Solution (by K.

Singh)

Solution
Solution: - A homogeneous mixture of two or more substances is known as solution.
Solution = Solvent + Solute
Larger amount Smaller amount
& Physical state may same or difft as that of soln & Physical state
remains same as that of solution
Expressing concentration of solutions:- composition of a solution can be described
by expressing concentration. The latter can be expressed either qualitatively or
quantitatively. For example, qualitatively we can say that solution is dilute (i.e., relatively
very small quantity of solute) or it is concentrated (i.e., relatively very large quantity of
solute). But in real life these kinds of description can add to lot of confusion and thus the
need for a quantitative description of the solution.

There are several ways by which we can describe the concentration of the solution
quantitatively.

Mass percentage:-
(i) Mass % weight by weight :- It is the weight of substance in gms which is
dissolved in 100gm of soln
Mass % of a component = 100

(ii) Mass % weight by volume :- It is the weight of solute in gms which is

dissolved in 100ml of soln
Volume % of a component = 100

(iii) Mass % volume by volume :- It is the volume of a solute in ml which is

dissolved in 100ml of solution
=

1. Parts per million: When a solute is present in trace quantities, it is convenient to

express concentration in parts per million (ppm) and is defined as:
Parts per million =
= 106 (203)
As in the case of percentage concentration in parts per million can also be
expressed as mass to mass, volume to volume and mass to volume. A liter of
sea water (which weight 1030 g) contains about 6 10-3 g of dissolved oxygen
(O2). Such a small concentration is also expressed as 5.8 g per 106 g (5.8 ppm)
of sea water. The concentration of pollutants in water or atmosphere is often
expressed in terms of g mL-1 or ppm.

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For a solution containing i number of components, we have:

X1 = =
It can be shown that in a given solution sum of all the mole fraction is unity, i.e.
X1 + x2 + …………………..+ x1 = 1

Mole fraction unit is very useful in relating some physical properties of solutions, say
vapour pressure with the concentration of the solution and quite useful in describing the
calculations involving gas mixtures.

1. Molarity: - The number of moles of solute which are dissolved in 1000 ml (or 1 lit) of
solution is K/as molarity (M). Unit molar.

X = wt of Subs in gms
M= Molarity.
V= Volume of solution in ml.
Or W= Mol. mass of substance

n = no. of moles

Or

Q. 0.4 gm of NaOH is presence in 500ml of soln, Calculate M of the Soln

Sol. = = = 0.02 molar

2. Normality (N):- The number of gram equivalents Solute which are dissolved in
1000ml (or 1 lit) of soln is k/as Normality.

Where
N = normality
Or X = wt of subs in gm, E = Equivalent wt

Eqt wt(E) =

Or V = Volume of Soln in ml.

Normality = Valency factor X Molarity

3. Molality (m):- The number of moles of a Solute which are dissolved in 1000gm (or
1Kg) of Solvent is K/as molality.

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 Solution (by K.Singh)

or m= Where M = molality
W = mol. mass of subs V' = wt of solvent
m = n × 1000/v X = wt of subs in gm. n = no. of moles.

4. Formality (F):- The number of gram formula mass of a solute which are present in
1000ml (or 1 lit) of solution is K/as formality (F)

Where = x = wt of subs in gm
F = formality
W = formula mass
V = volume of soln in ml
Or

5. Normality & molarity change on dilution:-

N1V1 = N2V2 & M1V1 = M2V2

6. Resultant normality of a mixture which contains either all acids or all bases.
N1V1 + N2V2 + N3V3 + ………….. = N V
Where N = resultant normality
V = V1+V2+V3 + ………… = Total volume

7. Resultant normality of mixture which contains both acids as well as bases.

(N1V1 + N2V2 + ……..) ~ (N1V1 + N2V2 + ……….) = NV

Acids Bases
Where N = resultant normality.
V = [V1 + V2 + ………] + [V1+V2 + ………]

Mole-fraction (χ):- It is the ratio of number of moles of a particular component to the

total number of moles of all the components of a soln
For Ex. A soln contains two components A & B then.

= nA = no. of moles of Sub A

nB = ,, ,, ,, B
nA + nB = ,, ,, Soln

Note: - Mole fraction of a complete Soln = Unity = 1

i.e. χ A + χ B = 1
For a solution containing i number of components, we have:
X1 = =
It can be shown that in a given solution sum of all the mole fraction is unity, i.e.

