CLASS 12th Sub: Chemistry Solutions Notes: Henry’s law (Effect of pressure on the solubility of the gases) :

Since the gases are compressible, their solubility in the liquids is influenced by external
pressure of the gas. The solubility of gases increases with the increase in pressure.
Q. Why naphthalene dissolves in benzene but not in water ?
Henry’s law states that the solubility of a gas in a liquid at constant temperature is
Ans- Since naphthalene is a covalent non-polar substance’ it is soluble in a non-polar
proportional to the pressure of the gas above the solution.
solvent like benzene but insoluble in polar solvent like water.
If S is the solubility of a gas in mol dm-3 at a pressure P and constant temperature
Q. Anhydrous sodium sulphate dissolves in water with the evolution of heat. What is
then by Henry’s law,
the effect of temperature on its solubility ?
S P or S = KH x P , where KH is called Henry’s law constant.
Ans. Since the dissolution of anhydrous sodium sulphate in water is an exothermic
process due to evolution of heat, according to Le Chatelier’s principle its solubility If P = 1 atm, then S = KH.
decreases with the increase in temperature.
If several gases are present, then the solubility of any gas in the mixture is
Solubility of gases in liquids : proportional to its partial pressure at given temperature.

Gases are soluble in water and other liquids and their solubility depends upon the
nature of the gas.
Illustration of Henry’s law : In case of aerated or carbonated drink beverage, the bottle
Non-polar gases like O2, have less solubility in polar solvents. is filled by dissolving CO2 gas at high pressure and then sealed.

Polar gases like CO2, NH3, HCl, etc. are more Soluble in polar solvent like water. CO2 Above the liquid surface there is air and undissolved CO2. Due to high pressure, the
forms H2CO3, while NH3 forms NH4OH in aqueous solutions. amount of dissolved CO2 is large.

The solubility of gases in liquids increases with the increase in pressure and the When the cap of the aerated bottle is removed, the pressure on the solution is
decrease in temperature. lowered, hence excess of CO2 and air escape out in the form of effervescence. Thus by
decreasing the pressure, solubility of CO2 is decreased.

Effects of temperature on solubility of a gas in water :

Exceptions to Henry's law :
The gases are soluble in water and other liquids.
The gases like NH3 and CO2 do not obey Henry’s law. This is because, these gases react
According to Charles’ law, the volume of a given mass of a gas increases with the
with water,
increase in temperature at constant pressure.
NH3(g) + H2O(l) --> NH4+(aq) + OH-(aq)
Hence, the volume of the dissolved gas increases with the increase in temperature.
CO2(g) + H2O(l) —> H2CO3(aq)
Solutions and colligative properties.

This enormous increase in volume of the gases cannot be accommodated by the

solvent molecules, hence excess of the gases escape out in the form of bubbles. Due to reactions of the gases like NH3, CO2(g), they have higher solubility than
expected by Henry’s law. Solutions and colligative properties.
Therefore, the solubility of gases in liquids decreases with temperature.
Units of Henry’s law constant : x1 and x2 are their mole fractions in solution.

By Henry’s law, S = KH x R where S is solubility of the gas in mol dm-3, P is the pressure Then according to Raoult’s law,
of the gas in atmosphere (or in bar) and KH is Henry’s law constant.
we write P1 = x1P01 and P2 = x2P02 ….. (1)
S(mol dm-3)
where P01 and P02 are vapour pressures of pure liquids A1 and A2, respectively.
KH = 𝑆𝑚𝑜𝑙 𝑑𝑚−3𝑃𝑎𝑡𝑚 mol dm-3 atm-1 or mol dm-3 bar-1
According to Dalton’s law of partial pressures, the total pressure P above the solution is,
Hence the units of Henry’s law constant KH are mol dm-3 atm-1
PT = P1 + P2 = x1P01 + x2P02 ……(2)
Q. Why Oxygen gas is slightly soluble in water but it is highly soluble in blood.
Since x1 + x2 = 1 x1 = 1 x2, the Eq. (1) can also be written as
Ans. The O2 gas has very low solubility in water. However, its solubility in blood is
PT = (1 x2) P01 + x2P02
exceedingly high. This is because of binding of O2 molecule to haemoglobin present in
blood. Haemoglobin is a vital constituent of blood, reacts with oxygen increasing the = P01 x2P01 + x2P02
solubility of oxygen.
= (P02 - P01) x2 + P01 ….. (3)
Haemoglobin + 4O2(g) —> Haemoglobin O8
With the help of above equation, the vapour pressures of solutions having different
This oxygenated blood is circulated to various parts of the body, for the supply of concentrations (or mole fractions) can be calculated.
oxygen.
USE CLASS NOTES derivation FOR THE ABOVE AND BELOW DATA:
Q. Explain, why do aquatic animals prefer to stay at lower level of water during
summer ? Variation of vapour pressure with mole fraction of a solute in a liquid mixture :

