UNIT-2 (SOLUTION)

Introduction:

Mixture: when two or more non reacting chemical substance mix together they are formed as mixtures.
There are two types of mixtures homogenous and heterogeneous.

Homogeneous mixture: The mixtures in which composition and properties are uniform are called homogenous
mixture. Ex- salt solution, sugar solution, milk in water

Heterogeneous mixture: The mixture in which composition and properties are not uniform are called
heterogeneous mixture. Ex- sand in water

Solutions: it is the homogenous mixture two or more chemically not reacting substance are known as
solutions.

 Solution contain two components one solute and another one is solvent
 Solute: The small amount of component present in solution is known as solute.
 Solvent: The large amount of substance present in solution is known as solvent.
Ex- In sugar solution sugar -solute, water - solvent

Types of solution:

Binary solution: the solutions which contain only two component are known as binary solution

a. Solid solution
b. Liquid solution
c. Gaseous solution

Different types of binary solution

Type of solution Solute Solvent Common example

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

Concentration of solution: composition of solution can be explained by concentration of solution.

i. mass percentage:
It is defined as the amount of solute in grams present in 100 grams of the solution.

Mass percentage of solute =

Ex- 10% w/w aqueous NaCl solution means 10gm of NaCl is dissolved in 90gm of water.
ii. mass to volume percentage:
It is defined as the mass of solute in grams present in 100ml of solutions.

Percentage of solute mass by volume =

Ex- 10% w/v aqueous NaCl solution means 10gm of NaCl is dissolved in 100ml of solution.

iii. Volume to mass percentage:

It is defined as the volume of solute in ml present in 100gm of solution.

Percentage of solute volume by mass =

Ex- 10% v/w aqueous ethanol means 10ml of ethanol is dissolved in 90gm of water.
iv. Volume to volume percentage:
It is defined as the volume of solute in ml present in 100ml of solution.

Percentage of solute volume by volume =

Ex- 10% v/v aqueous ethanol means 10ml of ethanol dissolved in 90ml of solution.

v. Parts per million (ppm):

It is defined as the no of grams of the solute in one million gm. of the solutions. This method is used
when the solute present in solution is trace amount.

PPM =

vi. Mole fraction:

It is defined as the ratio of the number of moles of one component (solute or solvent) to the total
number of moles of all the components (solute + solvent) present in the solution
 It is denoted by x.
 Moles of solute = n1 , moles of solvent = n2

 Xsolute = =

 Xsolvent = = (xsolute+ xsolvent = 1)

 It has no unit.
vii. Molarity:
It is defined as the number of moles of solute present per litre of solution. It is represented by symbol
(M).

Molarity =

M= X1000 , w = weight of solute, m = molecular mass of solute

v = volume of solution
 The unit of molarity is mol litre -1
viii. Molality:
It is defined as the number of moles of solute per 1kg of solvent. It is represented by (m).

Molality =

m= X1000 , w = weight of solute, M= molecular mass of solute

W = weight of solvent
ix. Normality:
It is defined as the no of gram equivalents of solute present per litre of solution. It is denoted by ‘N’

Normality =

N=
Where, WB = given mass of solute, EB = equivalent mass of solute, v = volume of solution in litre
x. Formality:
It is the number of formula mass of solute in grams present per litre of solution. It is denoted by ‘F’

Formality =

Resultant normality =

Solubility:
The maximum amount of solute that can be dissolved in 100g of solvent to make a saturated solution at a
given temperature

Solubility of solid in liquid:

In these solution, solute is solid and solvent is liquid.

Depending upon the quantity of solute present in the solution, the solution is of two types

i. Unsaturated solution/dilute solution: it is the solution in which the quantity of solute is very small
and the quantity of solvent is very large. The solvent can dissolve more quantity of solute in it at
room temperature. These solutions are stable and called as dilute solution.
ii. Concentrated solution: it is the solution which contain large amount of solute as compare to dilute
solution
 it is of two types
1. Saturated solution: It is the solution which contain maximum amount of solute at room
temperature i.e., the solvent can’t dissolve in more quantity of solute at room temperature.
2. Super saturated solutions: It is the solution which contain maximum amount of solute .and
these solutes can’t dissolve completely in solvent and solution converted into precipitation.
  This solution is unstable.

Cause of solubility:
There are three types of force operate when a solute is mixed with solvent.

i. Inter-ionic attraction in the solute molecules.

In ionic solids the attraction between ions is of electrostatic nature and it is responsible for holding the
crystal lattice.
ii. inter -molecular attraction between solvent molecules.
Due to polar nature of solvents dipole created then dipole-dipole interaction will be created
iii. force of attraction between solute and solvent molecules (hydration energy):
If the hydration energy is higher than the lattice energy then lattice get dissolution and make a better
solution.

