SOLUTION Types of solution

Depending upon the nature of the solvent

Definition of Solution solutions is up to the following types.
“A solution is a homogeneous mixture of one i) Gases solution
or more solute dissolved in solvent” All the gases & vapours form homogeneous
mixture. Therefore, mixture of gases regarded as
Solvent solution.
The substance in which a solute dissolve to
produce a homogeneous mixture. ii) Liquid solution
Solute These solutions can be obtained by mixing solid
The substance that dissolves in a solvent to produce or gases in liquids or two substances of which are
a homogeneous mixture. themselves liquids.
e.g., sugar solution, vinegar.
Binary solution
A solution consisting of two components is iii) Solid solution
called binary solution. The components of binary When two different types of solids mixed in
solution are called solute & solvent. their molten state, they form solid solution.
Depending up on the physical state of solute & e.g. Alloy of bronze is a mixture of Cu & Sn.
solvent, solutions are classified as follows.
Note.
Types of Solute Solvent Example Like dissolves like
solution Polar solute dissolves more in polar solvent &
Gas Gas Mixture of gases or non-polar solute dissolves more in non-polar
vapors solvent. They dissolve more due to their similar
Gaseous Liquid Gas Chloroform(CHCl3 ) structure & electrical properties.
solution & N2 gas mixture
Solid Gas Camphor in N2 in Methods of expressing concentration of solution
gas. The various methods of expressing concentration
Gas Liquid Soda bottle contains of solution as follows: -
CO2 gas.
Liquid i) Strength of solution (s)
solution Liquid Liquid Vinegar (Solution of The strength of the solution is always expressed
H2O & CH3COOH) as amount of solute in gram dissolved per litre of
solution. It is denoted as ‘s’.
Solid Liquid Sugar solution.
Mathematically,

Gas Solid H2 absorbed on Amount of solute in gram

Strength (S) = Volume of solution in litre
palladium &
platinum
➢ The unit of strength is gm L−1.
Solid Liquid Solid Amalgam of Hg &
solution e.g. if 4gm of NaOH is dissolved in one
Na
litre of solution, them it is written as 4gm/L.
Solid Solid Alloy (Bronze
mixture of Cu &
ii) Percentage of solution
Sn).
The concentration of solution in terms of
percentage can be expresses in the following ways.
In general, The component present in the same a) Mass to mass percentage (W/W)
physical state in a solution. The component present Mass of solute in gm
in large quantity is called solvent & the other = Mass of solution in gm × 100
component is called solute.
The solution in which water is solvent are ➢ It is represented by (W/W)
called aqueous solution, while those in which water
is not a solvent are called non-aqueous solution.

Page 1
b) Mass to volume percentage (W/V) 1gm equivalent of NaOH dissolved in 1 litre of
Mass of solute in gm solution = 1N NaOH
= Volume of solution in ml × 100
Or, 40 gm NaOH present in 1L solution = 1N
Or, 20gm NaOH present in 500 ml of solution= 1N
➢ It is denoted by (W/V)
Or, 20 gm NaOH present in 1000 ml of soln = 0.5 N
Or, 4 gm NaOH present in 100 ml of solution = 1N
Or, 4 gm NaOH present in 1 L of solution = 0.1 N
c) Volume to volume percentage (V/V)
Volume of solute in ml
= Volume of solution in ml × 100 iv) Molarity (M)
It is defined as the no. of moles of the solute
➢ It is represented by (V/V). present per litre of solution. It is denoted by the
letter ‘M’.
d) Volume to mass percentage (V/W)
Volume of solute in ml Note
= Mass of solution in gm × 100
Molar solution
When one mole of the solute is present in one
➢ It is represented as (V/W). litre of solution is called molar solution.
Examples:
❖ 5% (W/W) aqueous solution of NaCl No. of moles of solute
contains 5gm NaCl & 95gm water. Molarity (M) = × 1000
Volume of solution in ml
Total mass of solution = 100gm.
❖ 10% V/V aqueous solution of methanol ➢ Molarity of the solution can also be
contain 10ml of methanol & 90ml of water. calculated from its strength
Total volume of solution = 100ml Strength
M = molar mass of solute
❖ 10% (W/V) solution of Kl contain 10gm of
Kl & 100ml of water.
Density
Total volume of the solution =100ml. Or M = molar mass

