TOPIC-1 Solutions and its Expression of Concentration, Solubility of Gases

Concepts Covered
 Types of solution  Molarity  Normality  ppm  Mass by volume%  Mole Fraction  Volume by volume%  Henry’s Law

Revision Notes Note: Solvent determines the physical state of the


solution.
Solution:
  A homogeneous mixture of two or more Types
  of Solutions: Any state of
pure substances is known as solution. matter (solid, liquid or gas) can
 Two constituents of the solution are: act both as a solvent and solute
(i) Solute: A substance that is dissolved in another during the formation of a solution.
substance in lesser amount, forming a solution. For
Therefore, depending upon the
example: Sugar, salt, etc.
(ii) Solvent: A substance in which another substance is physical states of solute and
dissolved in larger amount, forming a solution. For solvent, there are following nine
example: Water, milk, etc. different types of solutions:

S. No. Types of Solution Solute Solvent Examples

1. Solid – Solid Solid Solid Alloys like brass, bronze, etc.
2. Solid – Liquid Solid Liquid Solution of sugar, salt, urea, etc., in water.
3. Solid – Gas Solid Gas Sublimation of substances like iodine, camphor etc.
into air, dust or smoke particles in air.
4. Liquid – Solid Liquid Solid Hydrated salts, mercury in amalgamated zinc etc.
5. Liquid – Liquid Liquid Liquid Alcohol in water, benzene in toluene.
6. Liquid – Gas Liquid Gas Aerosol, water vapour in air.
7. Gas – Solid Gas Solid Hydrogen adsorbed in palladium.
8. Gas – Liquid Gas Liquid Aerated drinks.
9. Gas – Gas Gas Gas Mixture of gases, etc.
Aqueous
  solution: A solution containing water as Unsaturated solution: A solution in which more amount
 
solvent is known as aqueous solution. For example: of solute can be dissolved at the same temperature is
sugar solution. known as unsaturated solution.
Non-aqueous solution: A solution containing solvent
    Method of expressing concentration of solution:
other than water is known as non-aqueous solution. For The concentration of solution is the amount of solute
example: iodine dissolved in alcohol. present in the given quantity of solute or solvent. It can
 Saturated solution: A solution in which no more solute be expressed in any of the following types:
can be dissolved at the same temperature is known as w
(i) Mass percentage : It is the amount of solute in grams
saturated solution. W
dissolved per 100 g of solution.
 Mass% of a solute = And
Mass of solute in the solution Weight of solute ( WB )
× 100  = Moles of solute
Total mass of the solution Molar mass of solute ( M B )
v (vii) Molality (m): It is defined as the number of moles of
(ii) Volume percentage : It is defined as volume of a
V solute dissolved per 1000 g or 1 kg of solvent.
solute dissolved per 100 mL of solution. Number of moles of solute
Volume% of a solute Molality =
Mass of solvent in kg
Volume of solute
= Total volume of the solution × 100 WB × 1000
m=
w M B × WA
(iii) Mass by volume percentage : It is defined as where, WB = Weight of the solute, MB = Molar mass of
V
mass of solute dissolved per 100 mL of solution. It is solute, WA = Mass of solvent in g
commonly used in medicine and pharmacy. Unit is mol kg–1 or molal (m). Molality and mole fraction
Mass by volume % of solute as they are independent of volume do not change with
Mass of solute change in temperature.
= × 100 (viii) Normality (N): It is defined as number of gram
Volume of solution
(iv) Parts per million (ppm): It can be defined as the parts equivalents of solute dissolved per litre of solution.
of a component per million (106) solution. It is used to Number of gram equivalents of solute
express the concentration of a solute present in trace Normality =
Volume of solution in Litre
quantities.
Number of the parts WB × 1000
N=
EB × V
of the component (A)
 ppm (A) = × 10 6
Total number of parrts of all the where, WB = Mass of solute, EB = Equivalent weight of
components of the solution solute, V = Volume of solution in mL
Parts per million can be expressed in three ways:  Relationship between Molarity (M) and Molality (m):
(a) Mass to mass 1 d M
= - B
Mass of a component m M 1000
ppm (mass to mass) = × 10 6
Total mass of solution where, m = Molality of solution, M = Molarity of
solution,
(b) Volume to volume
MB = Molar mass of solute, d = Density of solution in
ppm (volume to volume)
g ml–1
Volume of a component
= × 10 6 Relationship between Mole fraction of solute (χB) and
 