Factor affecting solubility of solid in liquid:

1. Nature of solute and solvent:
Polar solute dissolve in polar solvent and non- polar solute dissolve in non-polar solvent easily but non
polar solute can’t dissolve in polar solvent and vice versa.
2. Temperature:
If temperature increase then solubility of solute in solvent decrease in this solution

Solubility of liquid in liquid:

When two liquids are mixed to each other then we get three types of mixture.

a. The two liquid do not mix but form two separate layer. These are termed as immiscible.
b. The two liquid may be partially miscible.
c. The two liquid are dissolve in each other in all proportion. These are termed as miscible.

Solubility of a gas in a liquid:

All gases are soluble in water as well as in other liquids to a greater or lesser extent. Solutions of gases in water
play an important role in our daily life.

Factor affecting solubility of a gas in a liquid:

Nature of gas: generally, gases which can be easily liquefied are more soluble in common solvents. Ex- CO2 is
more soluble in water than hydrogen and oxygen.

 Gases which are capable of forming ions in aqueous solution are much more soluble in water than in
other solvent.

Effect of temperature: the solubility of gas in liquid decrease with increase in temperature.

Effect of pressure: It is the most important factor that influences the solubility of the gas in liquids. Henry’s law
relates the solubility of gas with pressure quantitatively.

Henry’s law:
Mole fraction of the gas in a solution is proportional to the partial pressure of the gas.

Xαp
 X = k’p

P= x

P = KHx (KH = ) , p = partial pressure , KH = henry’s law constant , x = mole fraction of the gas
limitation o f henry’s law:
i. The pressure of gas is not too high.
ii. The temperature is not too low.
iii. The gas does not dissociate in solution.
iv. The gas does not chemically interact with the solvent.

Application of henry’s law:

i. Carbonated beverages: Effect of pressure on solubility of gas, is used in producing carbonated
beverages like soft drink, beer etc.
ii. Deep sea diving: the solubility of gas increase with increase pressure .that used in deep sea diving in
blood of diver

Evaporation and vapour pressure:

Vapour pressure: the pressure exerted by the vapours in equilibrium with liquid at a given temperature is
called the vapour pressure.

Ex. When the amount of water vapour increase then pressure will increase in a closed vessel

Evaporation: the process of change of liquid into vapour state is called evaporation.

Condensation: the return of the molecules from the vapour state to the liquid state is known as condensation.

→ →

Factor affecting vapour pressure:

i. Nature of liquid: the evaporation depends upon the strength of intermolecular forces (cohesive forces).
The liquid having low intermolecular forces evaporate faster in comparison to the liquids having high
intermolecular forces.
ii. Temperature: Rate of evaporation increase with increase of temperature as the kinetic energy of the
molecules increases with the rise of temperature.

Vapour pressure of solutions:

 Volatile: the solute which have low intermolecular force and moves freely to each direction.
 Non-Volatile: Solutes which have high intermolecular force and do not moves freely to each direction.
 When a non-volatile solute added to the solvent then vapour pressure of solution always less than pure
solvent

Raoult’s law:
The vapour pressure of a solution containing non- volatile solute is proportional to the mole fraction of the
solvent.
 PA α XA ------------- (I)

PA = PA0XA (PA = vapour pressure of solution, PA0 = vapour

pressure of pure solvent, XA = mole fraction of solvent)

a) For solutions containing volatile solute:

Let’s us consider a solution containing certain quantity of volatile solute.
Let PA = partial VP of volatile liquid A (partial means separate)
PB = partial VP of volatile liquid B
XA = mole fraction of liquid A
XB = mole fraction of liquid B
According to Raoult’s law, in the solution

PA α XA P B α XB

=> PA = PA0XA --------1 => P B = PB0XB -------------2

Where PA0 and PB0 are the VP of pure liquid A and B respectively
The vapour pressure (PS) of solution equal to
PS = PA+PB
 PS = PA0XA + PB0XB
 PS = PA0XA + PB0XB ( XA+XB = 1)
 PS = (PA0 – PB0)XA + PB0
b) For solutions containing non-volatile solute:
Let’s us consider a solution containing certain quantity of non-volatile solute.

In this solution VP of solution depends upon only solvent not in solute, VP of non-volatile solute is zero
 PS = P A + PB
 PS = P A (PB = 0, it is due to the solute B is non-volatile)
0
 PS = PA XA
 = XA --------------------------------------- 1

 = 1-XB

 = XB

 = XB

VP diagram for Raoult’s law:

 PS =PA+PB

PB
VP

PA

Raoult’s law versus Henry’s law:

Similarities: Both these law state that vapour pressure of volatile component is directly proportional to the
mole fraction of that component

Difference: There is difference of proportionality constant i.e., and KH are the proportionality constants in
Raoult’s Law and Henry’s law respectively

PA = XA (Raoult’s law)

PA = KHXA (Henry’s law)

IDEAL AND NON-IDEAL SOLUTIONS:

Ideal solution:
A solution is said to be ideal which obeys Raoult’s law in the entire concentration range and at all temperatures.