iii) Normality ➢ If W gm of the solute is present in V ml of

Normality is defined as the number of gram the solution, then,
equivalent of the solute present per litre of solution.
It is denoted by letter “N”. W 1000
M = molecular mass × V
Note Unit:-
Normal solution ➢ The unit of molarity is mol. L−1 .
When 1gm equivalent of solute dissolved in one ➢ molarity is also represented as mol. cm−3 .
liter of solution is called a normal solution. Example:-
1mole of CH3COOH present in 1 ltr solution = 1 M
60 gm of CH3COOH present in 1 litre solution=1M
amount of solute in gm
No of gm equivalent = equivalent mass of solution 6 gm of CH3COOH present in 1 L = 0.1 M
6 gm of CH3COOH present in 100 ml = 1 M
No.of gm equivalent
N= × 1000 vi) Molality (m)
volume of solution in ml
Molality is the number of moles of the solute
No.of gm equivalent of solute present in 1000 gm of solvent. It is denoted by ‘m’.
N= volume of solution in litre
Note
strength of solution
N = equivalent mass of solute Molal solution
When one mole of solute is dissolved in 1000gm of
solvent, it is called one molal solution.
Unit of normality (N) is gm equivalent 𝐿−1 .
Example: no. of moles of the solute
molecular mass of NaOH Molality = × 1000
Eq. Mass of NaOH = mass of the solvent in gm
Acidity
40
= 1 = 40

Page 2
The molality of given solution does not change Remember
with temperature, because in such solution mass is
form the basis. No Mode of Definition Units
𝑤×1000 expressing
M = M×W
conc.
Where, w = mass of the solute
1 Percentage Mass of solute in % by mass
W = mass of the solvent by mass gm present in dimension
M = molecular mass of the solute (solid liquid 100gm of less
The unit of molality is mol. kg −1. in liquid) solution.
2 Percentage Volume of solute % by
Mole fraction by volume in ml present in volume
It is the ratio of the numbers of moles of solute (n1) (liquid in 100ml of dimension
or solvent (n2) to the total number of moles in the liquid) solution. less
solution.
3 Strength Mass of solute in
Let , n1 = no. of moles of solute (s) gm present in 1L gm L−1
n2 = no. of moles of solvent of solution.
n
mole fraction of solute, XA = 1 4 Molarity No.of Moles of mol L−1
n1 +n2
similarly, mole fraction of solvent is (M) solute present in or M
n2 1L of solution.
XB = n +n
1 2
5 Normality No.of gram gm eq L−1
(N) equivalent of or N
XA + XB = 1 solute present in
1L of solution.
Note:-
6 Molality No.of Moles of mol kg −1
❖ The sum of the mole fraction of all the (m) solute present in or m
components in solution is always equal to 1kg of solvent.
one.
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 7 Mole fraction Individual Moles
❖ 𝑁𝑜. 𝑜𝑓 𝑚𝑜𝑙𝑒 = 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 (X) of that component Dimension
divided by total less
moles of all the
Parts per million (PPM) components.
It is the number of parts of a component per million
parts of the solution. 8 Mass fraction Mass of that
Let us consider a component ‘A’ present in a component Dimension
solution. divided by total less
mass of component mass of all the
PPM of A = total mass of solution × 106 components.
9 Parts per Mass of that
Example:- million parts component in one PPM by
Calculate the PPM of chlorine, in one litre of by mass million parts of mass
public supply water contains 3 × 10−3 gm of (PPM) mass of all the
components.
chlorine solution.
3×10−3 10 Parts per Vol of that
PPM of chlorine = 1000 × 106
million parts component in 1 PPM by
= 3 PPM by volume million parts by volume
vi) Formality (F) (PPM) volume of all the
Formality is the number of formula mass of the components.
solute dissolved per litre of the solution. 11 Formality No. of gram
(for only formula masses
no.of formula mass of solute ionic species of the solute F
Formality =
volume of the solution in litre or present in 1L of
Note:- compounds) the solution.
Formality is used to express the concentration (F)
of ionic substances like NaCl, CuSO4 etc. because
these substances do not exist as distinct molecule.

Page 3
Relationship between Concentration terms:
(A) Solubility of a solid in a liquid
1. Relationship between volume & normality i.) When a solid-solute is added continuously to a
If V1 ml of solution of normality N1 react exactly liquid solvent, the solute keeps on dissolving & the
with V2 ml of solution of normality N2. Then we concentration of the solution keeps on increasing.
have This process is known as dissolution.
N1 V1 = N2 V2 ii.) At a stage, when no more solution dissolves at
This equation is called normality equation. the given temperature from the solution, due to the
solute particle keeps on colliding on the surface of
2. Relationship between volume & molarity the solute particle and get separated out from the
If V1 ml of solution of molarity M1 react solution. The process is known as crystallization.
exactly with V2 ml of solution of molarity M2. iii.) At dynamic equilibrium, no more solute
Then we have dissolves because the rate of dissolution becomes
M1 V1 = M2 V2 equal to the rate of crystallization.

This equation is called morality equation. Dissolution

solute + solvent ⇌ solution
3. Relationship between normality & molarity crystalization
Normality = molarity × basicity iv.) At the dynamic equilibrium point the solution
Or Normality = molarity × acidity becomes saturated.