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X1 + x2 + …………………..+ x1 = 1
Mole fraction unit is very useful in relating some physical properties of solutions,
say vapour pressure with the concentration of the solution and quite useful in
describing the calculations involving gas mixtures.

Relationship between mole-fraction of solute (χ B) & molality (m)

Where = χ B = mole-fraction of solute
m = molality
W = molar mass of solute.
Relation ship between Molarity (M) & molality (m).

Where m = molality
M = molarity
d = density of soln
W = molar mass of solute.
Solubility: - At given tempr the amount of solute dissolved in 100gm of solvent to form
saturated solution is K/as solubility.

Solubility α Hydration energy

α 1/Lattice energy
α temperature endothermic process.
α for exothermic process.
Solubility of gases in gas: - At given conditions all the gases are soluble in all
proportion.
Dalton’s law of partial pressure states that two or more volatile compounds are enclosed
in a vessel then total pressure is equal to the sum of partial pressure of each
component
If PA , PB & PC are the partial pressures of gases A , B & C respectively that are present
in a mixture. Then total pressure of mixture is.
P = PA + PB + PC = P˚A χ A + P˚B χ B + P˚C χ C
Solubility of gases in liquid: - It depends upon 4-factors.
1. Nature of gases
2. Nature of solvent
3. Temperature
4. Pressure

1. Nature of gases :- (i) those gases which are dissociates or ionized into their ions
or reacts with solvent are highly soluble in liquids
Ex. (1) NH3 + H2O NH4OH
(2) HCl + H2O H3O+ + Cl-
(3) CO2 + H2O H2CO3
(ii) Those gases which do not dissociate or ionized into their ions & not react with
solvent are less soluble in liquids.
Ex. H2, O2, N2, O3, Cl2, I2 etc.

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(iii) Solubility Coefficient of gas: - At const tempr & pressure the volume of any
gas which is present or soluble in a particular solvent

(2) Nature of Solvent:-

Solubility α Ionic nature of solvent eg. H2O

(3) Temperature: - for gases solubility α

(4) Pressure: - Henry`s law. The law states that at a constant temperature, the
solubility of a gas in a liquid is directly proportional to the pressure of the gas. Dalton, a
contemporary of Henry, also concluded independently that the solubility of a gas in a
liquid solution is a function of partial pressure of the gas. If we use the mole fraction of a
gas in the solution as a measure of its solubility, then it can be said that the mole
fraction of gas in the solution is proportional to the partial pressure of the gas over the
solution. The most commonly used from og Henry’s law states that “the partial pressure
of the gas in vapour phase (p) is proportional to the mole fraction of the gas(x) in the
solution” and is expresses as:

P = KH x
Here KH is the Henry’s law constant. If we draw a graph between partial pressure
of the gas versus mole fraction of the gas in solution, then we should get a plot.
Different gases have different KH values at the same temperature. Thus suggests
that kH is a function of the nature of the gas.
It is obvious from equation that higher the value of KH at a given pressure, the
lower is the solubility of the gas in the liquid. KH values for both N2 and O2
increases with increase of temperature indicating that the solubility of gases
increases with decreases of temperature. It is due to this reason that aquatic
species are more comfortable in cold waters rather than in warm waters.

Henry’s law finds several applications in industry and explains some biological
phenomena. Notable among these are:
• To increase the solubility of CO2 in soft drinks and soda water, the bottle
is sealed under high pressure.
• Scuba divers must cope with high concentration of dissolved gases while
breathing air at high pressure underwater. Increased pressure increases
the solubility of atmospheric gases in blood. When the divers come
towards surface, the pressure gradually decreases. This releases the
dissolved gases and leads to the formation of bubbles of nitrogen in the
blood. This blocks capillaries and creates a medical condition known as
bends, which are painful and dangerous to life. to avoid bends, as well
as, the toxic effects of high concentrations of nitrogen in the blood, the

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tanks used by scuba divers are filled with air diluted with helium(11.7%
helium, 56.2% nitrogen and 32.1% oxygen).
• At high altitude the partial pressure of oxygen is less than that at the
ground level. This leads to low concentrations of oxygen in the blood and
tissues of people living at high altitudes or climbers. Low blood oxygen
causes climbers to become weak and unable to think clearly symptoms of
a condition known as anoxia.

Effects of Temperature

Solubility of gases in liquids decreases with rise in temperature, when

dissolved. The gas molecules are present in liquid phase and the process of
dissolution can be considered similar to condensation and heat is evolved in
this process. We have learnt in the last section that dissolution process
involves dynamic equilibrium and thus must follow Le Chaterlier’s Principle.
As dissolution is an exothermic process, the solubility should decreases with
increases of temperature.

