SOLUTIONS & COLLIGATIVE PROPERTIES
INTRODUCTION
In normal life we rarely come across pure substances. Most of these are mixtures containing two or more
pure substances. Their utility or importance in life depends on their composition. The air around us is a
mixture of gases primarily oxygen and nitrogen; the water we drink contains very small amounts of various
salts dissolved in it. Our blood is a mixture of different components. Alloys such as brass, bronze, stainless
steel, etc. are also mixtures. In this Unit, we will consider mostly liquid solutions and their properties.
1. SOLUTIONS
A solution is a homogeneous mixture of two or more than two components.
For example, common salt in water.
Solutions which contain two components in it are called Binary Solutions.
Substances which are used to prepare a solution are called as Components.
The component that is present in the largest quantity is known as Solvent. Solvent determines the
physical state in which solution exists.
The other component present in lesser quantity in the solution is termed as Solute.
Each component may be solid, liquid or in gaseous state.
Strength of Solutions
The amount of solute dissolved per unit solution or solvent is called Strength of solution. There are various
methods of measuring strength of a solution.
2. Volume percentage (%v/v):
“It represents volume of a component in 100 mL of solution”
Vol. % of a component = Vol. of component × 100
Total vol. of solution
3. Mass by volume percentage (%w/v):
“It represents mass of solute in grams present in 100 mL of solution”
Mass by vol. percent = Mass of solute in g ×100
Vol. of sol. in mL
4. Parts per Million (ppm)
Concentration in parts per million can be expressed as mass to mass, volume to volume and mass to
volume.
Questions:
1)Sugar Solution is 10% (w/v) whose density is 1.25 g/ml. calculate (w/w) % .
2) Sugar Solution is 10% (w/w) whose density is 1.2 g/ml. calculate (w/v) % .
3) A solution of HNO3 of 5%(w/w) having density 1.4g/ml .Calculate the mass of HNO3 present in
100 ml solution.
5. Mole Fraction (x)
“It represents the moles of a solute present in one mole of solution”
Mole fraction = No. of moles of the component
Total no. of moles all the components
For example, in a binary mixture, if the number of moles of A and B are nA and nB respectively, the
mole fraction of A will be
2. Molarity, M
“It represents moles of solute present in 1 L of solution”
Molarity, M = Moles of solute
Vol. of sol. in L
Units of Molarity are mol/L also represented by ‘M’ or ‘Molar’.
“Density of a solution is mass of the solution per unit volume”
Density, d = = m/V
Mass of sol.
Vol. of sol.
Molality, m
“It represents moles of solute present per kg of solvent”
Units of molality are mol/kg which is also represented by ‘m’ or ‘molal’.
6. Normality, N
It represents no. of equivalents of solute present in 1 L of solution.
2. VAPOUR PRESSURE
Vapour pressure of a liquid/solution is the pressure exerted by the vapours in equilibrium with the
liquid/solution at a particular temperature. Vapour pressure is escaping tendency.
Vapour pressure of liquid solutions and Raoult’s Law :(Raoult’s law for volatile solutes)
Raoult’s law states that for a solution of volatile liquids,the partial vapour pressure of each
component in the solution is directly proportional to its mole [Link] a solution
containing two volatile components 1and 2 with mole fractions x1 and x2 respectively. Suppose at a
particular temperature, their partial vapour pressures are
P1 and p2 and the vapour pressure in pure state are p10 and p20 .
The plot of vapour pressure and mole fraction of an ideal solution at constant temperature.
The dashed line I and II represent the partial pressure of the components. It can be seen from
the plot that p1 and p2 are directly proportional to x1 and x2, respectively. The total vapour
pressure is given by line marked III in the figure.
Mole fraction in vapour phase
If y1 and y2 are the mole fractions of the components 1 and 2 respectively in the vapour phase then,
using Dalton's law of partial pressures:
p1 = y1 ptotal p2 = y2 ptotal
In general
pi = yi ptotal
Vapour pressures of solutions of solids
in liquids and Raoult’s Law
(Raoult’s law for non volatile solutes)
If a non-volatile solute is added to a solvent to give a solution, the number of solvent molecules
escaping from the surface is correspondingly reduced, thus, the vapour pressure is also reduced.