The solubility of oxygen gas decreases with the increase in temperature. Because P01 and P02 are constants, a plot of PT versus x2 is a straight line as shown in
the Fig The figure also shows the plots of P1 versus x1 and P2 versus x2 according to the
In sea or lake water, the temperature of upper level is higher than the lower level. equations 1. These are straight lines passing through origin. Solutions and colligative
properties.
Therefore the dissolved oxygen content in water is more at lower level than at higher
level required for the marine life.

Hence marine life like fish prefers to stay at lower level than upper level of water. When x1= 1, x2=0, PT = P01 and when x1=0, x2 = 1, PT = P02 as shown by lines I and II
in Fig.
Vapour pressure of solutions of liquids in liquids :
Composition of vapour phase above a liquid mixture.
Raoult’s law : The law states that, at constant temperature, the partial vapour pressure
of any volatile component of a solution is equal to the product of vapour pressure of Consider a liquid mixture of two liquids A and B having vapour pressures P0A and P0B
the pure component and the mole fraction of that component in the solution. Solutions and mole fractions x1 and x2 respectively in the liquid phase.
and colligative properties.
By Raoult’s law, the vapour pressures of two liquids will be,

PA = x1 P0A and PB = x2 P0B

Suppose that for a binary solution of two volatile liquids A1 and A2,
The total vapour pressure of this liquid mixture is,
P1 and P2 are their partial vapour pressures
PT = PA + PB Characteristics of nonideal solutions :

Pr = x1P0A + x2P0B Nonideal solutions do not obey Raoult’s law over the entire range of concentrations.

The vapour above liquid surface contains A and B. The vapour pressures of these solutions may be higher or lower than ideal solutions.

If y1 and y2 are the mole fractions of A and B components respectively in the vapour These solutions exhibit two types of deviations from Raoult’s law namely (a) positive
phase, then by Dalton’s law of partial pressures, deviation and (b) negative deviation.

PA = y1PT and PB = y2PT These solutions give azeotropic mixtures.

and total vapour pressure is,

PT =y1PT + y2PT Solutions with positive deviations from Raoult’s law :

Ideal solutions : These are solutions which obey Raoult’s law over an entire range of A solution or a liquid mixture which has higher vapour pressure than theoretically
concentrations at constant temperature. calculated by Raoult’s law or higher than those of pure components is called a nonideal
solution with positive deviation.
Example : A liquid mixture of benzene and toluene which have nearly identical
physical properties and intermolecular forces forms an ideal solution. In these solutions, solute-solvent intermolecular attractions are weaker than those
between solvent-solvent and solute-solute interactions.

For example, solutions of acetone and ethanol, carbon disulphide and acetone, etc.
Characteristics of ideal solutions :
Solutions and colligative properties.
The ideal solutions obey Raoult’s law over entire range of concentrations at constant
temperature.