Solubility of solids: - It depends upon three factors.

1. Nature of solid:- Solubility α Polar nature of solids

2. Nature of solvent :- Solubility α Polar nature of solvent
3. Temperature :-

Those subs which shows those subs which shows

Endothermic nature on exothermic nature on
Dissolving in solvent dissolving in solvent
Solubility α Temperature solubility α
Eg. Sugar in water, eg. CaO + H2O
Salt in water MgO + H2O

Raoult’s Law: - At const tempr the partial pressure of any component is given by
the product of vapour pressure in pure state and mole fraction of that component. It
is k/as Raoult’s law.
i.e.
PA = P˚A χ A where PA = Partial pressure of A.
PB = ,, ,, ,, B.
PB = P˚B χ B P˚A = Vapour pressure in pure state of A
B˚B = ,, ,, ,, ,, B
χ A = Mole fraction of A
χ B = ,, ,, ,, B
Let a solution contains two components A & B. So total pressure ‘P’ is
P = PA + PB
P = P˚A χ A P = P˚B χ B

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P = P˚A χ A + P˚B χ B

Ideal & Non-Ideal Solutions:-

Ideal Solutions:-The solution which follows Raoults law at all temperatures and at
all concn is k/as ideal solution.
At the time of manufacturing the change in volume & change in enthalpy is zero.

A
Ex. 1 C6H6 + C6H5-CH3 P = P˚A χ A + P˚Bχ B
2 C2H5Cl + C2H5Br
3 C2H6 + C3H8
B

vapour
Characteristics of Ideal solution:- pressure

1. It follows Rault’s law.

2. ∆ Vmixing = O i.e. Volume remains constant. χ A= 1 χ B= 1

3. ∆Hmixing = O i.e. Enthalpy remains constant. χ B= 0 χ A= 0

4. Force of interaction between (A-B) =force of interaction between (A-A)

= force of interaction between (B-B)

Non-Ideal Solution: - those solutions which do not follow Raoults law at any tempr &
concn are k/as non-ideal solutions.
At the time of manufacturing the change in volume and change in enthalpy is not zero.
Non-Ideal solutions are of two types.
(i) Positive deviation Non-Ideal solution.
(ii) Negative deviation Non-Ideal solution.

(i) Positive deviation Non-Ideal solution: -

Characteristics: - (a) It does not follow Raoults law (i.e. PA > P˚A χ A
(b) ∆Vmixing ≠ 0 but positive , it means at the time of manufacturing volume of
resultant solution increases.
(c) ∆ Hmixing ≠ 0 but positive, it means Endothermic Rxn.
(d) [A-B]Force of interaction < [A-A]force of intn & [B-B]force of intn

i.e. [A-B] force of intn < [A-A]force of intn

,, < [B-B] force of intn
Diagrammatic representation of positive deviation non-Ideal soln

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1. C2H5OH + HOH P > P˚A χ A + P˚B χ B

A
2. C2H5OH + R-OH
3. C2H5OH + CH3-Cl
B
4. C2H5OH + CH2Cl2
5. C2H5OH + CH3-CO-CH3 vapour
6. C2H5OH + CHCl3 pressure
7. CS2 + CHCl3
8. CCl4 + CHCl3

χ A= 1 χ B= 1
χ B= 0 χ A= 0

(ii). Characteristics of negative deviation non-ideal soln:-

(a) Does not follows Rault’s law (i.e. PA < P˚A χA)
(b) ∆ Vmixing ≠ O but negative it means at the time of manufacturing volume of
resultant soln decreases.
(c) ∆ Hmixing ≠ 0 but (-)ve it means Exothermic Rxn
(d) [A-B]force of interaction > [A-A]force of interaction.
,, .. > [B-B]force of interaction.

Diagrammatic representation of negative deviation non-Ideal soln

A

1. HCl + H2O P < P˚AχA + P˚BχB

B
2. H2SO4 + H2O
3. HNO3 + H2O vapour
4. CHCl3 + CH3-CO-CH3 pressure
5. CHCl3 + Benzene
6. CHCl3 + Pyridine
7. CH3-C-CH3 + Aniline
χ A= 1 χ B= 1
χ B= 0 χ A= 0
Azeotropic Mixtures: - The mixture of misseable two or more than two liquids which
boils at same temperature it is called azeotropic mixture.
The component of azeotropic mixture does not separate by fractional distillation
method.

