Solutions

CHAP T ER :1

Solutions
Solutions are homogeneous mixtures of two or more than two components. Homogeneous mixture
have its composition and properties uniform throughout the mixture.
Solvent Solute

In a solution, the component which is present in Another component of solution which is

larger quantity is known as solvent and it present in smaller quantity is known as solute.
determines the physical state of a solution.
Types of Solution
Type of Solution Solute Solvent Common Examples
Gaseous Solutions Gas Gas Mixture of oxygen and nitrogen gases
Liquid Gas Chloroform mixed with nitrogen gas
Solid Gas Camphor in nitrogen gas

Liquid Solutions Gas Liquid Oxygen dissolved in water

Liquid Liquid Ethanol dissolved in water
Solid Liquid Glucose dissolved in water

Solid Solutions Gas Solid Solution of hydrogen in palladium

Liquid Solid Amalgam of mercury with sodium
Solid Solid Copper dissolved in gold

Solid Solutions
Substitutional Solid Solution e.g. Brass Interstitial Solid Solution e.g. Steel (Smaller
(Components have almost similar size). component occupies the interstitial voids).

EXPRESSING CONCENTRATION OF SOLUTIONS OF SOLIDS IN LIQUIDS

• Mass percentage (w/w):
Mass of the component in the solution × 100
Mass % of a component = ——————————————————
Total mass of the solution
• Volume percentage (V/V):
Volume of the component in the solution × 100
Volume % of a component = ———————————————————
Total volume of the solution
• Parts per million (ppm): It is used to express the concentration when a solute is present in trace
quantities.
Number of parts of the component in the solution
Parts per million = ————————————————————————— × 106
Total number of parts of all components of the solution
• Mole fraction (X):
Number of moles of the component
Mole fraction of a component = ————————————————————
Total number of moles of all the components
It has no unit

• Molarity (M):
Moles of solute
Molarity = ————————————
Volume of solution in litre
Unit is mol/L or mol L-1. Molarity is temperature dependent.

• Molality (m):
Moles of solute
Molality (m) = ——————————
Mass of solvent in kg
Unit is mol/kg or mol kg-1. It does not change with temperatures as it is mass to mass ratio. Thus, it is
temperature independent.

SOLUBILITY OF A GAS IN A LIQUID

Henry’s Law
The law states that at a constant temperature, the solubility of a gas in a liquid is directly proportional to
the partial pressure of the gas present above the surface of liquid or solution.

If we use the mole fraction of a gas in the solution as a measure of its solubility, then it can be said that the
mole fraction of gas in the solution is proportional to the partial pressure of the gas over the solution.

The most commonly used form of Henery’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” and is expressed as :
p = KH X
Where p is partial pressure of gas
• KH is the Henry’s law constant and function of the nature of the gas.
• X is mole fraction of the gas in solution.
• Significance of KH: Higher the value of KH at a given pressure, lower is the solubility of the gas in the liquid.
• KH values increase with increase of temperature indicating that the solubility of gases decrease with
decrease of temperature.
• It is due to this reason that aquatic species are more comfortable in cold water rather than in warm water.

Limitations of Henry’s Law

• This law is only applicable when the molecules of the system are in a state of equilibrium.
• This law does not hold true when gases are placed under extremely high pressure.
• This law is not applicable when the gas particles and the solution participate in chemical reactions with each
other.

VAPOUR PRESSURE
It is defined as the pressure exerted (in a system featuring thermodynamics equilibrium) by vapour of gas
with its condensed phases (solid or liquid) in a closed system at a given temperature.
• Vapour pressure of liquid depends upon the nature of liquid and temperature.
 RAOULT’S LAW
• For the solution containing non-volatile solute, the vapour pressure of the solution is directly proportional to
the mole fraction of solvent at a particular temperature.
PA ∝ XA
PA = P0A . XA P0A
+ PB

Vapour Pressure
• For the solution consisting of volatile liquids, the partial vapour pressure P
= A
P Total
of each component is directly proportional to its own mole P0B PA
fraction in the solution at particular temperature.
PA = P0A . XA PB = PB0 . XB PB

