Solutions

Solution is a homogeneous mixture of two or more substances in same or different

physical phases. The substances forming the solution are called components of the
solution.
On the basis of number of components a solution of two components is called
binary solution.
The two components ofbinary solution are,
a) solute : - ➔It is present in smaller quantity.
b) solvent: - ➔ It is the component which is present in large quantity

Types of solutions:-
a) On the basis of physical state of solute and solvent

Type of Solution Solute Solvent Common Examples

Gaseous Solutions Gas Gas Mixture of oxygen and nitrogen gases
liquid Gas Liquid Gas Chloroform mixed with nitrogen gas.
solid Gas Solid Gas Camphor in nitrogen gas
Liquid Solutions Gas liquid Oxygen dissolved in water
liquid liquid Liquid Liquid Ethanol dissolved in water
solid liquid Solid Liquid Glucose dissolved in water
Solid Solutions Gas solid Solution of hydrogen in palladium
liquid solid Liquid Solid Amalgam of mercury with sodium
solid solid Solid Copper dissolved in gold

(b) Depending upon the amount of solute dissolved in a solvent:-

Solutions are classified as,
➢ (i) Unsaturated solution: -
“A solution in which more solute can be dissolved without raising temperature is
called an unsaturated solution”.
➢ (ii) Saturated solution: -
“A solution in which no solute can be dissolved further at a given temperature is
called a saturated solution”.
➢ (iii) Supersaturated solution: -
“A solution which contains more solute than that would be necessary to saturate it
at a given temperature is called a supersaturated solution”.
Concentration of Solutions
“The concentration of a solution is defined as the relative amount of solute present
in a solution”.
On the basis of concentration of solution there are two types of solutions.
(i) Dilute solution and (ii) Concentrated solution
Concentration of Solutions is expressed as
1) Mass percentage or percentage by weight(w/w% mass): -
2) Weight –volume percentage(% w/v): -
3) Volume percentage(% v/v): -
4) Molarity [M]: -
5) Normaity [N]: -
6) Molality [m]: -
7) Mole fraction [𝝌]: -
8) Formality [F]: -
9) Parts per million[ppm]:-

Concentration of Solutions is expressed as

1)Mass percentage or percentage by weight(w/w% mass): -
“It is defined as the amount of solute present in 100 g of solution”.
Or
“It is defined as the number of parts by mass of the solute per 100g mass of
the solution”
weight of solute
w/w%= x100
weight of solution
or
𝐖𝐁
mass percentage of solute = x100 ; { 𝐖𝐁 → mass of solute ; 𝐖𝐀 → mass
𝐖𝐀 +𝐖𝐁
of solvent}
Weight –volume percentage(% w/v): -
“It is defined as the weight of solute present in 100 mL of solution”.
or
“It is defined as the number of parts by mass of the solute per 100 parts by
volume of the solution”
weight of solute
w/V%= x100 ;
Volume of solution
or
W
w/V% = x 100
V

Volume percentage(% v/v): -

“It is defined as the volume of solute present in 100 mL of solution.”
Or
“It is defined as the number of parts by volume of the solute per 100 parts by
volume of the solution”
volume of solute
v/V%= x 100 ; or
volume of solution
𝐯𝐁
v/V% = x 100
𝐯𝐀 +𝐯𝐁
Molarity [M]: -
“It is the number of moles of solute present in 1L(dm3) of the solution.
number of moles of solute n
M= =
volume of solution (L) V(L)
mass of solute (in gram) x 1000 wx 1000
M= = ➔ Mol L-1 (unit)
mol. wt. of solute x volume of solution (in mL) GMW x V(in mL)

➢ Molarity varies with temperature due to change in volume of solution.

