Solutions

A solution is a homogeneous mixture of two or more substances.

A solution consisting of two components is called a binary solution and that consisting of three
components is called a ternary solution.
In a binary solution, the component present in small amount is called solute and the one present in
excess is known as the solvent.
Depending upon the nature of the solute and solvent, there are nine (9) different types of solutions.
Solutions are classified as solid, liquid or gaseous solutions depending upon the nature of the
substance acting as the solvent.
Solid solutions in which atoms or ions of one substance occupy the sites of other similar substances
in its crystal lattice are known as substitutional solid solutions.
Solutions in which atoms of one kind occupy the voids that exist between the atoms of the host
lattice are called interstitial solutions.

The amount of solute dissolved in a unit volume of the solvent (or solution) is called the concentration
of solution.
Solutions having a small amount of the solute is called a dilute solution and that containing a large
amount of the solute is called a concentrated solution.
Expressing concentration of solutions
1. Percent concentration (%)
(i) Mass percent (w/w) = Mass of solute x 100 / Mass of solution
(ii) Mass- volume percent (w/v) = Mass of solute x 100 / Volume of solution in mL
(iii) Volume percent (v/v) = Volume of solute x 100 / Volume of solute + Vol. of solvent
2. Parts per million (ppm)
(i) ppm (w/w) = Wt of solute (g) x 106 / Wt of solution (g)
(ii) ppm (w/v) = Wt of solute (g) x 106 / volume of solution (mL)
3. Strength of Solution = Weight of Solute (g) / Volume of solution (L)
4. Molarity (M) = No of moles of solute / Volume of solution (L)
5. Molality (m) = No of moles of solute x 1000 / Mass of solvent (g)
6. Formality (F) = No of gram formula weight of solute / volume of solution (L)
7. Normality (N) = No of gram equivalents of solute / Volume of solution (L)
8. Mole fraction of a component (𝛘)
= No. of moles of the component / Total no. of moles in the mixture
For solutions containing n2 moles of solute and n1 moles of solvent, mole fraction of solute
(𝛘2) = n2 / (n1 +n2) and mole fraction of solvent (𝛘1) = n1 / (n1 +n2).
9. Mass fraction of solute and solvent for a solution containing w2 g solute in w1 g of solvent,
mass fraction of solute = w2 / (w1 +w2) and mass fraction of solvent =w2 / (w1 +w2)
Concentration terms involving volume, i.e., molarity, normality and formality change with change in
temperature whereas molality, mole fraction and ppm which do not involve volumes but involve
weights are independent of temperature.
Molar aqueous solutions are more concentrated than molal solutions.
Normality equation: N1V1 = N2V2
Molarity equation: M1V1 = M2V2
Solubility of a solid in a liquid is the maximum amount of the solute in grams which can dissolve in
100 g of the solvent to form a saturated solution at that particular temperature.
Factors affecting solubility of a solid in a liquid

(i) Nature of the solute and solvent (like dissolves like), i.e., polar solutes are more soluble in polar
solvents and non-polar solute are soluble in non-polar solvents.

(ii) Temperature: Solubility increases with temperature if the dissolution process is endothermic and
decreases if the dissolution process is exothermic. For substances like hydrated sodium sulphate
Na2SO4.10H2O, CaCl2.6H2O, etc. the temperature at which trend changes is called transition
temperature.

(iii) Pressure: There is no appreciable effect of pressure on the solubility of solids in liquids because
solids and liquids are highly incompressible and remain unaffected by changes in pressure

Henry’s Law - Henry law gives relationship between solubility of gas in a liquid pressure and states
that the mass of a gas dissolved in a given volume of the liquid at constant temperature is directly
proportional to the pressure of the gas in equilibrium with the liquid.

Mathematically,
m 𝛂 p or m = Kp. p, where K is a constant.