4. Relationship between molarity(M) & molality(m) Factor affecting the solubility of a solid in liquid
molarity mass of solvent in kg The important factors on which the solubility of
= volume of solution in litre
molality a solid in a liquid depends are
i) Nature of the solute & solvent
mass of solution−mass of solute
= i.) A solid dissolve in a liquid which is chemically
volume of solution in litre
similar to it.
Density of solution Moles of solute ii.) We know that, “like dissolves like”, it means
( × )−( × )
volume of solution molar mass of solute that, the polar compounds are dissolved in polar
=
volume of solution in litre solvent and non-polar compound dissolved in non-
polar solvent.
5. If volume V1 ml of a solution of normality N1 is
mixed with V2 ml of a non-reacting solution of Example:-1.
normality N2, then final solution will have Polar compounds like NaCl are easily
normality dissolve in polar solvent like water & insoluble in
𝑁1 𝑉1 + 𝑁2 𝑉2
non-polar solvent like benzene.
N3 = Where V3 = V1+ V2 Example:-2
𝑉3
Similarly, Molarity will be A non-polar compounds like Naphthalene
are soluble in non-polar solvents like benzene but
M3 =
𝑀1 𝑉1 + 𝑀2 𝑉2
Where V3 = V1+ V2 insoluble in polar solvent like water.
𝑉3
ii) Effect of temperature on solubility
Solubility The solubility of the solid in a liquid solvent is
It is defined as the maximum amount of solute largely affected the temperature change.
that can be dissolved in a specific amount of Let us consider a dynamic equilibrium
solvent at a given temperature. condition which follows Le-Chatelier principle
OR arises two cases.
The solubility of a solid in a liquid at any Case-1
temperature is defined as the maximum amount of If the dissolution process is exothermic (i.e.
solid (solute) in grams. Which can dissolve in ∆H < 0), the solubility decreases with increase in
100gm of liquid (solvent) to form the saturated temperature.
solution at that particular temperature. Case-2
If the dissolution process is endothermic (i.e.
The solubility depends upon the nature of the ∆H > 0), then solubility increases with increase in
solute, solvent and also on temperature. temperature.

Page 4
iii) Effect of pressure on solubility Henry Law may be also stated as :-
Pressure does not have any significant effect on “The solubility of a gas in a liquid at a given
the solubility of solids in liquids. This is because temperature is directly proportional to the partial
solid and liquids are highly incompressible & pressure of the gas present above the surface of the
almost remained unaffected by change in pressure. liquid.”
Dalton during the same period had concluded
independently that, “if a mixture of gases are
B) Solubility of gas in a liquid simultaneously in equilibrium with the liquid at a
The solubility of any gas in a particular liquid is particular temperature, the solubility of any gas in
the volume of the gas in cubic centimeter that can mixture is directly proportional to partial pressure
dissolved in unit volume (1cc) of the liquid to form of that gas in mixture”.
the saturated solution at a temperature and under a Henry Law can be written as in terms of mole
pressure of one atm. fraction of the gas in solution as follows:-
Gas like HCl , SO2, NH3 etc. are highly soluble
in water. The solubility of gasses in liquid is XA = k1 PA …….. (ii)
largely affected by pressure and temperature.
Where, XA = mole fraction of gas
Factors affecting the solubility of a gas in a PA = partial pressure of the gas above the
liquid solution
The important factors on which the solubility of k1 = proportionality constant
a solid in a liquid depends are (Depends on temperature)

i) Nature of the gas & solvent 1

PA = k1 XA
Gases like Hydrogen, Oxygen, Nitrogen etc.
dissolved in water only a small extent whereas
gases like CO2, HCl, NH3 etc. are highly soluble.
Or PA = k H XA
The solubility of gas in a highly soluble the
chemical similarity between the gas & the solvent. 1
Where, k H = k1 & known as Henry constant.
ii) Effect of temperature
The solubility of a gas decreases with increase Henry Law can also be defined as, “The partial
in temperature because the dissolution of a gas in a pressure of the gas in vapour phase is directly
liquid is an exothermic process. proportional to the mole fraction of the gas in the
Gas + Solvent ⇌ Solution + Heat solution”.
Appling Le-Chatelier principle, with increase in
temperature in an exothermic reaction, the Limitation of Henry’s Law
equilibrium shift in the backward direction i.e. This law is applicable only if the following
solubility decreases. conditions are satisfied.
i) The pressure should be low and the temperature
iii) Effect of pressure (Henry’s Law) should be high i.e. the gas should be behave as an
The effect of pressure on the solubility of a gas ideal gas.
was studied by Henry’s Law. It state that, ii) The gas should not undergo compound
“The mass of a gas dissolved in a given volume of formation with solvent or dissociation with solvent.
liquid at constant temperature is directly
proportional to pressure of the gas present Application of Henry’s Law
equilibrium with liquid”. i) In the production of carbonated beverages to
Mathematically, increase the solubility of carbon dioxide in soft
m∝P drinks, Soda water etc. the bottle is sealed under
m = kP …… (i) high pressure, when the bottle is opened to air the
where, partial pressure of the solution decreases and hence
m = mass of the gas dissolved in a unit volume CO2 bubbles out.
of the solvent.
P = Pressure of the gas in equilibrium with ii) In the function of lungs, air when enters the
solvent. lung. Partial pressure of oxygen is high. The
k = constant of proportionality oxygen combines with hemoglobin; partial