➢ {When molarity of a solution is 1 M, it is called a molar solution.
➢ 0.1 M solution is called a decimolar solution, while
➢ 0.5 M solution is known as semi molar solution}
Percent by mass x density x 10
➢ Molarity =
molecular weight

Normality [N]: -

“Number of gram equivalent of a substance present in one litre of the

solution”
number of grams equivalent of solute n
Normality = =
volume of solution in L v( in L)

w 1
N= x w→ weight of the solute ; GEW → gram equivalent
GEW v( in L)
weight

w 1000
Or N= x ➔ unit→ g-equivalent L-1
GEW v( in L)

{Normality depends on temperature.}

mass of solute in gram
Number of gram-equivalents of solute = .
equivalent weight
Molality [m]: -
“It is the number of moles of solute per kilogram of the solvent”.
number of moles of solute n
Molality = =
mass of solvent (in kg) w( in kg)
w 1
m = GEW x v( in L) w→ weight of the solute; GEW → gram equivalent weight
w 1 w
Or m= x ➔ unit→ g-equivalent L-1 [∵ n= ]
GEW w( in kg) GEW

w→ weight of the solute ; GEW → gram equivalent weight ;w= weight of the solvent
{molality is independent of temperature.}
When solvent used is water, a molar (1 M) solution is more concentrated than a molal(1 M)
solution.
Mole fraction [𝝌]: -
“It is the ratio of number of moles of the given component to the total number of
moles of the solution”
If, A➔ solvent and B➔ solute Then,
𝒏𝐵
mole fraction of the solute=𝝌B =
𝒏𝐴 +𝒏𝐵
𝒏𝐴
mole fraction of the solvent=𝝌A =
𝒏𝐴 +𝒏𝐵
Sum of the mole fraction of solute and solvent in a binary solution is unity.
𝛘A + 𝛘B =1.
{Mole fraction is independent of temperature.}
Formality [F]: -
“It is defined as the number of gram molecular masses(moles) of ionic solute present in
one litre of the solution”
𝐰 𝟏𝟎𝟎𝟎
F= x
𝐆𝐅𝐖 𝐕(𝐢𝐧 𝐦𝐋)
W➔ weight of solute ; GFW➔ gram formula weight; V➔ volume of the solution.

Parts per million[ppm]:-

“It is defined as the number of parts by mass of the solute per million (106) parts by mass
of the solution.”
𝐖𝐁
ppm= 𝐖 +𝐖 x 106; {WB → Weight of the solute; WA → Weight of the solvent}.
𝐀 𝐁
Classification of solution based on quantity of solute dissolved in it

i) Unsaturated solution: - (ii) Saturated solution (iii) Supersaturated solution

“A solution in which some more “A solution in which no “A solution which contains more
solute can be dissolved without solute can be dissolved solute than that would be
raising temperature is called an further at a given necessary to saturate it at a
unsaturated solution”. temperature is called a given temperature is called a
saturated solution supersaturated solution”.
amount of solute <solvent in Amount of solute =solvent amount of solute > solvent in
dissolved state at a given in dissolved state at a given dissolved state at a given
temperature. temperature. temperature.

∴ Rate of dissolution of solute > ∴ Rate of dissolution of ∴ Rate of dissolution of solute

Rate of precipitation solute = Rate of precipitation < Rate of precipitation Or Vice-
versa.

Solubility: -
“it is defined as the maximum amount of the solute that can be completely dissolved in
specified amount of solvent at a given temperature.”
Ex:
At 20℃, the maximum amount of NaCl (common salt) that can be dissolved in one liter of
water is 23g.
Solubility expression: -
1) Number of grams of solute in 100mL of solvent at a given temperature.
2) g/L→ maximum number of grams of solute dissolved in one liter of the solution at a
given temperature.
3) Mol/L → maximum number of moles of solute dissolved in one liter of the solution
at a given temperature.
4) Mole fraction of solute in solution → convenient for expressing solubility of gases in
liquids.

Reason for solubility of solid in liquid: -

solubility of solid in liquid occurs when,
Solute – solvent interaction > solute - solute interaction.
a) Ionic solids: -
Ionic solids dissolution ➔ due to hydration of ions {oppositely charged ends of the ions are
attracted by dipoles of water molecules.}
➔hydration of ions is an exothermic process {it supplies energy to
dissolution of the lattice and is given by the expression}
 𝚫sol H = 𝚫L H + 𝚫hydH

Δsol H → dissolution enthalpy or enthalpy of solution

ΔL H → lattice dissolution enthalpy.(+ve)
ΔhydH →enthalpy of hydration(-ve)