For a mixture of gases in equilibrium with a liquid, the mass of each gas dissolved is directly
proportional to its partial pressure or partial pressure of the gas is directly proportional to the mole
fraction of the gas in solution.
pA 𝛂 𝛘A or p = K 𝛘
A H. where KH is called Henry’s constant.
A

Unit of Henry’s constant p = KH . 𝛘A or K = pA / 𝛘A . Since 𝛘A is dimensionless, units of K will be same

A H H

as that of pressure, i.e., atm, bar or k bar.

Characteristics of Henry’s Constant

(i) KH is a function of the nature of the gas.
(ii) The greater the value of K at a given pressure, the lower is the solubility of gas
H

(iii) KH increases with increase of temperature implying that solubility decreases with increase
of temperature.
Limitations of Henry’s Law- Henry’s law is valid only if: (i) the gas is only sparingly soluble (ii)
pressure of the gas is not too high and the temperature is not too low (iii) gas does not enter into
chemical combination with the solvent and (iv) gas does not dissociate or associate in the solvent.

Applications of Henry’s law-

(i) In the production of carbonated beverages
(ii) In deep sea diving (scuba diving)
(iii) In the manufacture of hydrogen
(iv) In the storage of ethyne gas
(v) For climbers or people living at high altitudes where there is low concentration of oxygen
is low in blood and tissues causing a disease called anoxia
(vi) In function of lungs
(vii) In removal of highly soluble gases like ammonia from solution.

Vapour Pressure is the pressure exerted by the vapours in equilibrium with a liquid / solution at a
given temperature. Lowering of vapour pressure occurs on dissolving a non-volatile solute in a liquid
solvent because some of the molecules of the volatile solvent on the surface are replaced by those
of the non-volatile solute.
Raoult’s Law for binary solutions of volatile liquids
In a solution, the partial vapour pressure of a volatile component at a given temperature is equal to
the product of mole fraction of the component and the vapour pressure of that component in the
pure state. For a solution of component A and B having mole fractions 𝛘A and 𝛘B respectively.
pA = p°A . 𝛘A and pB = p°B . 𝛘B
Where p°A and p°B are the vapour pressures of pure liquids A and B respectively.
Total vapour pressure, p = pA + pB = p°A . 𝛘A + p°B . 𝛘B
Or p°A . 𝛘B (p°B –p°A )
Thus, plot of p vs 𝛘 , p vs 𝛘 , and p vs 𝛘 or 𝛘 will be linear.
A A B B total A B

Mole fraction in the vapour phase will be

Y =p /p A A total

Or p=Y xp A A total

And Y =p /p B B total

Or p=Y xp . B B tota

Raoult’s Law for Solutions containing non-volatile solute.

The vapour pressure of a solution containing non-volatile solute is directly proportional to the mole
fraction of the solvent at a given temperature, i.e.,
p = p°. 𝛘 A

It can also be written as (p° –p) / p° = n /(n +n ) = 𝛘 B A B B

Here, (p° –p) is lowering of vapour pressure and (p° –p) / p° is the relative lowering of vapour
pressure.
For very dilute solution, if (nA +nB) is considered equal to nA,
(p° –p) / p° = nB /nA
Or (p° –p) / p° = (w /w ) x M /M B A A B

In fact Raoult’s law is a special case of Henry’s law in which K is equal to p° H

Ideal Solutions- A solution formed by mixing two liquids A and B will be an ideal solution if A and
B have identical molecular size, structure and the attractive forces among the solute and solvent
molecules are of the same order as that of solute–solute and solvent–solvent interactions.
Characteristics of Ideal solution-
(i) It should obey Raoult’s law at all concentrations and at all temperatures
(ii) ∆mixV = 0, i.e.,total volume of solution should be equal to the sum of the volumes of the
components mixed
(iii) ∆ H = 0, i.e., there should be no evolution or absorption of heat on mixing the two pure
mix

components.

Non-Ideal Solutions- A non-ideal solution is that solution for which

(i) None of the components obey Raoult’s Law
(ii) ∆mixV is not zero and
(iii) ∆mixH is also not zero.