In the formation of an ideal solution, heat is neither evolved nor absorbed and Solutions with negative deviations from Raoult’s law :
enthalpy change for mixing is zero, i.e. mixH = 0.
A solution or a liquid mixture which has lower vapour pressure than theoretically
In the formation of an ideal solution, there is no volume change on mixing two liquid calculated by Raoult’s law or lower than those of pure components is called a nonideal
components and the volume of solution is equal to the sum of volumes of two liquid solution with negative deviation.
components. mixV = 0
In these solutions, the intermolecular interactions between solvent and solute
In the ideal solution, solvent-solvent, solute-solute and solvent-solute interactions are molecules are stronger than solvent-solvent or solute-solute interactions.
comparable.
For example, solutions of phenol and aniline, chloroform and acetone, etc.
Solutions and colligative properties.

The vapour pressure of an ideal solution lies between vapour pressures of two pure
Colligative properties of nonelectrolyte solutions :
components.
Colligative Property : The property of a solution which depends on the total number of
particles of the solute (molecules, ions) present in the solution and does not depend on
Nonideal solutions : These are solutions which do not obey Raoult’s law over the entire the nature or chemical composition of solute particles is called colligative property of
range of concentrations. the solution.
Examples of colligative properties : If P0 is the vapour pressure of a pure solvent (liquid) and P is the vapour pressure of
the solution, where P < P0, then, (P0 — P) is the lowering of the vapour pressure.
lowering or relative lowering of vapour pressure of a solution

elevation in the boiling point

Relative lowering of vapour pressure : If Po and P are the respective vapour pressures
depression in the freezing point
of a pure liquid (solvent) and the solution containing a nonvolatile solute Solutions and
osmotic pressure. colligative properties.

Solutions and colligative properties.

then P < P0. Hence, P0 — P represents the lowering of the vapour pressure due to
addition of a nonvolatile solute.
Vapour pressure of a liquid :
Relative lowering of vapour pressure = 𝑃0−𝑃𝑃0=Δ𝑃𝑃0
If a volatile liquid is placed in an open vessel, the liquid molecules have a tendency to
escape in a gaseous state forming vapour and diffuse into surroundings. Hence Raoult’s law for solutions of nonvolatile solutes :
evaporation takes place continuously and no equilibrium is attained.
Statement of Raoult’s law : The law states that the vapour pressure of a solvent over
If a liquid is placed in a closed vessel, the vapour molecules get accumulated on its the solution of a nonvolatile solute is equal to the vapour pressure of the pure solvent
surface. These vapour molecules are in continuous random motion. They collide with multiplied by mole fraction of the solvent at constant temperature.
each other, with walls of a container and surface of the liquid, and return to the liquid
Explanation : Let P0 and P be the vapour pressures of a pure solvent and a solution
state. This reverse phenomenon is called condensation.
respectively. If x1 is the mole fraction of the solvent then Raoult’s law can be
After some time, rates of evaporation and condensation become equal and an represented as, P = x1P0
equilibrium is established between liquid and vapour phases. At this stage the vapour
For a binary solution containing one solute, if x1 and x2 are mole fractions of a solvent
exerts a constant pressure called vapour pressure on liquid surface at constant
and a solute respectively then,
temperature.
x1 + x2 = 1
Vapour pressure: The pressure exerted by the vapour of a liquid (or solid) when it is in
equilibrium with the liquid (or solid) phase at a constant temperature is called the x1 = 1 x2
vapour pressure of the liquid (or solid).
P = x1P0
The vapour pressure of a liquid increases with the increase in temperature.
= (1 x2)P0

= P0 x2P0
Relative vapour pressure of a solution : If P0 is the vapour pressure of a pure liquid
P0 P = x2P0
(solvent) and P is the vapour pressure of a solution after adding a nonvolatile solute,
then, relative vapour pressure P = P/P0 x2 = 𝑃0−𝑃𝑃0
Lowering of vapour pressure of a solution : When a nonvolatile solute is added to a P0 P = P is the lowering of vapour pressure
pure solvent, the surface area is covered by the solute molecule decreasing the rate of
evaporation, hence its vapour pressure decreases. This decrease in vapour pressure is x2 = Δ𝑃𝑃0
called lowering of vapour pressure. In the equation, 𝑃0−𝑃𝑃0 is called relative lowering of vapour pressure.
Hence Raoult’s law can also be stated as the relative lowering of vapour pressure is Then number of moles of a solvent = n1 = W1/ M1
equal to mole fraction of the solute.
Number of moles of a solute = n2 = W2/ M2
Q. Show that relative lowering of vapour pressure is a colligative property. Ans.
Total number of moles = n = n1 + n2
Consider a binary solution containing a nonvolatile solute. If P0 and P are Solutions and
colligative properties. Mole fraction of the solvent = x1 = n1/n