 No solution is perfectly ideal solution, following solutions are nearly ideal solution
 Ex. – Benzene + Toluene , methanol + ethanol , n-hexane + n-heptane , chlorobenzene + bromobenzene

Characteristics of ideal solution:

 The volume of solution is equal to the sum of volume of solute and solvent ( ∆v = 0)
 In an ideal solution itermolecular forces of type A and B (A-B) are of same straegth as A-A and B-B
present before mixing
∆H = 0 (no energy or heat evolved or abserved )
Non Ideal solution:
The solutions which do not obey Raoult’s law are called non-ideal solutions.

i. Heat is either absorbed or evolved during formation solution.

∆H ≠ 0

ii. The volume change is not zero.

∆v ≠ 0
Total volume of solution = volume of solvent + volume of solute
iii. Non- ideal solution is of two types.
a. Solution showing positive deviation
b. Solution showing negative deviation

a. Solution showing positive deviation:

In a non-ideal solution with positive deviation, the partial pressure of each component is greater than
the vapour pressure as expected according to Raoult’s law.
PA > PA0XA ; PB > PB0 XB
P > PA+PB ∆H > 0
0 0
P > PA XA + PB XB
∆v > 0

In this figure, bold lines represent positive deviation and dotted line represent an ideal solution.

b. Solution showing positive deviation:

In a non-ideal solution with positive deviation, the partial pressure of each component is less than the
vapour pressure as expected according to Raoult’s law.
PA < PA0XA ; PB < PB0 XB
P < PA+PB ∆H < 0
0 0
P < PA XA + PB XB
∆v < 0

In this figure, bold lines represent negative deviation and dotted line represents an ideal solution.

Azeotropic mixture: The Azeotropic mixtures are the mixtures of liquids which boils at constant
temperature like a pure liquid without undergoing any change in the composition.

 The term zoeotrope means constant boiling mixtures

 These mixtures cannot be separated into individual pure component by fractional distillation.

Azeotropes are of two types:

i. Minimum boiling Azeotropes

ii. Maximum boiling Azeotropes
i. Minimum boiling Azeotropes:
These are formed by those liquid pairs which show a positive deviation from ideal behaviour.
 These Azeotropes have boiling points lower than either of the components.
 C2H5OH (B.P- 351K) + H20 (B.P-373K) = Azeotrope (B.P – 351.1K)
ii. Maximum boiling Azeotropes:
These are formed by those liquid pairs which show a negative deviation from ideal behaviour.
 These Azeotropes have boiling points higher than either of the components.
HCL (B.P- 188K) + H20 (B.P-373K) = Azeotrope (B.P – 383K)

Colligative properties:
It is the physical properties of dilute solution whose value depends upon the number of solute particles
present in it
Colligative properties are of four types:
a. Lowering of vapour pressure
b. Elevation in boiling point
c. Depression in freezing point
d. Osmotic pressure
a.Relative lowering of vapour pressure:
When a non-volatile solute is added to a solvent, its vapour pressure is lowered.
 The vapour pressure of the solution is always less than the vapour pressure of the solvent at the same
temperature
 If P0 be the vapour pressure of pure solvent and P be the vapour pressure of solution, then
P0 – P = lowering in vapour pressure
–
= Relative lowering in vapour pressure
According to Raoult’s law, P = P0XA , where XA = mole fraction of solvent,
P0= Vapour pressure of pure solvent
 PS = P A + PB
 PS = P A (PB = 0, it is due to the solute B is non-volatile)
0
 PS = PA XA
 = XA --------------------------------------- 1

 = 1-XB

 = XB

 = XB

Is called as “lowering of vapour pressure” and is called as relative lowering of vapour pressure


Let n = number of moles of solute and N = number of moles of solvent
According to RLVP

 = XB We know that XB = Mole fraction of non-volatile solute

 XB =
 ,thus = ---------------1

 Since solution is very dilute, so N >> n and N + n ≈ N.