Types of Non-Ideal solutions

(i) Non-Ideal solution showing positive deviation from the Raoult’s Law, i.e., pA > p°A . 𝛘A and pB >
p°B . 𝛘B This is because their A—B interactions are weaker than A—A or B—B interactions. For such
.

solutions ∆ V and ∆ H are positive.

mix mix

Figure from book

(ii) Non-Ideal solutions showing negative deviation from the Raoult’s Law, i.e., pA < p°A . 𝛘A and pB
< p° . 𝛘 . This is because their A—B interactions are stronger than A—A or B—B
B B

interactions. For such solutions ∆ V and ∆ H are negative.

mix mix

Figure from book

Azeotropic mixture (Azeotropes)- Mixtures of liquids which boil at constant temperature like a
pure liquid such that the distillate has the same composition as that of liquid mixture are called
constant boiling mixtures or azeotropes. They are not definite compounds but are actually mixtures
of compounds. An azeotropic solution that has a boiling point lower than either of the components
shows positive deviation from Raoult’s law. Similarly, an azeotropic solution that has a boiling point
higher than either of the components shows negative deviation from Raoult’s law.

Colligative Properties- Properties of a dilute solution which depend entirely upon the number (or
moles) of solute particles (molecules or ions) contained in a known volume of the given solvent and
not at all upon the nature of the solute are called colligative properties. They are also known as
democratic properties. Properties such as relative lowering of vapour pressure, elevation of boiling
points, depression in freezing points and osmotic pressure are colligative properties. These
properties are interlinked together because all of them depend only upon the number of solute
particles present in a definite volume of solvent.

Calculation of molecular weight from relative lowering of vapour pressure can be done by the given
expression, if MA is molecular mass of solvent, MB is molecular mass of solute, WA is weight of
solvent, WB is weight of solute, p° is vapour pressure of pure solvent and p is vapour pressure of
solution, then for a very dilute solution
MB = (p°. WB. MA) / (p°–p) .WA

Elevation in boiling point – Boiling point of a substance is defined as the temperature at which its
vapour pressure becomes equal to the atmospheric pressure, usually one atmosphere. The addition
of non-volatile solute to the volatile solvent lowers its vapour pressure which is proportional to the
molal concentration, i.e.,
∆T 𝛂 m
b

Or ∆Tb = Kb . m
Here Kb is the molal elevation constant or ebullioscopic constant, m is molality of the solution and
∆Tb is elevation in boiling point. If the solution is one molal then ∆Tb is equal to the ebullioscopic
constant Kb. ∆Tb = Kb and the molal elevation constant or ebullioscopic constant may be defined
as the elevation of boiling point, when the molality of the solution is unity. This equation is valid to
the solutions which follow Raoult's law, should not undergo association or dissociation and should
be dilute. Molecular weight of solute can be calculated by the given equation

MB = WB. Kb. 1000 / ∆Tb .WA Figure from book

Depression in Freezing Point – Freezing point of a substance is defined as the temperature at

which the liquid and the solid states are in equilibrium with each other or it is the temperature at
which the liquid and the solid states of a substance have the same vapour pressure.
Mathematically, depression in freezing point ∆Tf of a solution is directly proportional to the molal
concentration of a solution. Thus:
∆Tf 𝛂 m
Or ∆Tf = Kf . m
Here, m is the molality of solution and Kf is called the molal depression constant or cryoscopic
constant of the solvent. If molality is one, then ∆Tf = Kf .Now, molal depression constant or
cryoscopic constant may be defined as the depression in freezing point when the molality of the
solution is unity. The above equation is valid for very dilute solutions obeying Raoult’s law. Molecular
weight of solute can be calculated by the given equation

MB = WB. Kf. 1000 / ∆Tf .WA Figure from book

Osmosis - Abbe Nollet observed that when a solution is separated from its pure solvent by a
semipermeable membrane (SPM), there is a spontaneous flow of solvent into the solution. This
process is known as osmosis.
Osmotic Pressure – the excess pressure which must be applied on the solution side to prevent the
flow of the solvent into it through a semipermeable membrane is called osmotic pressure of the
solution. Osmotic pressure is developed due to osmosis.
Osmotic pressure is the best colligative property to determine the molecular mass of polymers such
as proteins, nucleic acids etc.