Mole fraction of the solute = x2 = n2/n

vapour pressures of a pure solvent and the solution respectively then, Lowering of x1 + x2 = 𝑛1𝑛+𝑛2𝑛=𝑛1+𝑛2𝑛=𝑛𝑛=1
vapour pressure = P = P0 P
x1 + x2 =1
Relative lowering of vapour presure = 𝑃0−𝑃𝑃0
In the case of an ideal solution which is a dilute solution, the concentration and the
By Raoult’s law, number of moles of the solute are very low, i.e. n2 << n1
x2 = 𝑃0−𝑃𝑃0 n1 + n2 n1
where x2 is mole fraction of the solute. Therefore the relative lowering of vapour Now x2 = n2/n = 𝑛2𝑛1+𝑛2 ≅𝑛2𝑛1
pressure is a colligative property.
x2 = 𝑊2/𝑀2𝑊1/𝑀1=𝑊2𝑀1𝑊1𝑀2
Variation of vapour pressure with mole fraction of a solvent in solution. OR
If P0 and P are the vapour pressures of a pure solvent and a solution respectively, then
Variation of vapour pressure with the concentration of a solution : relative lowering of vapour pressure = 𝑃0−𝑃𝑃0
The vapour pressure of a pure solvent decreases when a nonvolatile solute is dissolved By Raoult’s law,
in it.
Δ𝑃𝑃0= 𝑃0−𝑃𝑃0 = x2
Consider a pure solvent with vapour pressure P0 and mole fraction x1.
∴𝑃0−𝑃𝑃0= 𝑊2/𝑀2𝑊1/𝑀1 𝑜𝑟 Δ𝑃𝑃0= 𝑊2/𝑀2𝑊1/𝑀1
For a solution containing a nonvolatile solute, if x1 and x2 are the mole fractions of a
solvent and a solute respectively, then x1 + x2 = 1 and x1 < 1. Hence by measuring the vapour pressure of a pure solvent and a solution, the molar
mass of the dissolved nonvolatile substances can be determined. .
By Raoult’s law, P = x1P0. As the mole fraction of a solvent in the solution increases the
vapour pressure increases as shown in the above Fig. When x1 becomes equal to 1, the Boiling point elevation : The boiling point of liquid is the temperature at which its
vapour pressure becomes P0, ie the vapour pressure of a pure solvent. vapour pressure equals the applied pressure. For liquids in open containers the applied
pressure is atmospheric pressure. Solutions and colligative properties.
If at any mole fraction of a solvent, the vapour of the solution is P, then the lowering of
vapour pressure will be, P = P0 P. Solutions and colligative properties.
Effect of temperature on the vapour pressure of a liquid :

Relation between relative lowering of vapour pressure and molar mass of nonvolatile The vapour pressure of a liquid is the pressure of the vapour in equilibrium with the
solute : liquid at a given temperature.

Consider a solution in which W1 gram of a solvent of molar mass (or molecular weight) The evaporation of a liquid requires thermal energy. Hence, as temperature rises, the
M1 contains W2 gram of a solute of molar mass M2. vapour pressure rises until it becomes equal to the external pressure, generally the
atmospheric pressure, 101.3 kNm-2 (1 atm). This temperature is called the normal ΔTb ∝ m or ΔTb = Kbm
boiling point of the liquid.
where m is the molality of solution. The proportionality constant Kb is called boiling
Elevation in the boiling point of a solution : point elevation constant or molal elevation constant or ebullioscopic constant.