For dissolution of salts,

𝚫hydH ≥ 𝚫L H ⇒ 𝚫solH –ve ⇒ dissolution takes place
𝚫hydH is lightly > 𝚫L H ⇒ 𝚫solH +ve ⇒ dissolution takes place
𝚫hydH is much much > 𝚫L H ⇒ 𝚫solH –ve ⇒ dissolution does not takes place
b) Molecular solids: -
They do not ionize, solubility is due to intermolecular hydrogen bonding with water
molecules.
Factors affecting solubility of a solute in a liquid: -
(i) Nature of the solute
(ii) Nature of the solvent
(iii) Temperature of the solution
(iv) Pressure (in case of gases)
(i) Nature of the solute
➢ Polar solutes like NaCl, KNO3,CuSO4
Soluble→polar solvents (water) and Insoluble → nonpolar solvent(Benzene,CCl4).
➢ Non Polar solutes like I2, S8
Highly Soluble →non polar solvents (Benzene,CCl4) and Insoluble → polar solvent(water).
➢ molecular solids:- like glucose, sugar, urea etc.
Highly Soluble in water due to formation of hydrogen bonding.
Temperature
Effect of temperature on solubility of solids in liquid depends on nature of process.
➢ For exothermic dissolution of solids: ∆H = -ve.
𝒅𝒊𝒔𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏
Solute + Solvent ⇌ solution ; ∆H = -ve.
Increase in temperature shifts equilibrium to endothermic(backward) direction.
⇒ Solubility decreases with increase in temperature.
➢ For endothermic dissolution of solids: ∆H = +ve.
𝒅𝒊𝒔𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏
Solute + Solvent ⇌ solution ; ∆H = +ve.
Increase in temperature shifts equilibrium to (forward) direction.
{⇒ Solubility decreases with increase in temperature.}
Henry’s Law [Solubility of gas in liquid]

“The partial pressure (P) of the gas in vapor phase is proportional to the mole fraction (𝝌)
of the gas in the solution”.
and is expressed as,

p
p∝𝝌 or p = KH . 𝝌 or KH =
𝝌

‘P’ denotes the partial pressure of the gas in the atmosphere above the liquid.
‘C’ denotes the concentration of the dissolved gas.
‘kH’ is the Henry’s law constant of the gas.

Greater the value of KH, higher the solubility of the gas.

The value of KH decreases with increase in the temperature.

Ex: KH of CO2 = 1.67 k bar; KH of O2 = 47kbar

⇒ CO2 is more soluble than O2 water.

Thus, aquatic species are more comfortable in cold water [more dissolved O 2] rather than
Warm water.

Applications
1. In manufacture of soft drinks and soda water, CO2 is passed at high pressure to
increase its solubility.
2. To minimize the painful effects (bends) accompanying the decompression of deep sea
divers O2 is diluted with less soluble Helium (11.7% helium, 56.2% nitrogen and 32.1%
oxygen) gas is used as breathing gas.
3. At high altitudes, the partial pressure of O2 is less than that at the ground level. This
leads to low concentrations of O2 in the blood of climbers which causes “anoxia.”
Characteristics of KH :-
1) As mole fraction has no unit, Henry’s law constant has the same unit as pressure ie..
Torr or kbar.
2) Value of KH is different for different solvent.
3) Value of KH increases with increase in temperature.
4) As temperature increases solubility decreases but KH increases.
Higher the value of KH lower is the solubility.
Limitations:-
Not applicable at,
1) too low temperature.
2) at high temperature.
3) when no chemical reaction (ie.. No interaction) takes place between solute and
solvent molecules.
4) No dissociation of solute in solution takes place.

Solution of liquid in liquid :-

Here since both are liquid vapour pressure of solution depends on both the
components(solute and solvent).
According to Daltons law of partial pressure
Total vapour pressure is the sum of the partial pressure of solute and solvent it is given by
p =pA0+ pB0
Hence, vapour pressure of liquid – liquid solution is given by Raoult’s law.