Page 5
pressure of O2 in tissue is low. Hence O2 is If 𝑃 𝑠 is the vapour pressure of the solvent over a
released from oxyhemoglobin which is utilized for solution and 𝑋𝐴 is the mole fraction of solvent.
function of the cell. Then according to Raoult law
𝑃 𝑠 ∝ 𝑋𝐴
Vapour pressure Or 𝑃 𝑠 = 𝑃° 𝑋𝐴
The pressure exerted by the gas in equilibrium Where, 𝑃° = vapour pressure of the pure solvent.
with a solid or a liquid in a closed container at a The law can also be stated as the vapour
given temperature is called the vapour pressure. pressure of the solution is equal to the product of
the mole fraction of solvent and vapour pressure of
Factor affecting vapour pressure pure solvent at a particular temperature.
The vapour pressure of a liquid depends upon
the following factors. Hence,
i) Nature of liquid & ii) Temperature V. P of solution =
V. P. of pure solvent × mole fraction of solvent
i) Nature of liquid
Weaker are the intermolecular forces, greater is Ps = P° × XA
the amount of vapour because more molecules can Ps
leave the liquid & come into the vapour phase. Or = XA
P°
Ps
e.g. Diethyl ether having more vapour pressure Or 1 − P° = 1 − XA
than ethyl alcohol. P° −Ps
Or = Xsolute (∵ X solute + Xsolvent = 1)
P°
ii) Temperature
Higher the temperature greater is the vapour Here,
pressure because with increase in temperature, P ° − P s = lowering vapour pressure
kinetic energy of the molecules leaves the surface P° −Ps
= relative lowering vapour pressure
of the liquid and come into the vapour phase. P°
The change of vapour pressure with temperature
of a liquid is given by Clausius Clapeyron Raoult’s law can also be stated as :-
equation. “The relative lower in vapour pressure of a solution
containing non-volatile solute is always equal to
P ∆Hvap T −T the mole fraction of the solute in solution.”
log P2 = 2.303R [ T2 T 1 ]
1 1 2 If 𝑛1 is the number of moles of the solute & 𝑛2 is
the number of moles of the solvent in solution then,
Where,
P1 & P2 are the vapour pressure at temperature P° − Ps n1
at T1 & T2 respectively. °
=
P n1 + n2
∆Hvap is the enthalpy of vapourization of the
liquid.
Raoult’s law for containing volatile solute
Let the solution containing two miscible liquids A
Vapour pressure & Raoult’s Law & B having mole fraction X A & XB .
When a non-volatile solute is added to a solvent Let 𝑃𝐴° & 𝑃𝐵° is the vapour pressure of the liquid
its vapour pressure is lower. The quantitative in the pure state at a certain temperature.
relationship between vapour pressure of the According to Raoult’s Law:-
solution and the amount of the solute dissolved is V. P of component A in solution
given by Raoult’s Law. = V. P. of liquid at pure state
× mole fraction of A in solution
Raoult’s Law for solution containing non-
volatile solutes
PA = PA° × XA
“The vapour pressure of a solvent over a
Similarly,
solution containing non-volatile solute is directly
proportional to the mole fraction of the solvent at a PB = PB° × XB
particular temperature”.

Page 6
Raoult’s Law for volatile solute can be stated as For ideal solution: -
“In a solution containing volatile solute, the i) ∆Vmix = 0
vapour pressure of a component at a given ii) ∆Hmix = 0
temperature is equal to the product of mole iii) PA = PA° × XA & PB = PB° × XB
fraction in solution & vapour pressure of the pure Where, PA & PB are vapour pressure of
state”. component A & B respectively.
e.g. Mixture of benzene & toluene
Ideal and Non-Ideal Solutions
(b) Non-ideal Solution: A solution which does not
(a.) Ideal Solution: A solution is called an ideal obey Raoult’s law for all concentration is called a
solution if it obeys Raoult’s law over a wide range non-ideal solution.
of concentration at a specific temperature. For non-ideal solution
P = PA +PB i) ∆Vmix ≠ 0
ii) ∆Hmix ≠ 0
= P°A XA+ P°B XB iii) PA ≠ PA° ∙ XA & PB ≠ PB° ∙ XB
e.g. Mixture benzene & Acetone.
Liquids having similar nature and structure are A non-ideal solution can show either positive or
likely to form ideal solutions. negative deviation from Raoult’s law
Examples are:
i. Positive Deviation:
• Mixture of methanol and ethanol
• Mixture of n-hexane and n-heptane
• Mixture of benzene and toluene