The elevation in the boiling point of a solution is defined as the difference between the If m = 1, ΔTb = Kb
boiling points of the solution and the pure solvents at a given pressure, e.g. If To and T
Thus, ebullioscopic constant is the boiling point elevation produced by 1 molal solution.
are the boiling points of a pure solvent and a solution, then the elevation in boiling
point, T = T— T0. It is a colligative property. Units of Kb : Kb = ΔTb/m = K/mol kg-1= K kg mol-1 (or 0C kg mol-1)
Boiling point elevation as a consequence of vapour pressure lowering : Therefore, molal elevation constant is the elevation in boiling point produced by 1
molal solution of a nonvolatile solute.
The boiling point of a liquid is the temperature at which the vapour pressure of the
liquid becomes equal to the external pressure, generally 1 atm (101.3 x 103 Nm-2). Relation between molar mass of the solute and boiling point elevation :
When a liquid is heated, its vapour pressure rises till it becomes equal to the external
pressure. The boiling point elevation, ΔTb of a solution is directly proportional to molality (m) of
the solution. ΔTb ∝ m
If the liquid has a low vapour pressure, it has a higher boiling point.
ΔTb = Kbm Solutions and colligative properties.
Solutions and colligative properties.

where Kb is a proportionality constant

To understand the elevation of boiling point, let us compare the vapour pressures of
solution and those of pure solvent. The vapour pressures of solution and of pure If m = 1 molal, then
solvent are plotted as a function of temperature as shown in Fig. K ΔTb = Kb.
When a nonvolatile solute is added to a solvent, its vapour pressure decreases, hence where K is called molal elevation constant.
the boiling point increases.
The molality of the solution is given by,
If T0 and T are the boiling points of a pure solvent and a solution, then the elevation in
the boiling point is given by, m = 𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑒𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑖𝑛 𝑘𝑔

Tb = T — T0 Let W1 = Weight (in gram) of a solvent,

The curve AB, represents the variation in the vapour pressure of a pure solvent with W2 = Weight (in gram) of a solute
temperature while curve CD represents the variation in the vapour pressure of the M2 = Molecular weight of the solute
solution.
Then the molality (m) of the solution is given by
This elevation in the boiling point is proportional to the lowering of the vapour
pressure, i.e., P0—P, where P0 and P are the vapour pressures of the pure solvent and m = 𝑊2×1000𝑊1𝑀2= 𝑊2𝑊1𝑀2 𝑚𝑜𝑙 𝑘𝑔−1
the solution. [ Tb (P0—P) or Tb P]
ΔTb = Kb x 𝑊2×1000𝑊1𝑀2
Boiling point elevation and concentration of solute : The boiling point elevation is
M2 = 𝑘𝑏×𝑊2×1000𝑊1Δ𝑇𝑏 or M2 = 𝑘𝑏×𝑊2𝑊1Δ𝑇𝑏 𝑚𝑜𝑙 𝑘𝑔−1
directly proportional to the molality of the solution. Thus,
If the weights and molecular weight are expressed in kg, then, Freezing point depression as a consequence of vapour pressure lowering :

ΔTb = Kb x 𝑊2𝑊1𝑀2 The effect of dissolution of a nonvolatile solute into a solvent on freezing point of
solvent can be understood in terms of the vapour pressure lowering.
Molal elevation constant (Ebullioscopic constant) : It is defined as the elevation in
boiling point, produced by dissolving one mole of a solute in 1 kg (or 1000 gram) of a The freezing point of a liquid is the temperature at which the liquid and the solid have
solvent (i.e. 1 molal solution). the same vapour pressure.

The elevation in the boiling point, Addition of a nonvolatile solute to a liquid decreases the freezing point, i.e. the freezing
point of the solution is less than that of the pure solvent.
ΔTb is given by
This is due to the lowering of the vapour pressure of the solvent by the addition of the
ΔTb = Kb x m
nonvolatile solute. Solutions and colligative properties.
where Kb is molal elevation constant and m is molality of the solution.

When m =1, ΔTb = Kb

When a liquid is cooled from the point A, its vapour pressure decreases and at the point
Kb depends only on the nature of the solvent. B, it freezes (solidifies).

