point of the solution. Since T2 is less
than T1, the depression in the freezing point of the solution (Tf) is given by Tf = (T1 − T2).

MOLAL DEPRESSION CONSTANT:

TF is directly proportional to the lowering of the vapour pressure which in turn depends upon
the mole fraction (XB) of the solute in the solution.
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ELEMENTS OF +2 CHEMISTRY SOLUTIONS

Therefore, Tf  XB or Tf = K . XB ….. (i)

where K is the proportionality constant.

For dilute solution

nB nB M
XB = = = nB  A ……. (ii)
n A WA / MA WA
Molality (m) of the solution is given by

nB m  WA
m=  1000 or nB =
WA 1000

Putting the value of nB in Eq. (ii), we get

K  m  MA
Tf = = Kf . m (here Kf = K . MA, the product of two constant terms)
1000

Tf
or K f = , where constant K is known as Molal Depression Constant.
m

If m = 1; Tf = Kf

Thus molal depression constant is the depression in freezing point of solution where one mole of
solute is present in 1 kg or 1000 g of pure solvent (i.e. when molality of the solution is 1).

The value of Kf is difference for different solvent. For water, ethyl alcohol and benzene, the
value of Kf respectively are 1.86, 1.99 and 5.1 K/m.

CALCULATION OF MOLECULAR MASS OF SOLUTE FROM Tf:

We know that

1000  WB
Tf = Kf . m But m =
MB  WA

K f  1000
Therefore, Tf =  WB
MB  WA

K f  1000 WB
or MB = 
Tf WA

The relation is used to determine the molecular mass of non-volatile solute.

ABNORMAL MOLECULAR MASSES: The molecular masses can be determined from the relation
derived from colligative properties in which the molecular mass is inversely proportional to the
value of colligative property. Since the colligative property is directly proportional to mole fraction
of solute in a dilute solution. Therefore, when a solute undergoes association or dissociation in

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ELEMENTS OF +2 CHEMISTRY SOLUTIONS

solution, then the mole fraction of solute decreases or increases respectively. As a result of the
value for colligative property will also change and hence it will change the abnormal molecular
mass.

The main factors responsible for abnormality in molecular masses of solute are:

1. Association of solute molecules in solution.

2. Dissociation of solute molecules in solution.

1. ASSOCIATION OF SOLUTE MOLECULES IN SOLUTION: there are certain molecules like

alcohol, phenol, carboxylic acid, ammonia etc. which have tendency for the formation of H-bond
between their molecules in the solution and combine together to form bigger molecules or
aggregated molecules. This phenomenon is known as association. As a result of association, the total
No. of solute molecules in the solution decreases which cause decrease in value of colligative
property. Since the value of colligative property is inversely proportional to molecular mass of
solute, therefore, the molecular mass of solute will increase than its normal value.

For example, Acetic acid and Benzoic acid when dissolve in benzene they exist as dimmer by
forming H-bonds and therefore, the value of colligative property reduce to half where as the
molecular masses increases to double than normal.

2. DISSOCIATION OF SOLUTE MOLECULES IN SOLUTION: There are certain electrolytic

compounds which dissociate or ionize in solution forming two or more species per molecule. This
phenomenon is known as dissociation. As a result of dissociation, the total No. of solute molecules
in the solution increases which cause increase in value of colligative property. Since colligative
property is inversely proportional to molecular mass of the solute, therefore, the molecular mass of
solute will decrease than its normal value.

KCl dissociates to give K+ and Cl− ion in aqueous solution

KCl (aq.) K+ + Cl− (aq.)

Since each KCl molecule ionized into two ions, hence observed molecular mass of KCl must be
half of its normal value (74.5). Its observed value is 37.5.
22 Compiled By: Amit Kumar Phone no. 9796232077, 9797514942
 ELEMENTS OF +2 CHEMISTRY SOLUTIONS

Vant Hoff’s Factor: The Vant Hoff’s Factor which is represented by ‘i’ was introduced by Vant
Hoff in 1886. In order to express the extent of dissociation or association of a solute in a solution, it
is defined as. “The ratio between normal molecular mass obtained from molecular formula and
observed molecular mass, determined from colligative property experimentally.”

normal molecular mass

 i=
Observed molecular mass

Since molecular masses are inversely proportional to colligative properties,

abnormal colligative property

 i=
normal colligative property

Due to association and dissociation the values of Vant Hoff factor can be represented in three types
as follows:

(i) i = 1, when there is no association or dissociation.

(ii) i < 1, when solute molecules associate

(iii) i > 1, when solute molecule dissociate

DEGREE OF DISSOCIATION: It is defined as “the fraction of the total number of molecules

which dissociate into simple ions or molecules.”

Mathematically: It is represented by  and given as:

No. of solute molecules dissociate in solution

=
Total No. of solute molecules taken in solution

DEGREE OF ASSOCIATION: It is defined as, “the fraction of the total number of molecules
which associate into aggregated molecules.”

Mathematically: It is also represented by  and given as

No. of solute molecules associate in solution

=
Total No. of solute molecule taken in solution

RELATION B/W VANT HOFF FACTOR (i) AND DEGREE OF DISSOCIATION ():

Consider AB as an electrolytic solution taken in solution dissociate gives No. of ions. Let

a molecule of an electrolyte dissociate giving ‘n’ ions and  be the degree of dissociation

AB (aq.) Ao+ + O− (before dissociation)

(1 − )   (after dissociation)
No. of moles before dissociation = 1 mole
No. of moles after dissociation = (1 − ) + n = 1 + (n − 1) 

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ELEMENTS OF +2 CHEMISTRY SOLUTIONS

1 + (n − 1)  i −1
Therefore, i = or  =
1 n −1
Normal Mol. mass M
But i = = C
Observed Mol. mass MO
MC MC
 = 1+ (n − 1)  or − 1 = (n − 1) 
MO MO
MC − MO
or (n − 1)  = (here MC > MO)
MO
MC − MO
or =
MO (n − 1)
From this equation, degree of dissociation () can be easily calculated.
CALCULATION OF DEGREE OF ASSSOCIATION:
Let n molecules of solute associate to form one molecule and  is the degree of association.
nA (A)n
Initial No. of moles 1 0
No. of molecules at
equilibrium 1− /n
Therefore, total No. of moles at equilibrium (i.e. after dissociation) = 1 −  + /n
(1 − ) +  / n
Now, i= or  −  / n = 1− i
1
(n − 1)
or = i −1
n
MC MC
Also i =  = 1−  +  / n
MO MO

  (n − 1) MO − MC
or  − = 1− C or = (here MO > MC)
n MO n MO
MO − MC (n)
or  =  . From this Eq. degree of association () can be calculated.
MO n −1

24 Compiled By: Amit Kumar Phone no. 9796232077, 9797514942