The deviation will be called positive when the

partial pressure of each component and the
resultant total pressure are greater than the pressure
expected on the basis of Raoult’s law.
Reason for formation of ideal solution:
In such cases, the intermolecular forces between
A solution of two miscible liquids A and B will be solvent-solute molecules (FA-B) are weaker than
ideal if two essential conditions are fulfilled. those between solvent-solvent (FA-A) and solute-
solute (FB-B) molecules
i. If FA-A is the force of attraction between i.e FA-B < FA-A & FB-B
molecules of A and FB-B is that of molecule of B, This shows that the molecules of A or B will
then A and B will form an ideal solution only if, escape more easily from the surface of the solution,
i.e, the vapour pressure of solution will be higher.
FA-B = FA-A = FB-B
ii. The solution of A and B liquids will be ideal if For positive deviation
A and B have similar structure and polarity. i) ∆Vmix > 0
ii) ∆Hmix > 0
Example : iii) PA > PA° ∙ XA & PB > PB° ∙ XB
Methanol and ethanol have the same functional Examples:
group and almost same polarity and therefore, form • Ethyl alcohol and water
ideal solution. • Acetone and Carbon disulphide

Page 7
 • Carbon tetrachloride and benzene Boiling point
• Acetone and Benzene The temperature at which the vapour pressure
of the liquid is equal to the atmospheric pressure is
ii. Negative Deviation: called the boiling of the liquid.
At this temperature both the liquids & vapour
co-exist. The greater is the vapour pressure of a
liquid at a given temperature lesser will be its
boiling point.
e.g. The vapour pressure of CCl4 is more than
that of water at 333K. Therefore, boiling point of
CCl4 is less than that of water.

Freezing point
The temperature at which the solid & liquid
state of the substance have the same vapour
pressure.

Colligative properties of dilute solutions

“The properties of the dilute solution which
The deviation is called negative deviation, if the depends upon the number of particles (molecules
partial pressure of each component (A and B) and or ions) of solute in solution are called colligative
resultant total vapour pressure are less than the properties”.
pressure expected on the basis of Raoult’s Law. The important colligative properties are
This type of deviation is shown by the solution i) Relative lowering in vapour pressure
in which ii) Elevation in boiling point.
FA-B >FA-A & FB-B iii) Depression in freezing point
Due to this, there is decrease in the escaping iv) Osmotic pressure.
tendency of A & B molecules from the surface of If two solutions contain equal number of
solution. i.e the vapour pressure of the solution will particles A & B, then the two solutions will have
be lower. same colligative properties irrespective of nature of
the A & B.
For negative deviation The colligative properties are useful to determine
i) ∆Vmix < 0 the molecular masses of the non-volatile solutes &
ii) ∆Hmix < 0 also helps to determine the degree of dissociation
iii) PA < PA° ∙ XA & PB < PB° ∙ XB or association of electrolyte in solutions.
Examples:
• HNO3 and Water i) Relative lowering in vapour pressure
• Chloroform and Acetone According to Raoult’s Law the relative lowering
in vapour pressure of a solution is equal to the mole
• Acetic acid and Pyridine
fraction of the solute.
• Hydrochloric acid and Water
We know that, P s = P ° × Xsolvent
Where,
Azeotropic Mixture or Azeotropes
P s = V.P. of solution
Mixture of liquids which boils at constant
temperature like a pure liquid such that the P ° = V.P. of pure solvent
distillate has the same composition as that of liquid Xsolvent = mole fraction of solvent
mixture are called azeotropic mixture or Ps
azeotropes. Or = Xsolvent
P°
Ps
Or 1 − P° = 1 − Xsolvent
Note :
In Greek word azeotropes means “to boil
P° −Ps
unchanged”. Or = Xsolute …… (i)
P°

From the above expression,

P ° − P s = lower in vapour pressure

Page 8
 Reason for elevation in boiling point
P° −Ps
= relative lower in vapour pressure We know that, the vapour pressure of a solution
P°
The relative lowering in vapour pressure is containing non-volatile solute is less than that of
equal to the mole fraction of the solute. pure solvent at each temperature.
The vapour pressure of the solution will be
Determination of molecular mass from relative equal to that of pure solvent at a higher
lowering vapour pressure temperature. So, that it may start boiling. This is
Let, n be the number of moles of the solute the reason due to which boiling point of a solution
dissolved in N moles of solvent. The mole fraction is higher than that of pure solvent.
of the solute is
Boiling point vapour pressure graph
n On plotting a graph between vapour pressure
Xsolute = n+N ………. (ii)
and temperature for a pure solvent & a solution, the
following curves are obtained.
If ‘w’ gm of non-volatile solute having molecular
mass ‘m’ be dissolved in ‘W’gm of solvent having
molecular mass ‘M’ then,
w W
n=m & N= M