Kb does not depend on the nature of the solute. In case of a solution, since the vapour pressure is lowered, the freezing point decreases.
Hence, if the solution is cooled from the point F, it freezes at lower temperature E, than
It does not depend on concentration of the solution. the pure liquid. This is also due to separation of solvent molecules due to solute
molecules decreasing their intermolecular attraction.

The units of molal elevation constant are : (A) K kg mol-1 and (B) K m-1 Solutions and If T0 and T are the freezing points of a pure solvent and the solution, then, the
colligative properties. depression in the freezing point is given by,

ΔTf = T0 — T.

Depression in freezing point : This depression ΔTf depends on the lowering of the vapour pressure (P0 — P)

Freezing point of a liquid : The freezing point of a liquid is defined as the temperature ΔTf (P0 — P),
at which the solid coexists in the equilibrium with the liquid and the vapour pressure of where P0 and P are the vapour pressures of the pure liquid and the solution.
the liquid and the solid are equal.
Freezing point depression and concentration of solute :
Depression in the freezing point of a solution : The depression in the freezing point of
a solution is defined as the difference between the freezing points of a pure solvent and As verified experimentally for a dilute solution the freezing point depression (ΔTf) is
that of the solution. directly proportional to the molality of solution. Thus,

If T0 and T are the respective freezing points of a pure solvent and a solution, then the ΔTf ∝ m or ΔTf = Kf m
depression in the freezing point ΔTf is given by,
where m is the molality of the solution, Kf is a constant of proportionality.
ΔTf = T0 — T (….T < T0)
If m = 1 molal,
The depression in the freezing point (ΔTf) is a colligative property.
ΔTf = Kf. Hence Kf is called the cryoscopic constant or molal depression constant. Kf is Besides the boiling point elevation and freezing point depression, the osmotic pressure
characteristic of the solvent. is associated with vapour pressure lowering and can be used to determine molar
masses of dissolved solutes.
Cryoscopic constant Kf (or molal depression constant) : Molal depression constant is
defined as the depression in freezing point, produced by dissolving one mole of a solute Permeable membrane : A membrane which allows free transfer of the solute molecules
in 1 kg (or 1000 g) of a solvent (i.e. 1 molal solution). from a solution of a higher concentration to a solution of a lower concentration through
it is called a permeable membrane and the transfer is called diffusion, e.g., a membrane
Unit of Kf : ΔTf/m = (K or 0C)/(mol kg-1)= K kg mol-1 or 0C kg mol-1
of a paper.
Relationship between freezing point depression of a solution containing non-volatile
Semipermeable membrane : A membrane which allows free passage of only the
nonelectrolyte and its molar mass :
solvent molecules but not the large solute molecules or ions of large molecular mass
The freezing point depression, ΔTf of a solution is directly proportional to molality (m) from a solution of a lower concentration (or a pure solvent) to a solution of higher
of the solution. concentration through it, is called a semipermeable membrane, e.g. parchment paper,
complex like Cu2[Fe (CN)6], etc. Solutions and colligative properties.
ΔTf m Solutions and colligative properties.

Osmosis : It is defined as the net spontaneous flow of solvent molecules into the
ΔTf = Kf m solution or from more dilute solution to more concentrated solution through a
where Kf is a molal depression constant. semipermeable membrane is called osmosis.

The molality of a solution is given by, Consider a vessel divided into two compartments by a semipermeable membrane.

m = 𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑒𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑖𝑛 𝑘𝑔 When one compartment is filled with a pure solvent or a dilute solution and another by
concentrated solution, there is a spontaneous flow of solvent molecules to the
If W1 grams of a solvent contain W2 grams of a solute of the molar mass M2, then the concentrated solution. This arises due to higher vapour pressure of a pure solvent or
molality m of the solution is given by, dilute solution than concentrated solution.
m = 𝑊2×1000𝑊1𝑀2= 𝑊2𝑊1𝑀2 𝑚𝑜𝑙 𝑘𝑔−1 Example : A flow of water molecules from a dilute solution into a concentrated glucose
ΔTf = Kf x 𝑊2×1000𝑊1𝑀2 solution through a parchment paper.