Ex.1 C2H5OH + H2O + C6H6

Boiling pt 88˚C 100˚C 80˚C
Ratio =1 : 0.4 : 4

It is an example of ternary azeotropic mixture which boils at 68˚C

Ex.2 C2H5OH + C6H6 it is binary azeotropic mixture

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1 : 4 which boils at 65˚C

Azeotropic mixtures are of two types.
(i) Low Boiling Azeotropic mixtures: - The B.pt. of azeotropic mixture is less than
that of B.pt. of components.
Ex. All positive deviation non-ideal solution.
(ii) High Boiling Azeotropic mixture: - The B.pt. of azeotropic mixture is greater
than that of B.pt. of components.
Ex. All (-)ve deviation non-ideal solution.

Osmosis: - The phenomenon in which the movement of solvent particles takes places
from dilute solution to concentrate solution through a semi-permeable membrane is k/as
osmosis.

Semi-Permeable or (SPM) Membrane: - It is a membrane which allow to passage only

solvent molecules through them but not solute particles, is called SPM.

Ex. Of organic SPM. :- (i) Parchment paper

(ii) Animal membrane
(iii) Gallbladder.

Ex. Of Inorganic SPM:- (i) Cellulose nitrate

(ii) Copper Ferro cyanide
(iii) Calcium phosphate

Reverse Osmosis: - The phenomenon in which solvent particles migrates or move

from the concentrated solution to dilute solution. This is called reverse osmosis.
Its main application is to makes sea water fit for drinking purpose with the help of
reverse osmosis.

Osmotic Pressure (π) :- The extra pressure that must be applied to the solution side to
prevent the flow of solvent into solution through a semi-permeable membrane is k/as
osmotic pressure.

Colligative Properties:- Those physical properties which are depends upon the
number of ions (for electrolytes eg. NaCl , KCl etc.) & number of molecules (for non-
electrolyte eg. Glucose, Gum, Starch, fructose etc.) are considered as colligative
properties.
Example of Colligative Properties:-
(i) Osmotic pressure (π)
(ii) Depression in vapour pressure (∆P)
(iii) Elevation in boiling points. (∆Tb)
(iv) Depression in freezing points (∆Tf)

Vant Hoff’s Theory of Dilute solution :- It state that the solute particles of very dilute
solution migrates or moves from one position to another position just like the gaseous
molecules moves in gaseous mixture. Vant Hoff’s give following conclusion:-

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1. Boyl Vant Hoff’s Theory :- IT state that at constant temperature the osmotic
pressure is directly proportional to concentration i.e.
π α c or c α 1/V
π α 1/ V ……………. (i)

2. Temperature- Pressure vant Hoff’s Theory: - At const pressure & const

concentration the osmotic pressure directly proportional to tempr.
π α T …………..(ii)
From eqn (i) & (ii) we have general eqn

π α T/V
or π α RT/V where R = Vant Hoff’s const. = 0.082 lit atm
for 1 mole π V = RT …………(iii)

for ‘n’ moles the above equation becomes.

π V = n RT (we know n = )
πV = or π =
π = CRT (where C = )

Isotonic solutions: - Those solution which have same osmotic pressure are
considered as isotonic soln if the π1 of one soln at temp T is
π1 = C1RT …………..(i)
n
if the π2 of sec. sol at temperature T is
π2 = C2RT …………..(ii)
we know that π1 = π2 (isotonic soln)
C1RT = C2RT
C1 = C2

Thus concn of isotonic solutions are also equal.

i.e.

Depression in vapour pressure: - When we add non-volatile substances in a pure

solvent then the vapour pressure of soln is decreases.
if the vapour pressure of pure solvent = P
If vapour pressure of solution is = Ps

Ps < P always
∆ P = P - Ps ………….(i)

Relative change in vapour pressure.

………….. (ii)

The relative lowering in vapour pressure and mole fraction of solute.

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(iii) Where n = no. of moles of solute

N = ,, ,, ,, solvent
We know n = w/m & N = W/M
Where w = wt of solute, m = molecular mass of solute.
W = wt of solvent, M = molecular mass of solvent
For very dilute solution n << N. so eqn (iii) becomes as
or ……………….. (iv)

This relation used to calculate molecular wt of solute from depression in vapour

pressure.

Elevation in Boiling points ( Tb) :- The temperature at which the vapour pressure of
any solvent equal to 1 atm pressure it is called boiling point.