Total volume of solution Molality (m):
(c) Mass to volume χ B × 1000
m=
Mass of a component (1 − χ B ) × M A
ppm (mass to volume) = × 10 6
Volume of solution where χB is mole fraction of solute, m is molality and
(v) Mole Fraction: It is the ratio of number of moles of a MA is molar mass of solvent.
particular component to the total number of moles of Solubility: Solubility can be
 
all the components. e.g., mole fraction of component A. defined as the maximum amount
nA
χA = , of solute that can be dissolved in
n A + nB 100 g of solvent to form a saturated
where nA is the number of moles of component ‘A’ and solution at a given temperature.
nB is the number of moles of component ‘B’.  Factors affecting Solubility:
nB
Similarly, χB = (i) Nature of Solute and Solvent: “Like dissolves like”
nA + nB i.e., polar solvents like water and ammonia can dissolve
Sum of mole fractions of all the components is always polar solute or ionic solute while non- polar solvents can
one. dissolve non- polar organic solutes.
χA + χB = 1 (ii) Temperature: Solubility increases with increase in
(vi) Molarity (M): It is defined as the number of moles of temperature. It increases for endothermic reaction
solute dissolved per litre of solution. while it decreases for exothermic reaction.
Number of moles of solute (iii) Pressure: The solubility of solid in liquid is not
Molarity = affected significantly by pressure because solids and
Volume of solution (in Litre)
liquids cannot be compressed. [Board 2023]
WB × 1000 Henry’s Law:
M=
MB × V 
The relationship between pressure and solubility is
where, WB = Weight of solute, V = Volume of solution guided by Henry’s Law. According to this law, ‘‘The
in mL, MB = Molar mass of solute. mass of a gas dissolved in given volume of the liquid
Unit is mol L–1 or M (molar). Molarity is dependent on at a constant temperature depends upon the pressure
changes in temperature. applied.’’
 It can also be stated as the partial pressure of the gas (p)
in vapour phase is proportional to the mole fraction of Solution: The solubility of gas is related to the mole
the gas (χ) in the solution. fraction in aqueous solution. The mole fraction of
p = K Hχ the gas in the solution is calculated by applying
where, KH = Henry’s constant. Henry’s law.
Thus, x (Nitrogen) = p (Nitrogen) /KH
 Applications of Henry’s law:
0.987 bar
(i) To increase the solubility of CO2 in soda water and soft = = 1.29 × 10 −5
drinks, the bottle is sealed under high pressure. 76 , 480 bar
(ii) To avoid the toxic effects As 1 litre of water contains 55.5 mol of it, therefore if
n represents number of moles of N2 in solution,

Partial pressure (p)

of high concentration of
nitrogen in blood, the x (Nitrogen) = n mole/n mole + 55.5 = 1.29 × 10–5 (n
in denominator is neglected as it is < < 55.5)
tanks used by scuba divers
Thus, n = 1.29 × 10–5 × 55.5 mol
are filled with air diluted
= 7.16 × 10–4 mol
with helium (11.7%),
(mole fraction) = 7.16 × 10−4 mol × 1000 mmol/1 mol
nitrogen (56.2%) and The slope of the line in = 0.716 mm
oxygen (32.1%). Henry’s constant, (K H)
(iii) At high altitudes, low Limitations
  of Henry’s law: This
blood oxygen level in law is applicable only when:
climbers cause Anoxia and make them unable to think (i) The pressure of gas is not too high
clearly. and temperature is not too low.
(ii) 
The gas should not undergo any
Example 1 chemical change.