And total vapour pressure is equal to sum of partial pressure, Ptotal = PA + PB

XA = 0 Mole Fraction XA = 1
XB = 1 XB = 0

TYPES OF SOLUTIONS
Ideal Solution
The solution which obeys Raoult’s law under all conditions of temperature and concentration and during the
preparation of which there is no change in enthalpy and volume on mixing the component.
Conditions :
PA = P A . XA
0
PB = P0B . XB
∆Hmix(enthalpy of mixing) = 0 (it means that no heat is absorbed or released)
∆Vmix (Volume of mixing) = 0 (it means that the volume of the solution is equal to the sum of the volume of
components). This is only possible if A-B interaction is same as A-A and B-B interaction nearly.
E.g. Benzene and Toluene, Chlorobenzene and Bromobenzene
Very dilute solution exhibit ideal behavior to greater extent.
Non-Ideal Solution
When a solution does not obey Raoult’s law for all concentration and temperature ranges.
May show positive or negative deviation from Raoult’s law.
(a) PA ≠ P0A . XA (b) PB ≠ P0B . XB (c) ∆Hmix ≠ 0 (d) ∆Vmix ≠ 0
For non-ideal solution the A-B interaction is different from A-A and B-B interactions
(i) For solution showing positive deviation
PA > PA0 . XA , PB > PB0 . XB
∆Hmix = Positive, ∆Vmix = Positive (A-B interaction is weaker than A-A and B-B)
E.g. alcohol and water, aectone and benzene.
(ii) For the solution showing negative deviation
PA < PA . XA , PB < PB . XB , ∆Hmix= negative, ∆Vmix= negative(A-B interaction is stronger than A-A and B-B
0 0

interactions). E.g.: Chloroform and acetone, HCl and water

AZEOTROPES
The mixture of liquids at particular composition that has a constant boiling point and behaves like a single
liquid and cannot be separated by simple distillation. Azeotropes are of two types :
• Minimum boiling Azeotrope (mixture which shows positive deviations) example: alcohol and water.
• Maximum boiling Azeotrope (which shows negative deviations) example: acetone and chloroform.
 COLLIGATIVE PROPERTIES
The properties of solution which depends upon the number of solute particles (molecules or ions), but not
upon their chemical nature are called Colligative Properties. There are four colligative properties. They are :
• Relative lowering of vapour pressure : According to Raoult’s Law, the relative lowering of vapour pres-
sure is equal to the mole fraction of the solute in the solution and is given by :
P° - P = χ
——— (∴χsolute = ———n )
P° solute n +N
Where, P° = Vapour pressure of pure solvent
P = Vapour pressure of solution
and χsolute = Mole fraction of solute in solution
1000Kf . w
• Depression of freezing point : M = —————
∆Tf W
Where, Kf = cryoscopic constant (or molal depression constant), w = weight of solute, W = weight of solvent
(where M = molecular weight of solute) (∆Tf = Tf° - Tf ) depression in freezing point.
1000 x Kb x w
• Elevation in boiling point : ∆Tb = ——————— ,
MxW
(Where ∆Tb = Tb - Tb°) (elevation of boiling point)
Where, Kb = Ebullioscopic constant (or model elevation constant), M = molecular mass of solute, W = weight
of solvent, w = weight of solute

• Osmotic Pressure : π = CRT

weight in gms/litre
where, C = —————————
Molecular weight
π = osmotic pressure, C = molarity of solution, T = temperature of the solution on kelvin scale, R = gas
constant.
Osmotic pressure is also defined as the hydrostatic pressure built up on the solution which just stops the
osmosis.

ABNORMAL MOLECULAR MASS

In solution when the substance undergoes dissociation or association, there is discrepancy between observed
colligative property and calculated colligative property and the molecular weights are lower and higher
respectively than expected. This is known as abnormal molecular masses-e.g., Al2Cl6, P4O6, As4O6.

VAN’T HOFF FACTOR

To account for abnormal cases, Van’t Hoff introduced a factor (i) known as the Van’t Hoff factor.
Observed Colligative Property
i = ———————————————————
Calculated (normal) Colligative Property
1-α+— α
∴ Van’t Hoff Factors (i) = ————— n (where -n = Number of molecules or ions in solution
1
Relation between degree of dissociation, and vant Hoff factors (i).
1 - α + nα
∴ Van’t Hoff Factors (i) = ————— (where n = Number of molecules or ions in solution)
1
• For association, i < 1. • For dissociation, i > 1 • For no association and no dissociation, i = 1