Substituting the value of the n and N in equation

(ii) we get
𝑤

Xsolute = 𝑚
w W ……… (iii)
+
m M

From equation (i) and (iii) we get From the above curves the vapour pressure of a
𝑤
solvent at any temperature is more than of the
P° −Ps solution. So, that the boiling point of the solution
= 𝑚
w W …….. (iv)
P° + will be higher than that of pure solvent.
m M
Form the curve the boiling point of the solution
If the solution is very diluted
𝑤
can be neglect is 𝑇2 and that of pure solvent is 𝑇1 .
𝑚
from the denominator. ∴ elevation in boiling point (∆Tb ) is,
𝑤
P° − Ps 𝑚 ∆Tb =T2 -T1
=
P° 𝑊 It has been found that the elevation in boiling
𝑀
point is directly in proportional to the molality of
P° −Ps w.M the solute.
Or = W∙m ∆Tb ∝m'
P°
Or ∆Tb =k b m'
If all other factors are known, the molecular
mass of the non-volatile solute (m) can be Where, 𝑚′ = molality of the solution.
calculated. 𝑘𝑏 = molal elevation constant or it is called as
Here, the relative lowering in vapour pressure ebullioscopic constant.
depends upon the number of solute particles and Molal elevation constant is define as the elevation
not on their nature. So, it is a colligative property. in boiling point when, 1 mole of non-volatile solute
is dissolved in 1000 gm of solvent.
Elevation in boiling point
i.) Boiling point of a liquid is defined as the Derivation of ∆𝐓𝐛 = 𝐤 𝐛 𝐦′
temperature at which its vapour pressure becomes We know that greater the lowering in the vapour
equal to atmosphere pressure. pressure higher is the elevation in boiling point.
ii.) Boiling point of a solution is always more than Thus, ∆Tb ∝∆P ……… (i)
of its pure solvent. (∵∆P=P ° -P s )

Page 9
But, According to Raoult’s Law From this relation we concluded the elevation
P ° -P s ∝Xsolute in boiling point of dilute solution is directly
proportional to the number of moles of solute
Or, ∆P∝Xsolute ……. (ii) dissolved in given mass of solvent so elevation in
boiling point is colligative property.
From equation (i) & (ii) we get,
∆Tb ∝ Xsolute Depression in freezing point
Freezing point is defined as the temperature
Or ∆Tb = k . Xsolute ………. (iii) at which both solid & liquid co-exists and have the
same vapour pressure. Freezing point of a solution
Where, k is constant of proportionality. is always less than that of its pure solvent.
Also, we know that,
n
Xsolute = n+N Reason for depression in freezing point
Where, n = no. of moles of non volatile solute. The vapour pressure of a solution is less than
N= no.of moles of solvent in solution that of a pure solvent at each temperature. It means
For dilute solution, that the vapour pressure of solution becomes equal
n to the pure solid solvent only at lower temperature.
X solute = N
n So that it may starts freezing. Thus, the freezing
Or, Xsolute = W/M point of solution is less than that of its pure solvent.
n
Or, Xsolute = M ∙ W ……. (iv) Freezing point-vapour pressure relationship
If a graph is plotted between the different
value of temperature and the corresponding vapour
Where, W = amount of solvent
pressure of the pure solvent we get, the following
M = molecular mass of solvent
graphs.
Substituting the value of Xsolute equation (iii)
we get
n
∆Tb = k . M ∙
W
𝑛
If W = 1000 gm them 𝑊 is known as molality
′
(𝑚 ) of solution.

Now, equation (iv) becomes

∆𝑇𝑏 = 𝑘 ∙ 𝑀 ∙ 𝑚′
Or, ∆𝑇𝑏 = 𝑘𝑏 ∙ 𝑚′ ………. (v)
Where,
𝑘𝑏 = 𝑘 ∙ 𝑀 (for a given solvent ‘M’ is constant)
From the above graph T0 is the freezing point
of the pure liquid & T is the freezing point of the
Calculation for molality (𝒎′ ) solution. Clearly, we can see that, the freezing
Let, w gm of non-volatile solute (m) is dissolved in
point of the solution is less than that of liquid.
‘W’gm of solvent, then,
𝑤 Therefore, depression in freezing point
‘W’gm of solvent contain = 𝑚 solute (∆Tb ) = T0 − T
Experimentally found that,
𝑤
1gm of solvent contain = ∆𝑇𝑓 ∝ 𝑀′
𝑚×𝑊
′
𝑤×1000
1000gm of solvent contain = 𝑚×𝑊 = 𝑚′ Where, 𝑀 = molality of the solution
𝑘𝑓 = molal depression constant or molal
Substituting the value of 𝑚′ in equation (v) we get,
cryoscopic constant.
w×1000 The molal depression constant is define as the
∆Tb = k b ∙ depression in freezing point when one mole of the
m∙W
non-volatile solute is dissolved in 1000gm of the
1000×w×kb solvent.
∴ molecular mass of solute (m) = ∆Tb ×W