If N2 gas is bubbled through water at 293 K, how (iii) The gas should not undergo
many millimoles of N2 gas would dissolve in 1 litre association or dissociation in the
of water? Assume that N2 exerts a partial pressure of solution.
0.987 bar. Given that Henry’s law constant for N2 at
293 K is 76.48 k bar. Ap


TOPIC-2 Raoult’s Law, Ideal and Non-Ideal Solutions

Concepts Covered
 Raoult’s law  Ideal solutions  Non - Ideal Solutions  Azeotropes- Maximum boiling and Minimum Boiling
(ii) Temperature: Vapour pressure of a liquid increases
Revision Notes with increase in temperature.
Vapour pressure is the pressure exerted by vapours over
 
Raoult’s
  law for a solution of volatile liquids: It states
a liquid at equilibrium state at constant temperature.
that for a solution of volatile liquids, the partial vapour
  Vapour pressure depends on the following factors: pressure of each component of the solution is directly
(i) Nature of the liquid: Liquids having weak proportional to its mole fraction in solution.
intermolecular forces are volatile and possess higher  [Board 2023]
vapour pressure.

Example 2
Suppose a solution is prepared by mixing two volatile o
ptotal = χA pA + χB pB
o
liquids A and B. Let χA and χB respectively be their
mole fractions, and let pA and pB be their partial
o o
= (1 – χB) pA + χB pB
vapour pressures respectively in the solution at a o o o
particular temperature. = pA + ( pB – pA )χB
o o The composition of the vapour phase in equilibrium
Ans. If pA and pB are their vapour pressures in the pure with the solution can be determined from the partial
state respectively, then according to Raoult’s law: pressure of the two components. If χA and χB are the
o
pA = pA χA mole fractions of components A and B respectively in
o the vapour phase, then
pB = pB χB
pA = χAptotal
Considering Dalton’s law of partial pressure,
and pB = χBptotal
ptotal = pA + pB
Substituting values of pA and pB, In general pi = χi ptotal

Raoult’s law as a special case of Henry’s law: According

  pA = KHχA
to Raoult’s law, the vapour pressure of volatile o
On comparing both expressions pA is equal to KH.
component (A) in a given solution is given as:
o Raoult’s
  law for non-volatile solute: For a solution
pA = pA χA
containing non-volatile solute present in a volatile
According to Henry’s law, in the solution of a gas in a solvent, Raoult’s law may be stated as the relative
liquid, the gaseous component is normally so volatile lowering of vapour pressure for a solution is equal to
that it exists as a gas and solubility depends upon the mole fraction of solute.
Henry’s law to which:
This Question is for practice and its solution is given at the end of the chapter.
 pA0 - pA (vi) Acetic acid and toluene.
χB = ,   Negative deviation from Raoult’s law: In this type of
pA0
deviation in non-ideal solutions, the intermolecular
where, χB = Mole fraction of solute,
attractive forces between A-A and B-B are weaker than
pAo – pA = Lowering of vapour pressure. those between A-B and leads to decrease in vapour
 Ideal solution: A solution which obeys Raoult’s pressure.
law over a wide range of concentration at specific Some examples are:
temperature is called ideal solution.
(i) Chloroform and acetone,
(ii) Chloroform and methyl acetate,
(iii) H2O and HCl,
(iv) H2O and HNO3,
(v) Acetic acid and pyridine,
(vi) Chloroform and benzene.

o o
(i) Raoult’s law is obeyed. pA = pA χA, pB = pB χB
(ii) ∆mixH = 0,
(iii) ∆mixV = 0,
(iv) The force of attraction between A-A and B-B is nearly
equal to A-B.
Some examples of ideal solutions are:
(i) n-hexane and n-heptane,
(ii) Ethyl bromide and ethyl chloride, Vapour pressure
of solution Vapour pressure
(iii) Benzene and toluene, of solution

(iv) Chlorobenzene and bromobenzene.