M2 = 𝐾𝑓×𝑊2×1000𝑊1Δ𝑇𝑓 or M2 = 𝐾𝑓×𝑊2𝑊1Δ𝑇𝑓 𝑚𝑜𝑙 𝑘𝑔−1 Osmotic pressure : The osmotic pressure is defined as the excess mechanical pressure
required to be applied to a solution separated by a semipermeable membrane from
If the weights and molecular weight are expressed in kg, then, pure solvent or a dilute solution to prevent the osmosis or free passage of the solvent
molecules at a given temperature. The osmotic pressure is a colligative property.
ΔTf = Kf x 𝑊2𝑊1𝑀2
Osmosis can be demonstrated with experimental set up shown in Fig.
The unit of Kf is K kg mol-1 .
Consider an inverted thistle funnel on the mouth of which a semipermeable
Hence, from the measurement of the depression in the freezing point of the solution,
membrane is firmly fastened.
the molar mass of the substance can be determined.
It is filled with the experimental solution and immersed in a solvent like water.
Osmotic pressure :
Solutions and colligative properties.
 Relation between osmotic pressure and molar mass of a solute :

Consider V dm3 (litres) of a solution containing W2 mass of a solute of molar mass M2

at a temperature T.
As a result, solvent molecules pass through the membrane into the solution in the
funnel causing rising of level in the arm of thistle funnel. Number of moles of solute, n2 = W2/M2

This increases the hydrostatic pressure. The osmotic pressure is given by,

At a certain stage this rising level stops indicating an equilibrium between the rates of = 𝑊2𝑅𝑇𝑀2𝑉
flow of solvent molecules from solvent to solution and from solution to solvent. The
𝑀2= 𝑊2𝑅𝑇𝜋𝑉
hydrostatic pressure at this stage represents osmotic pressure of the solution in the
thistle funnel. By measuring osmotic pressure of a solution, the molar mass of a solute can be
calculated.

Since osmotic pressure can be measured more precisely, it is widely used to measure
Remember : It is important to note that osmotic pressure is not the pressure produced
molar masses of the substances
by a solution. It exists only when the solution is separated from the solvent by a
suitable kind of semipermeable membrane. Isotonic solutions : The solutions having the same osmotic pressure at a given
temperature are called isotonic solutions.
Relation between osmotic pressure and concentration of solution :
Explanation : If two solutions of substances A and B contain nA and nB moles dissolved
Consider V dm3 of a solution in which n1 moles of a solvent contains n2 moles of a
in volume V (in dm3) of the solutions, then their concentrations are,
nonvolatile solute at absolute temperature T.
CA = nA/V (in mol dm-3) and CB = nB/V (in mol dm-3)
The osmotic pressure, of a solution is given by,
If the absolute temperature of both the solutions is T, then by the van’t Hof equation,
= nRT/V
A = CART and B = CBRT, where A and B are their osmotic pressures.
R is gas constant having value 0.08206 dm3 atm K-1 mol-1 (OR L atm K-1 mol-1). Since
concentration, C of a solution is in mol dm-3 or molarity is, For the isotonic solutions,
C = n/V mol dm-3 or M A= B
= CRT, (If concentration C is expressed in mol m-3 and R = 8.314 J K-1 mol-1, then CA = CB
will be in SI units, pascals or Nm-2.) Solutions and colligative properties.
𝑛𝐴𝑉=𝑛𝐵𝑉 Solutions and colligative properties.