Boyle-van’t Hoff Law - It states that if the temperature remains constant, the osmotic pressure (π)
of a dilute solution is directly proportional to the concentration of the solution. i.e.,
π 𝛂 C or π /C = constant at constant temperature
If one mole of solute is dissolved in V litres of the solution then
C=1/V
Or π = 1 / V
or π . V = constant at constant temperature
In other words, “temperature remaining constant, the osmotic pressure of a dilute solution is
inversely proportional to the volume of the solution containing one mole of solute dissolved in it”.

Charles - van’t Hoff Law - It states that concentration remaining constant, the osmotic pressure of
a dilute solution is directly proportional to absolute temperature.
Mathematically
π 𝛂 T or π /T = constant
van’t Hoff Equation - Combining Boyle -van’t Hoff law and Charles - van’t Hoff law, we get
π 𝛂 CT or π = CRT
Since, C=n/V
π = nRT/ V
Or πV = nRT
This equation πV = nRT is generally known as the van't Hoff equation.

Avogadro’s - van’t Hoff law - If two solutions have the same osmotic pressure and temperature,
their equal volumes contain equal number of moles.

Isotonic solutions - Two solutions having same molar concentration and thus same osmotic
pressure, are called isotonic or iso-osmotic solutions. Isotonic solutions do not involve any flow of
solvent molecules through a semipermeable membrane.

Hypertonic and hypotonic solutions - A solution having lower osmotic pressure (lower molar
concentration) with respect to the other is called a hypotonic solution with respect to the more
concentrated solutions. The more concentrated solution (having higher value of osmotic pressure)
is said to be hypertonic with respect to less concentrated solution.
Isotonic solutions of non-volatile, non-electrolytic solutes have the same molar concentration, i.e.,C
1

= C . However, C may not be equal to C if the solute dissociates or associates in the solvent. A
2 1 2

0.91% or 0.16 M NaCl aqueous solution is isotonic with human RBCs.

Exo-osmosis is the outward osmotic flow of water from a cell containing an aqueous solution
through a semipermeable membrane, i.e., an egg (after removing the hard shell) placed in
concentrated NaCl solution.

Endo-osmosis is the inward flow of water into a cell containing an aqueous solution through a
semipermeable membrane, i.e., an egg (after removing the hard shell) placed in distilled water.
The swelling and bursting of cells when placed in hypotonic solutions is known as haemolysis.
The shrinking of a cell due to flow of water out of the cell is called plasmolysis.
The pressure developed inside a cell due to inflow of water into a cell is called turgor.
Reverse Osmosis - When external pressure applied on a solution exceeds its osmotic pressure,
the solvent starts flowing from the solution to the pure solvent. It is called reverse osmosis. It is used
in the desalination of seawater to get pure water. Figure from book

Gelatinous Cu2[Fe(CN)6] and gelatinous Ca3(PO4)2 are artificially prepared semipermeable

membranes. Semipermeable membrane of Cu2[Fe(CN)6] does not work in non-aqueous solutions
because it dissolves in non-aqueous solvents.
Determination of molar mass of solute from osmotic pressure can be done by the following equation
MB = WB.RT / πV
For solutions showing dissociation, experimental molar mass is less than the calculated value and i
> 1. For solutes undergoing association, experimental molar mass is greater than the calculated
value and i < 1. Here, i , stands for van’t Hoff factor and is defined as “the ratio of the normal (or
theoretical) and experimental (or observed) molar masses”.
i = Theoretical molar mass / Experimental molar mass
Or, i = Experimental value of colligative property / Theoretical value of colligative property.

For electrolytes:
∆Tb = i Kb . m,
∆T = i Kf . m
f

π = i CRT

Degree of dissociation, 𝛂 = (i –1) / (n–1), where n is the number of total number of particles
furnished by one formula unit of the electrolyte.
Degree of association, 𝛂 = (1– i ) / (1–1/n), where n is the number of molecules which get associated
to form a single molecule.