The decrease in the vapour pressure of solvent depends on the quantity of non-volatile solute present
in the solution, irrespective of its nature.
Raoult's law in its general form can be stated as, for any solution the partial vapour pressure of
each volatile component in the solution is directly proportional to its mole fraction.
In a binary solution, let us denote the solvent by 1 and solute by 2. When the solute is non-volatile, only the
solvent molecules are present in vapour phase and contribute to vapour pressure. Let1 p1 be the vapour
pressure of the solvent, x1 be its mole fraction, p10 be its vapour pressure in the pure state. Then
according to Raoult's law
Ideal and Non-ideal solutions
Ideal solutions :
• An ideal solution is the solution in which each component obeys Raoult's law under all conditions of
temperatures and concentrations. Solvent-Solute(A-B) type of force is weaker than Solute- Solute(B-
B) & Solvent-Solvent(A-A) forces.
Non – ideal solutions :
When a solution does not obey Raoult's law over the entire range of concentration, then it is called non-
ideal solution.
Solutions showing positive deviation from Raoult’s Law :
• Solvent-Solute(A-B) type of force is weaker than Solute- Solute(B-B) & Solvent-Solvent(A-A)
forces.
Positive Deviation :
Negative Deviation :
Azeotropes :
Azeotropes are binary mixtures having the same composition in liquid and vapour phase and boil
at a constant temperature.
Minimum boiling azeotrope
The solutions which show a large positive deviation from Raoult's law form minimum boiling
azeotrope at a specific [Link] example, ethanol-water mixture containing approximately
95% of ethanol forms an azeotrope with boiling point 351.15 K.
Maximum boiling azeotrope :
The solutions that show large negative deviation from Raoult's law form maximum boiling azeotrope at
a specific composition. Nitric acid and water mixture containing 68% nitric acid forms an azeotrope with
a boiling point of 393.5 K.
Solubility of a solid in liquid
Solubility of a substance is its maximum amount that can be dissolved in a specified amount of solvent.
Factors affecting the solubility of a solid in liquid :
Nature of solute and solvent :Like dissolves like. For example, While sodium chloride and sugar dissolve
readily in water, naphthalene and anthracene do not. On the other hand, naphthalene and anthracene dissolve
readily in benzene but sodium chloride and sugar do not.
Temperature :
In a nearly saturated solution
Henry’s law
Henry's law states that at a constant temperature, the solubility of a gas in a liquid is directly
proportional to the pressure of the gas.
The most commonly used form of Henry's law states that “the partial pressure of the gas in vapour
phase (p) is proportional to the mole fraction of the gas (x) in the solution”.
p = KH x
Here KH is the Henry's law constant.
Characteristics of KH :
• KH is a function of the nature of the gas.
• Higher the value of KH at a given pressure, the lower is the solubility of the gas in the liquid.
• K values increase with increase of temperature indicating
H that the solubility of gases increases with
decrease of temperature.
Applications of Henry’s law
1. In the production of carbonated beverages.
2. In the deep sea diving.
3. For climbers or people at high altitudes.
Colligative properties:
1. Relative Lowering of vapour Pressure
2. Elevation in Boiling Point
3. Depression in freezing point
4. Osmotic pressure
Relative Lowering of vapour Pressure :
When a non-volatile solute is added to a solvent, the vapour pressure decreases.
The lowering of vapour pressure w.r.t. the vapour pressure of the pure solvent is called “Relative
lowering in vapour pressure”.
Numericals :
1)
2)
3)
4)
Elevation in Boiling Point
v
1)
2)
3)
4)
5)
Depression in freezing point
Numericals:
1)
2)
3)
4)
5)
Osmotic Pressure :
1)
R = 0.083 Lbarmol-1
2)
3)
Abnormal Molar Masses
Association :
Dissociation :
An → nA
van’t Hoff Factor :