 = ----------------------------- 2

 Let w = weight of solute and m = molecular mass of solute n =

 W = weight of solvent and M = molecular mass of solvent N =
Then equation -2 becomes
⁄
= ⁄
= x ------------------------------- 3

b. Elevation in boiling point:

When a non-volatile solute is dissolved in a solvent, its boiling point decreases, i.e., the boiling point
of a solution is greater than boiling point of solvent. This increase in boiling point of solution is called
as ‘elevation in boiling point’
Boiling point: the temperature at which the vapour pressure becomes equal to the atmospheric
pressure
 the boiling point of liquid depends upon the atmospheric pressure (if ATP decrease then boiling point of
liquid decrease and vice-versa )
Explanation:

Where Tb0 is the boiling point of pure solvent, Tb is the boiling point of solution and ∆Tb is the elevation
in boiling point
 The elevation in boiling point of solution is directly proportional to the molality of the solution
 ∆Tbαmolality
 ∆Tb=Kb x molality (where Kb = ebullioscopic constant or boiling point elevation constant )
 Ebullioscopic constant: when one mole of non-volatile solute is dissolved in 1kg of solvent then
ebullioscopic constant is equal to the elevation in boiling point
 Calculate of molecular mass of solute:
∆Tb = Kb x => m = Kb x
c. Depression in freezing point:
Freezing point: the temperature at which the liquid just change into solid
 The temperature at which the vapour pressure of liquid becomes equal to the solid. When a non-
volatile solute is added to a solvent, its vapour pressure decrease i.e., the vapour pressure of solution
becomes lower than the solvent.
 Explanation: the depression in freezing point can be studied by plotting a graph between vapour pressure

and temperature of pure solvent and solution

 ∆p α ∆Tf α molality (∆Tf = depression in freezing point )HK.;’;L*OUURL*Y


 //.Tf α (molality = ) ( w = weight of solute, m = molar mass of solute, W = weight of solvent
)
 ∆Tf = Kf (Kf = cryopscopic constant )
 Cryopscopic constant: when one mole of non-volatile solute is dissolve in 1kg of solvent, then cryopscopic
constant is equal to depression in freezing point
Determination of molecular mass of solute:
 m = Kf
D. Osmosis: the spontaneous flow of solvent molecule into the solution side through a semipermeable
membrane is known as osmosis
 .semipermeable membrane: it is “ the membrane which allows the passage of only solvent
molecules through it not to the solute molecule at all”
 Difference between osmosis and diffusion:

L
 osmosis osmotic pressure reverse of osmosis

Osmotic pressure: the pressure which is applied at higher concentration side(solution side) to prevent
the flow of molecules from lower concentrated side ( solvent side ) is known as osmotic pressure.
a. Isotonic solution: the solution which have same osmotic pressure with other solution is known as
isotonic solution.
b. Hypertonic solution: the solution which have higher osmotic pressure than the other solution is
known as hypertonic solution.
c. Hypotonic solution: the solution which have lower osmotic pressure than the other solution is
known as hypotonic solution.
Determination of molecular mass of solute by osmotic pressure:
According to van’t Hoff equation π = CRT
 = RT ( c = , n = no mole of solute, v = volume of solution in litre )
 = nRT
 = RT ( n = , w = given mass of solute , m = molar mass of solute )
 determination of molecular mass of solute

Reverse of osmosis: the maximum pressure applied at higher concentrated side then molecules of higher
concentrated side flow to lower concentrated side it is known as reverse of osmosis

 it is used to purification of water in aqua purifier

ABNORMAL MOLAR MASSES

It is found that solutes undergo dissociation or association as a result, the observed colligative properties
deviate largely from theoretically calculated values. The molecular mass calculated from them must be
differ than actual values this is known as abnormal molar mass.

1. Abnormal molecular mass in case of dissociation:

In dissociation the ionic solute molecule dissociate into ions when dissolved in liquid solvent then the
number of effective particles increases, the colligative properties such as osmotic pressure, elevation in
boiling point, depression in freezing point are much higher than those calculated on the basis of
undissociated single molecules.

When colligative properties increase so that the molecular mass decrease

2. Abnormal molecular mass in case of Association:
 There are many organic solutes which undergoes association in solution i.e., two or more molecules
associate to form a bigger molecule, in this case number of solute particle decrease and consequently
the colligative properties, such as osmotic pressure, depression in freezing point, elevation in boiling
point are much smaller than that calculated on the basis of single molecule.

Van’t hoff factor:

In order to calculate the above abnormal colligative properties van’t hoff introduce a factor ‘i’ called as van’t
hoff factor.

 It is used to express the extent of association or dissociation a solute undergoes in the solution phase
 It is defined as (i) “ the ratio of observed colligative properties and the calculated (theoretically)
colligative properties”

i=

As, colligative property α

So, i=

i=

1. Degree of Dissociation:
Degree of association may be defined as the fraction of the total number of molecules which undergoes
dissociation into ions in the solution.

x=
Where, Let x = degree of dissociation, i= van’t hoff factor , n= no ions
2. Degree of Association:
Degree of Association may be defined as the fraction of the total number of molecules combine to form
bigger molecules.

x=

Where, Let x = degree of Association, i= van’t hoff factor , n= no ions

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