Raoult’s Law
The Raoult’s law states that,
“For a solution of two volatile liquids, the vapour pressure of each components of a
solution is directly proportional to its mole fraction.”
If A and B are two components
pA and pB are the partial vapor pressure of liquid A and B respectively
Then, pA ∝ 𝝌A
or pA = 𝒑𝟎𝑨 . 𝝌A {P𝑨∘ , the vapour pressure of solvent in pure liquid}
and
pB ∝ 𝝌B
or pB = 𝒑𝟎𝑩 .𝝌B {P∘𝑩 , the vapour pressure of solute in pure liquid}
According to Daltons law of partial pressure,
Total vapour pressure is the sum of the partial pressure of solution(solute and solvent)
It is given by ,
p =pA0+ pB0 .
Total vapour pressure of the solution,
pT = p = pA + pB ;
= p∘𝐀 𝛘A + p∘𝐁 𝛘B {Since , 𝛘A + 𝛘B = 1⇒ 𝛘A =1- 𝛘B and ⇒ 𝛘A =1- 𝛘B }
p = p∘𝐀 (1- 𝛘B ) + p∘𝐁 𝛘B
= p∘𝐀 - p∘𝐀 𝛘B + p∘𝐁 𝛘B
= p∘𝐀 − (p∘𝐁 -p∘𝐀 ) 𝛘B
p = (p∘𝐁-p∘A ) 𝛘B + p∘A
In terms of mole fraction of A,
p = (p∘𝐀-p∘B ) 𝛘A + p∘B .
Ideal Solution Non-ideal Solutions
(i) Solution must obey Raoult’s law. Those solutions which shows deviation from
pA = 𝒑𝟎𝑨 . 𝝌A ; pB = 𝒑𝟎𝑩 .𝝌B Raoult’s law is called non-ideal solution; pA ≠
𝒑𝟎𝑨 . 𝝌A ; pB≠ 𝒑𝟎𝑩 .𝝌B
pA > 𝒑𝟎𝑨 . 𝝌A ; pB > 𝒑𝟎𝑩 . 𝝌B → +Ve deviation
pA < 𝒑𝟎𝑨 . 𝝌A ; pB < 𝒑𝟎𝑩 . 𝝌B ; → -Ve deviation
(ii) ΔHmix = 0 (No energy evolved or absorbed) ΔHmix ≠ 0; ΔHmix > 0; +ve deviation
ΔHmix < 0; -ve deviation
(iii) ΔVmix = 0 (No expansion or contraction on ΔVmix ≠ 0; ΔVmix > 0; +ve deviation
mixing) ΔVmix < 0; -ve deviation
(iv) Identical molecular size must exit between There should be decrease or increase in
solvent and solute. molecular interaction.
Lower the concentration more ideal is the +ve deviation→breaking due to weakening of
solution will be. interaction
- ve deviation→if association takes place
e.g. benzene + toluene.(C6H6+C6H5CH3) Acetone+ Chlorofrom(CH3COOH+CHCl3)
n-hexane + nheptane, .(N-C6H12+N-C7H14) Diethylether+ Chlorofrom(C2H5OC2H5+CHCl3)
ethyl iodide + ethyl bromide, .(C2H5I+C2H5Br) Benzene+ Chlorofrom(C2H5OH+CHCl3)
chlorobenzene + bromobenzene. Acetic acid + Pyridine(CH3COOH + C6H5N)
.(C6H5Cl+C6H5Br) Water a+ Nitric acid(H2O + HNO3 )

Temp Temp
colligative properties
“The properties of dilute solutions of non-volatile solutes whose value depends only on
the number of solute particles, but not on the nature or total number of particles is called
colligative properties.”

Types of colligative properties: -

1) Relative lowering of vapour pressure(RLVP).
2) Elevation in boiling point(𝜟Tb) .
3) Depression in freezing point(𝜟Tf) .
4) Osmotic pressure (𝝅)

Applications of colligative properties: -

Determination of colligative properties of solid-liquid solution.
1) Helps to calculate molecular mass of non-volatile solute in unknown solution.
2) Determination of molecular formula.

Relative lowering of vapour pressure(RLVP): -

“It is defined as the ratio between the lowering of vapour pressure to the
vapour pressure of the pure solvent in solid-liquid solution.”
𝒑𝟎 −𝒑
given by→ = 𝝌𝑩
𝒑𝟎

The above expression shows that RLVP depends only on mole fraction of solute
and not on its nature, hence it is a colligative property.

Calculation of molar mass of the solute from RLVP: -

In a dilute solution, WB ➔ mass of the solute; dissolved in

WA ➔ mass of the solvent.