Vapour pressure

Vapour pressure
Non-ideal
  solution: A solution which does not obey p2
p1
Raoult’s law for all the concentrations is called a non- p
2
p1
ideal solution.
o o
(i) Raoult’s law is not obeyed, i.e., pA ≠ pA χA and pB ≠ pB χB
χ1 = 0 Mole fraction χ1 = 1 χ1 = 0 Mole fraction χ1 = 1
(ii) ∆ mixH ≠ 0, χ2 = 1 χ1 χ2 = 0 χ2 = 1 χ1 χ2 = 0
χ2 χ2
(iii) ∆ mixV ≠ 0,
(a) (b )
(iv) The force of attraction between A-A and B-B is not
equal to A-B.
The vapour pressures of two component systems as
Some examples of non-ideal solutions are:
a function of composition:
(i) Water and ethanol
(a) A solution that shows positive deviation from
(ii) Chloroform and acetone
Raoult’s law, and
(iii) Ethanol and cyclohexane
(b) A solution that shows negative deviation from
Raoult’s law.
 Azeotropes:
 Liquid mixtures
which distil over without change
in composition are called constant
boiling mixtures or azeotropes
or azeotropic mixtures. It means
that the vapor phase has the same
composition as the liquid phase
during the process of the distillation.
 A non-ideal solution can show either positive or  Minimum
 boiling azeotropes:
negative deviation from Raoult’s law. Non-ideal solutions showing large positive deviation
  Positive deviation from Raoult’s law: In this type from Raoult’s law form minimum boiling azeotropes
of deviation, A-B interactions are weaker than the at a specific composition. e.g., water and benzene,
interaction between A-A or B-B and leads to increase in chloroform and methanol.
vapour pressure.  Maximum boiling azeotropes: Non-ideal solutions

Some examples are:
showing large negative deviation from Raoult’s
(i) Water and ethanol,
law form maximum boiling azeotropes which boil
(ii) Chloroform and water,
at temperature higher than the boiling points of its
(iii) Ethanol and CCl4,
(iv) Methanol and chloroform, components. e.g., mixture of HNO3 and H2O.
(v) Benzene and methanol,
 TOPIC-3 C olligative Properties, Determination of Molecular Mass, abnormal Molecular Mass,
Van’t Hoff Factor
Concepts Covered
 Colligative Properties  Determination of Molecular Mass  abnormal Molecular Mass  Van’t Hoff Factor
solid solvent at lower temperature. Thus, the difference
Revision Notes in the freezing point of pure solvent and that of the
Colligative
  properties: Certain properties of solutions solution is known as depression of freezing point.
depend only on the number of particles of the solute o
The freezing point of pure solvent = T f
(molecules or ions) and do not depend on the nature of
 The freezing point when non-volatile solute is
solute, such properties are called colligative properties.
dissolved in it = Tf (Freezing point of solution)
These are:
Colligative properties are independent of the nature of
(i) Relative lowering of vapour pressure,
solute.
(ii) Depression of freezing point, The decrease in freezing point ∆Tf = T fo – Tf is known
(iii) Elevation of boiling point,
as depression in freezing point.
(iv) Osmotic pressure of the solution.
For dilute solution,
Relative
  lowering of vapour pressure: The relative    ∆Tf ∝ m
lowering of vapour pressure is the ratio of lowering of ∆Tf = K f m.
vapour pressure and vapour pressure of pure solvent
We know,
which is equal to the mole fraction of solute.
o WB × 1000
Vapour pressure of pure solvent = pA (i) = molality
MB × WA
o
Lowering of vapour pressure = pA – pA K f × 1000 × W2
Relative lowering of vapour pressure (ii) ∆Tf =
M2 × W1
pAo - p A n
= χsolute = Kf = Freezing point depression constant or molal
pAo N+n depression constant or Cryoscopic constant.