Page 10
Determination of molecular mass of a Law of osmotic pressure
solute from ∆𝑻𝒇 Van’t Hoff’s in 1886 was able to show that
We know that, there was a close similarity between pressure
∆𝑇𝑓 = 𝑚′ ∙ 𝑘𝑓 …….. (i) exerted by a gas & the osmotic pressure developed
𝑤×1000 by the dilute solution. He was explained few laws
But, 𝑚′ = by the help of Boyle’s Law & Charle’s Law which
𝑚×𝑊
are as follows.
Where, w = mass of solute
W = mass of solvent Boyle’s Van’t Hoff Law (Effect of conc. On
m =molecular mass of solute osmotic pressure)
It is state that, “At constant temperature the
Substituting the value of 𝑚′ in equation (i) we get, osmotic pressure (𝜋) of a dilute solution is directly
proportional to the concentration of the solution”.
𝑤×1000
∆𝑇𝑓 = × 𝑘𝑓
𝑚×𝑊
𝑤×1000×𝑘𝑓 Mathematically,
Molecular mass (m) = 𝜋 ∝ 𝑐 ( at constant ‘T’)
∆𝑇𝑓 ∙𝑊
𝜋
Or 𝑐 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ……… (i)
𝑤×1000×𝑘𝑓
Or 𝑚= If one mole of solute dissolved in ‘v’ litre of the
∆𝑇𝑓 ∙𝑊
solution then,
1
𝑐=𝑣
Osmosis 1
It is defined as the spontaneous flow of the ∴ 𝜋∝𝑣
solvent molecule towards the solution side when Or 𝜋𝑣 = constant
both are separated by semipermeable membrane.
OR This equation is similar to that of Boyle’s
it is the flow of the solvent molecule to the solution law for gases. Hence Boyle’s Vant Hoff Law may
of higher concentration where both are separated also state as “At constant temperature the osmotic
by a semipermeable membrane. pressure of a dilute solution is inversely
proportional to the volume of the solution
Note containing one mole of solute dissolve in it”.
Semipermeable membrane
It is a thin layer which permits the passage of Charl’s Van’t Hoff Law (Effect of temp. on
only one type of molecule generally the solvent. osmotic pressure)
Osmotic pressure It states that, “At constant concentration, the
The excess pressure exerted on solution site osmotic pressure of a dilute solution is directly
which just prevent the flow of the solvent molecule proportional to the absolute temperature”.
towards solution site is called osmotic pressure. It
is represented as ‘𝜋’. Mathematically,
𝜋 ∝ 𝑇 ……. (ii)
Isotonic solution 𝜋
Or 𝑇 = constant
A pair of solution having same osmotic
pressure which produce no flow of solvent Van’t Hoff theory for dilute solution
molecule through the semipermeable membrane According to Boyle’s Van’t Hoff Law,
called isotonic solution. 𝜋 ∝ 𝑐 …… (i) (T is constant)
Hypotonic solution According to Charl’s Van’t Hoff Law,
It is a solution whose osmotic pressure is 𝜋 ∝ 𝑇 …… (ii) (constant conc.)
lower than that of other solution. It is hypotonic Combining equation (i) & (ii) we get ,
with respect to the other solution. 𝜋 ∝ 𝑐𝑇
Hypertonic solution Or 𝜋 = 𝑐𝑅𝑇 ………. (iii)
It is a solution whose osmotic pressure is We know that,
higher than that of other solution. It is hypotonic 𝑐 = 𝑛⁄𝑣
with respect to the other solution.
Equation (iii) becomes, 𝜋 = 𝑛⁄𝑣 𝑅𝑇

Page 11
 iii) Reverse osmosis
Or 𝜋𝑣 = 𝑛𝑅𝑇 When a pressure higher than the osmotic
pressure is applied to the solution, the solvent from
Where, R is the proportionality constant, the solution starts flowing towards the pure solvent.
If w gm of a non-volatile solute having molecular The process is called reverse osmosis.
mass ‘m’ be dissolve in ‘v’ lit of solution. e.g. purification of pure water from sea water.
Then, 𝑛 = 𝑤⁄𝑚
Application of reverse osmosis
Thus, In the given figure sea water is separated from
𝑤
𝜋𝑣 = 𝑚 𝑅𝑇 pure water by a semi-permeable membrane. The
semipermeable membrane is made up of with
𝑤𝑅𝑇 cellulose acetate, which is allowed to pass water
or 𝜋= 𝑚𝑣 through it. But is not-permeable to impurities and
other ion present in sea water. When pressure is
apply more than the osmotic pressure through
𝑤𝑅𝑇
or 𝑚= piston the pure water molecule are passed through
𝜋𝑣
the semipermeable membrane & pure water are
collected from the water outlet.
Van’t Hoff Avogadro’s law for solution
It states that, “Equal volume of all solutions
having the same osmotic pressure and temperature
contains the same no. of particle”.
e.g. 1 litre solution of 1 M glucose & 1 M
sucrose having 6.02 × 1023 molecules where their
osmotic pressure are equal.