Then RLVP is determined experimentally by using the formula

𝒑𝟎 −𝒑 𝒏𝑩
= 𝝌 = ;{𝒏𝑨 = number of moles of solvent, 𝒏𝑩 = number of moles
𝒑𝟎 𝒏𝑩 +𝒏𝑨
of solute}
In dilute solution number of solute molecules is very less compared to
solvent
𝒏𝑨 + 𝒏𝑩 = 𝒏𝑨 {∵ 𝒏𝑩 ≪ 𝒏𝑨 .}
𝒑𝟎 −𝒑 𝒏𝑩 𝐖𝐀 𝐖𝐁
= ; But{𝐧𝐀 = and 𝐧𝐁 = }
𝒑𝟎 𝒏𝑨 𝐌𝐀 𝐌𝐁
Substituting,
𝐖𝐁
𝒑𝟎 −𝒑 𝐌𝐁 𝐖𝐁 𝐱𝐌𝐀
→ = 𝐖𝐀 =
𝒑𝟎 𝐖𝐀 𝐱 𝐌𝐁
𝐌𝐀

𝐖𝐁 𝐱𝐌𝐀 𝒑𝟎 −𝒑
→ 𝐌𝐁 = 𝒑𝟎 −𝒑
{ → can be determined experimentally,
𝐖𝐀 𝐱 ( ) 𝒑𝟎
𝒑𝟎

𝐖𝐀 and 𝐖𝐁 → known weights are taken;

𝐌𝐁 → can be determined using the above formula}

Elevation in boiling point [𝚫Tb ]: -

“Increase in boiling point observed when a dilute solution is prepared by dissolving non-
volatile solute is called Elevation in boiling point”

Addition of non-volatile solute to a liquid decreases vapour pressure of the solution

∴ pure solvent has higher vapour pressure than solution (ie..p0> p), at all temperature.

⇒ solution should be heated to higher temperature in order to make vapour pressure

equal to atmospheric pressure, which is called boiling point of a solution.

Thus Boiling point (Tb) for a solution > Pure solvent (𝐓𝐛𝟎 )

Tb > 𝐓𝐛𝟎

The rise in temperature Tb is inversely proportional to decrease in vapour pressure(𝚫𝐏)

Since in dilute solution,

𝚫𝐏 ∝ m (m→ molarity of the solution)

or

Kb → molal elevation or ebullioscopic constant

Molal elevation or ebullioscopic constant (Kb ) : -
“It is defined as the elevation in boiling point for 1 molal solution”
ie.. When 1kg of solute is dissolved in 1kg of solvent,
Then, molality =1.
⇒ 𝜟 Tb = Kb .
Calculation of molar mass of the solute by elevation in boiling point.
Or
To prove that 𝜟 Tb is a colligative property.
𝚫Tb ∝ 𝚫 𝐏 [Raoult’s law→ 𝚫 𝐏 ∝ 𝛘B]
𝚫Tb ∝ K. 𝛘B
𝒏𝐁 𝒏𝐁 𝒏𝐁 𝐱𝐌𝐀
𝚫Tb = K. = K. 𝐖𝐀 = K.
𝐧𝐀 𝐖𝐀
𝐌𝐀

𝐌𝐀
𝚫Tb = K.
𝒎

𝚫Tb = Kb x m
∴ 𝚫Tb is a colligative property.
Calculation of molecuar mass using elevation in boiling point( 𝚫Tb ):-
(by ebullioscopic method)
𝚫Tb = Kb x m ---- (1)
𝐖𝐁 𝟏𝟎𝟎𝟎
m= x
𝐌𝐁 𝐖𝑨

→ ∴ equation (1) can be written as,

𝐖𝐁 𝟏𝟎𝟎𝟎
𝚫Tb = Kb x x ;
𝐌𝐁 𝐖𝑨

𝐖𝐁 𝟏𝟎𝟎𝟎
→ 𝐌𝐁 = Kb x x Kb and Tb→ experimental; 𝐖𝐁 and 𝐖𝑨 → Known
𝚫Tb 𝐖𝑨
value.
This method of determination of molecular mass is called ebullioscopic
method.
Depression in freezing point [𝚫Tf ]: -
“The decrease in freezing point observed when a dilute solution is prepared
by dissolving non-volatile solute is called Depression in freezing point.”