where n and N are the number of moles of solute and
solvent respectively. solv
ent
uid
Elevation of the boiling point: The difference in boiling
 
Liq n
l utio
So
t
point of solution and pure solvent is called elevation of en
so
lv
en
Vapourpressure

oz
the boiling point. [Board 2023] Fr

Boiling point of pure solvent = Tb° f

Boiling point of solution = Tb

f f

Increase in boiling point ∆Tb = Tb – Tb° is known as Temperature/K

elevation of boiling point for dilute solution. Diagram showing Tf , depression of the
∆Tb ∝ m freezing point of a solvent in a solution.
∆Tb = Kbm
Osmosis:
  The process in which there is net flow of
K × 1000 × w2 solvent to the solution by a semipermeable membrane
∆Tb = b
M2 × w1 is called osmosis.
Osmotic pressure: The extra pressure that is applied to
 
Where, w2 = weight of solute in g
stop the flow of solvent to solution across a semipermeable
M2 = Molar mass of solute
membrane is called osmotic pressure of the solution.
w1 = weight of solvent in g
For dilute solution, osmotic pressure is proportional to
∆Tb = Kbm the molar concentration (C) of the solution at a given
Kb = Boiling point elevation constant or molal elevation temperature T.
constant or Ebullioscopic constant. Thus, π = CRT as π is the osmotic pressure and R is the
gas constant.
 π = ( nB / V ) R T (n is the number of moles, V is the
volume of solution)
P atm +  Patm

SPM

Elevation of boiling point

Solution Solvent

Depression
  of freezing point: According to Raoult’s The excess pressure equal to the osmotic
pressure must be applied on the solution side to
law, when a non-volatile solid is added to the solvent its prevent osmosis.
vapour pressure decreases and become equal to that of
 Reverse
  osmosis: The direction of osmosis can be ( ∆Tb )obs
reversed, if a pressure larger than the osmotic pressure (ii) For elevation of boiling point, i = ;
( ∆Tb )cal
is applied to the solution side. Now the pure solvent
flows out of the solution through the semipermeable ( ∆Tf )obs
(iii) For depression of freezing point, i = ;
membrane. This phenomenon is called reverse osmosis. ( ∆Tf )cal
π
Piston (iv) For osmotic pressure, i = obs ;
π cal
Pressure π Since a colligative property is proportional to number
of particles of solute.
Salt water Normal molecular mass
Fresh water i=
Observed molecular mass
Normal molecular mass = i × Calculated molecular mass.
Water
outlet Normally ionic compounds dissociate in water and will
SPM
have i>1
Reverse osmosis occurs when a pressure Total number of moles of particle
larger than the osmotic pressure is applied to
the solution. after association/dissocciation
i=
Total number of moles of particle
  bnormal molecular mass: When the molecular mass
A
before associationn/dissociation
calculated with the help of colligative property is
different from theoretical molecular mass, it is called   Hypertonic solution: A solution is called hypertonic,
abnormal molecular mass. if its solute concentration is higher than that of the
solution separating it by a semipermeable membrane.
 Van’t Hoff factor(i): The ratio of the observed
(experimental) value of a colligative property to the Hypotonic
  solution: A solution is called hypotonic,
normal (calculated) value of the same property is called if its solute concentration is lower than that of the
as Van’t Hoff factor. solution separating it by a semipermeable membrane.
Mathematically, Isotonic solution: Two solutions are called isotonic, if they
 
Observed (experimental ) exert the same osmotic pressure at a given temperature.
Isotonic solutions have same molar concentration.
value of a colligative property
i= When such solutions are separated by semipermeable
Normal ( calculated) value of membrane no osmosis occurs between them.
the same colligative property
∆
Or, i = obs
∆ cal
where Δobs and Δcal respectively represent the observed
and calculated value of a colligative property.
Thus,
( ∆p )obs
(i) For lowering of vapour pressure, i =
( ∆p )cal

SUBJECTIVE TYPE QUESTIONS