Boiling point of
Solvent solution

1 Atm

Vapour pressure

Tb Tb

Temperature / K

(The vapour pressure curve for solution lies below the curve for pure water. The
diagram shows that Tb denotes the elevation of boiling point of a solvent in solution.)

If P = Pressure of pure solvent.

Ps = Pressure of solution
Ps < P always
Therefore, more amount of energy is required to become the pressure of solution equal
to 1 atm.
If T = Boiling point of solvent & Ts = Boiling pt of soln and Ts > T
∆Tb = Ts – T
We know ∆Tb α ∆P/P & ∆Tb α m1 where m1 = molality of soln
Or
∆Tb = Kb m1 ------(i) where Kb = Molalelevation const or Ebullioscopic const.
For water Kb = 0.52

Calculation of molecular weight of solute:-

m = molecular mass of solute.
M = ,, ,, ,, solvent ------ (ii)

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w = wt of solute in gms
W = ,, ,, solvent in gms
On putting the value of m1 in eqn (i) we get
------------ (iii)

Relation betn

We know or -------- (iv)

From eqn (iii) & (iv) we have

--------------- (v)

Relationship between π &

We know π = --------- (vi)

From eqn (iii) & (vi) we have

Molal elevation constant: - The elevation in boiling point is equal to the molal elevation
is equal to the molal elevation constant when the molality of the solution becomes equal
to unity or one.

If m' = unity or 1 then

Depression in freezing point: - The tempr at which the vapour of any liquid becomes
equal to the vapour pressure of solid. It is called freezing point
If T = freezing point of solvent
Ts = ,, ,, solution
T > Ts

'
We know that (where m' = molality of solution
m' …… (i) Where Kf = molal depression const. or cryoscopic const.
For water Kf = 1.86.
If m1 = 1 then above
Eqn becomes
The depression in freezing points equal to the molal depression const. if molality of the
soln becomes one or unity it is called cryoscopic const.

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Liquid solvent

Frozen solvent Solution

Vapour pressure

Tf

Tr

Temperature/K

Diagram showing Tf , depression of the freezing point of a solvent in a solution.

Calculation of molecular wt of solute:-

m'
Put the value of m' = in above eqn
…………. (ii)

Relation betn ………… (iii)

From eqn (ii) & (iii) we have.

× ………… (iv)

Relation between π & f

We know π = RT or π=

…………. (v)
n
From eq (ii) & (v) we have

× ………….. (vi)

Abnormal Colligative properties:-

1. General or Theoretical colligative properties: - The colligative properties neither

dissociate in ions or particles nor associates in ions or particles. Such colligative

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 Solution (by K.Singh)

properties are called general colligative properties such as Glucose, starch,

gelatin etc.
2. Observed Colligative properties: - Those colligative properties which dissociates
in their ions or associates are called abnormal colligative properties or observed
colligative properties.
Eg. Electrolytes such as NaCl , KCl , CsCl , etc.
3. Vant Haff factor :- It is represented by ‘i’ it is the ratio of experimental value of a
colligative properties to the theoretical value (calculated value) of colligative
properties is called vant Haff factor (i)

Association of solute molecules: - In this two or more molecules associate to form a

bigger molecule.
(a) Degree of association: - The fraction of the total no. of moles which combine to
form bigger molecule is called the degree of association.
Suppose the ‘n’ molecules of compound ‘A’ associates and form one molecule of
B (n=degree of association).

nA Bn
n
(i) Initial conc 1 0
(ii) If degree of (1- α) 0 +

where i < 1 i = Vant Hoff factor.

(b) Degree of dissociation (α) with I :-

Suppose ‘A’ compound dissociates into ‘n’ ions of B.
A nB
(i) Initial concn 1 0
(ii) Degree of dissn is α (1- α) nα
n
Then conc
Where i >

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Compound - NaCl BaCl2 AlCl3

Al2(SO4)3

No. of ions (n) n=2 n=3 n=4 n=

5

Degree of dissn ( α)

Measurement of osmotic pressure: - It is based on the principle of applying pressure

on the
soln. So as to just avoid the entry of the solvent into the soln through the SPM.

Apparatus consists of:-

1. A porous tube containing copper cyanide deposited in it.
2. A bronze cylinder fitted with a piston & a pressure gauge.
3. A capillary indicator & a water reservoir.
Advantage of this method: (i) In this method there is no change in the dilution of soln so
we can determine accurate value of osmotic pressure.
(ii) The method is quick since the equilibrium is established.

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