➢ a non volatile solute in a liquid decreases vapour pressure p0> p

→ Freezing point of liquid is the temperature at which solid and liquid has the same
vapour pressure. [Liquid solvent and frozen solvent] is the same.

→ A-B is the vapour pressure of solid solvent.

→ pure solvent freezes at point B(at temperature Tf0) shown by decrease in vapour
pressure.

→ Solution freezes at point B (Temperaute Tf)

→ Lower value of Tf indicates solution has lower freezing point.

∴ Tf 0 - Tf is the depression in freezing point.

𝚫 Tf = Tf0 – Tf

Depression in freezing point (T0 – T1) depends on lowering of vapour pressure (𝚫P)

𝚫Tf ∝ 𝚫 P

[Raoult’s law→ 𝚫 𝐏 ∝ 𝛘B → the mole fraction]

𝚫Tf ∝ 𝛘B

𝚫Tf = k b . 𝛘B
𝒏𝑩
=kb x 𝒏𝑨

𝐖
Substituting the value of nA = 𝐌𝐀
𝐀
 𝒏𝑩 𝐧𝐁 .𝐌𝐀
𝚫Tf = K. 𝐖𝐀 = 𝑾𝐀
𝐌𝐀

𝚫Tf = K. MA .m

𝚫 Tf = Kf .m

Kf → molal depression constant or cryoscopic constant; when molarity is one 𝚫Tf = 𝐊 𝐟

“Kf is defined as the depression in freezing point of a solvent when one molal solution is
prepared using a solvent.”

Calculation of molecuar mass using depression in freezing point[𝚫Tf ]: -

(cryoscopic method)
𝐖 𝟏𝟎𝟎𝟎
𝚫Tf = Kf .m molality m = 𝐌𝐁 x
𝐁 𝐖𝑨

𝐖 𝟏𝟎𝟎𝟎
𝚫Tf = Kf x 𝐌𝐁 x
𝐁 𝐖𝑨

𝐖 𝟏𝟎𝟎𝟎
MB= Kf x 𝚫T𝐁 x
f 𝐖𝑨

This method of determining molecular mass is called cryoscopic method.

Osmotic pressure [𝛑]

Osmosis: -

“The phenomenon by which solvent flows from lower concentration or from pure
solvent into solution of higher concentration, when both of them are separated by a
semipermeable membrane is called Osmosis”
Osmotic pressure

‘It is the excess pressure that should be applied on to solution which is just sufficient to
prevent the flow of solvent due to osmosis.’

Classification of solutions based on Osmotic pressure

1) Isotonic solution: - Two solutions separated by semipermeable membrane processes

same osmotic pressure is called Isotonic solution”

2) Hypertonic solution: -Two solutions separated by semipermeable membrane, solution

with higher concentration is called Hypertonic solution.

3) Hypotonic solution: -Two solutions separated by semipermeable membrane, solution

with lower concentration is called Hypotonic solution.

Osmotic pressure is a colligative property as it depends on the number Of moles (solute

molecules) in solution.

as, 𝛑V =nRT ----(1)

nRT
𝛑= ----(2)
𝑽

n
Number of moles (n) in unit volume(V) is given by → 𝑽 = M(molarity)

⇒ 𝝅 =MRT → vant Hoff’s equation { R= 8.314 bar k-1 mol-1 ;M→concentration in mol L-1
and T→ Temperature in kelvin}

𝝅 =CRT or 𝐏 =CRT

Calculation of molecular mass of solute using Osmotic pressure

nBRT 𝐖
𝛑= ; nB = 𝐌 𝐁 ;
𝑽 𝐁

𝐖𝐁 RT
𝛑= 𝐌𝐁 𝑽

𝐖𝐁 RT
Or 𝐌𝐁 = 𝛑𝑽
Reverse Osmosis [Used in purification of sea water]

“If pressure greater than osmotic pressure is applied on the solution the solvent
starts flowing from solution to pure solvent. This is called reverse osmosis.”

sea water is separated from pure water by semi permeable membrane

when Pressure > Osmtic pressure is applied on sea water

Water flows from sea water to pure water leaving behind the impurities.

Limitations for the determination of molecular mass using colligative properties

1) The solution should be dilute.