Osmotic pressure is a colligative property

For dilute solution, the Van’t Hoff equation is,
𝑛
𝜋 = 𝑉 𝑅𝑇
From the above relation, it is cleared that, the
osmotic pressure of a dilute solution at a given
temperature T is directly proportional to the molar
concentration.
i.e. the osmotic pressure depend upon the no. Abnormal colligative properties
of moles of solute present in solution. Hence, The value of colligative properties of solution
osmotic pressure is a colligative property. of electrolyte obtain from experiment, are generally
higher than those calculated from their
Types of osmosis stochiometric molarity or molality.
i) Exo-osmosis This is because an electrolyte dissociates into
Outward osmotic flow of water from a cell ions in an aqueous solution and this increases the
containing an aqueous solution through a no. of solute particles in the solution. The
semi-permeable membrane (SPM). colligative properties are depending upon the no. of
e.g. after removing hard cell of an egg placed in solute particle but here experimental and
NaCl solution is called exo-osmosis. theoretical values are different therefore,
colligative properties are showing abnormal
ii) Endo-osmosis behavior.
The inward flow of water into a shell contains To explain the abnormal behavior of salt
an aqueous solution through a semi-permeable Van’t Hoff introduce a factor called as Van’t Hoff
membrane. factor in his equation.
e.g. An egg placed in a water called endosmosis. Thus, π = i cRT.

Page 12
Van’t Hoff factor (i) For normal behavior (no-association)
It is defined as the ratio of the experimental The number of moles would have been 1M.
value of a colligative property to the calculated or since the colligative properties is proportional to
theoretical value of colligative properties. the number of particles and the numbers of
particles are proportional to number of moles.
𝑖=
experimental value of the colligative property Van’t Hoff factor (i)
calculated value of the colligative property 𝑜𝑏𝑠𝑒𝑟𝑣𝑒𝑑 𝑐𝑜𝑙𝑙𝑖𝑔𝑎𝑡𝑖𝑣𝑒 𝑒𝑓𝑓𝑒𝑐𝑡
= 𝑛𝑜𝑟𝑚𝑎𝑙 𝑐𝑜𝑙𝑙𝑖𝑔𝑎𝑡𝑖𝑣𝑒 𝑒𝑓𝑓𝑒𝑐𝑡
no.of particles after dissociation 1−∝+∝⁄𝑛
or, 𝑖 = Or 𝑖=
no.of solute molecule taken 1
1
⇒ 𝑖 = 1 − 𝛼 (1 − 𝑛)
The molecular mass is inversely proportional to 1
the colligative property. ⇒ 1 − 𝑖 = 𝛼 (1 − 𝑛)
1−𝑖
The Van’t Hoff factor (i) can be express as ⇒ 𝛼 = 1−1⁄
𝑛

theoretical molecular mass 1−𝑖

𝑖= ⇒ 𝛼 = 1−1⁄ ……. (i)
experimental molecular mass 𝑛

(∆Tb )obs
Thus, 𝑖 = Also,
(∆Tb )cal 𝑀𝑜𝑏𝑠−𝑀𝑛𝑜𝑟 𝑛
⇒ 𝛼 = 𝑀𝑜𝑏𝑠 × 𝑛−1
(∆Tf )obs
𝑖= ii) Degree of dissociation
(∆Tf )cal
∆P It is defined as the fraction of the total number
( ° ) obs of molecules which dissolves into ions.
i = P
∆P Consider that ‘A’ molecule dissociated into “n”
( ° ) cal
P no. of particles.
π obs
𝑖 = πcal
Mcal 𝐴 ⟶ 𝐵 + 𝐶 + 𝐷 + ………
i = ( 1−∝) (𝑛 ∝)
Mobs
No. of particles degree dissociation = 1 mole
In case of association,
Mobs > Mcal
In case of dissociation, No. of particle after dissociation
Mobs < Mcal = 1−∝ +𝑛 ∝
= 1+∝ (𝑛 − 1)
Application of Van’t Hoff factor (i) Van’t Hoff factor(i)
no.of particles after dissociation
Van’t Hoff factor (i) can be used to calculate = no.of particle before dissociation
the degree of association and degree of
dissociation. 1+∝(𝑛−1)
=
i) Degree of association 1
It is defined as the fraction of total no. molecule
which combines to form associated molecule. Degree of dissociation (∝) is ,
Let us consider 1 mole of a solute A dissolved in 𝑖 = 1+∝ (𝑛 − 1)
a definite volume of solvent. ∝ (𝑛 − 1) = 𝑖 − 1
‘n’ molecules solute ‘A’ combines to form the
𝑖−1
associated molecule (An). According to the reaction ∝= 𝑛−1
let the degree of association is ∝.
𝑛𝐴 ⇌ (𝐴)𝑛
1−∝ ∝⁄ 𝑀𝑛𝑜𝑟−𝑀𝑜𝑏𝑠 𝑛
𝑛 Or, ∝= ×
The no. of associated moles is equal to ∝⁄𝑛 𝑀𝑜𝑏𝑠 𝑛−1
The no. of un associated moles is (1−∝)
Total no. of moles in the solution is 1−∝ + ∝⁄𝑛 *****

Page 13