2) Solute should be non volatile.

3) The solute should not undergo association and dissociation.

4) Solute should not react with solvent.

Abnormal molecular mass

Colligative properties (C.P)are inversely proportional to molecular mass.

1) If association of molecules is there in solvent. C.P <normal

∴ molecular mass > expected.

Ex: CH3COOH & C6H5 COOH shows molecular mass =120g mol-1.

Observed = 60g mol-1 [dimerization due to intermolecular hydrogen bonding]

2) If dissociation of molecules is there in solvent. C.P > normal

∴ molecular mass < expected.

Ex: Molar mass of KCl = 40.3g mol-1; observed = 74.5g mol-1.

[Due to undissociated molecules & ionic interaction]

Vant Hoff’s factor(i)

It is introduced to check abnormalities in molecular mass due to association and
dissociation of solute.

Given by
𝐍𝐨𝐫𝐦𝐚𝐥 𝐦𝐨𝐥𝐚𝐫 𝐦𝐚𝐬𝐬 (𝐌𝐧 )
i= ;
𝐎𝐛𝐬𝐞𝐫𝐯𝐞𝐝 𝐦𝐨𝐥𝐚𝐫 𝐦𝐚𝐬𝐬 (𝐌𝐎 )

𝐎𝐛𝐬𝐞𝐫𝐯𝐞𝐝 𝐯𝐚𝐥𝐮𝐞 𝐨𝐟 𝐜𝐨𝐥𝐥𝐢𝐠𝐚𝐭𝐢𝐯𝐞 𝐩𝐫𝐨𝐩𝐞𝐫𝐭𝐲

i= ;
𝐂𝐚𝐥𝐜𝐮𝐥𝐚𝐭𝐞𝐝 𝐯𝐚𝐥𝐮𝐞(𝐰𝐢𝐭𝐡𝐨𝐮𝐭 𝐚𝐬𝐬𝐨𝐜𝐢𝐚𝐭𝐢𝐨𝐧 𝐨𝐫 𝐝𝐢𝐬𝐬𝐨𝐜𝐢𝐚𝐭𝐢𝐨𝐧)

𝐍𝐮𝐦𝐛𝐞𝐫 𝐨𝐟 𝐩𝐚𝐫𝐭𝐢𝐜𝐥𝐞𝐬 𝐚𝐟𝐭𝐞𝐫 𝐚𝐬𝐬𝐨𝐜𝐢𝐚𝐭𝐢𝐨𝐧 𝐨𝐫 𝐝𝐢𝐬𝐬𝐨𝐜𝐢𝐚𝐭𝐢𝐨𝐧

i= ;
𝐍𝐮𝐦𝐛𝐞𝐫 𝐨𝐟 𝐩𝐚𝐫𝐭𝐢𝐜𝐥𝐞𝐬 𝐛𝐞𝐟𝐨𝐫𝐞 𝐚𝐬𝐬𝐨𝐜𝐢𝐚𝐭𝐢𝐨𝐧 𝐨𝐫𝐝𝐢𝐬𝐬𝐨𝐜𝐢𝐚𝐭𝐢𝐨𝐧

i < 1 ⇒ Association (0.5 for C2H5COOH & C6H6)

i = 1 ⇒ No Association or dissociation.
i > 1 ⇒ Dissociation (≃ 2) for KCl.

Association Dissociation
Observed molecular mass > Observed molecular mass <
predicted/normal value predicted/ normal value
The value of Vant Hoff’s factor(i) <1 The value of Vant Hoff’s factor(i) >1
The values of colligative properties The values of colligative properties
are lower than expected. are higher than expected.
Ex: reduced boiling and freezing Ex: higher boiling and freezing point
point than expected. than expected.

Applying Vant Hoff’s factor (i)

𝒑𝟎 −𝒑 𝒏𝑩
1) Relative lowering of vapour pressure(RLVP) → = i 𝝌 B=
𝒑𝟎 𝒏𝑨

2) Elevation in boiling point(𝜟Tb) → 𝚫Tb = i Kbm .

3) Depression in freezing point(𝜟Tf) → 𝚫Tf = 𝐢 Kf .m
nBRT
4) Osmotic pressure (𝝅) → 𝝅 = i CRT = i .
𝑽