nA = nB
Measurements of osmotic pressure are made at a certain constant temperature.
Hence, equal volumes of the isotonic solutions at the same temperature will contain
Molality depends upon temperature but molality is independent of temperature. equal number of moles (hence, equal number of molecules) of the substances.
Hence in osmotic pressure measurements, concentration is expressed in molarity.
Hypotonic solutions : When two solutions have different osmotic pressures, then the Remember : Osmotic pressure is much larger and therefore more precisely measurable
solution having lower osmotic pressure is said to be a hypotonic solution with respect property than other colligative properties. It is therefore, useful to determine molar
to the other solution. masses of very expensive substances and of the substances that can be prepared in
small quantities.
Explanation : Consider two solutions of the substances A and B having osmotic
pressures A and B. If B is less than A, then the solution B is a hypotonic solution Collgative properties of electrolytes : The study of colligative properties of electrolytes,
with respect to the solution A. however, require a different approach than used for colligative properties of
nonelectrolytes.
Hence, if CA and CB are their concentrations, then, CB < CA. Hence, for equal volumes
of the solutions, nB < nA. Following are the experimental observations for the colligative behavior of electrolytes.

Hypertonic solutions : When two solutions have different osmotic pressures, then the The electrolytic solutions do not exhibit colligative properties similar to
solution having higher osmotic pressure is said to be a hypertonic solution with respect nonelectrolytes.
to the other solution.
The colligative properties of electrolytes are higher than those shown by equimolar
Explanation : Consider two solutions of substances A and B having osmotic pressures solutions of nonelectrolytes.
A and B. If B is greater than A, then the solution B is a hypertonic solution with
The molar masses of electrolytes determined by colligative properties are found to be
respect to the solution A.
considerably lower than their actual molar masses.
Hence, if CA and CB are their concentrations, then, CB > CA. Hence, for equal volumes
of the solutions, nB > nA.
Q. Why are the colligative properties of electrolytic solutions greater than those for
Reverse osmosis : osmosis is a flow of solvent through a semipermeable membrane
nonelectrolytic solutions with same concentration ?
into the solution. The direction of osmosis can be reversed by applying a pressure larger
than the osmotic pressure. Ans. The electrolytes in polar solvents or aqueous solutions dissociate into two or more
ions whereas nonelectrolytes do not dissociate. Solutions and colligative properties.
The phenomenon of the passage of solvent like water under high pressure from the
concentrated aqueous solution like sea water into pure water through a semipermeable
membrane is called reverse osmosis.
Consequently the number of particles in electrolytic solutions are considerably higher
The osmotic pressure of sea water is about 30 atmospheres. Hence when pressure than equimolar nonelectrolytic solutions.
more than 30 atmospheres is applied on the solution side, regular osmosis stops and
reverse osmosis starts. Hence pure Water from sea water enters the other side of pure Therefore the colligative properties of electrolytes are greater than nonelectrolytes
water. Solutions and colligative properties. with same concentration in solution.

Abnormal colligative property : When the experimentally measured colligative

property of a solution is different from that calculated theoretically by the van’t Hoff
For this purpose a suitable semipermeable membrane is required which can withstand equation or by the laws of osmosis, then the solution is said to have abnormal
high pressure conditions over a long period. colligative property.
This method is used successfully in Florida since 1981 producing more than 10 million Explanation :
litres of pure water per day.
 The colligative property depends on the number of solute particles in the solution but It is defined as a ratio of the observed colligative property of the solution to the
it is independent of their nature. Abnormal values of them arise when the dissolved theoretically calculated colligative property of the solution without considering
solute undergoes a molecular change like dissociation or association in the solution. molecular change.

The observed colligative property (or abnormal colligative property) may be higher or The van’t Hoff factor can be represented as, 𝑖=𝑂𝑏𝑠𝑒𝑟𝑣𝑒𝑑 𝑣𝑎𝑙𝑢𝑒 𝑜𝑓 𝑐𝑜𝑙𝑙𝑖𝑔𝑎𝑡𝑖𝑣𝑒
lower than the theoretical value. 𝑝𝑟𝑜𝑝𝑒𝑟𝑡𝑦𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑣𝑎𝑙𝑢𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑙𝑙𝑖𝑔𝑎𝑡𝑖𝑣𝑒 𝑝𝑟𝑜𝑝𝑒𝑟𝑡𝑦
This colligative property may be the lowering of vapour pressure of a solution, the
osmotic pressure, the elevation in the boiling point or the depression in the freezing
Dissociation of the solute molecules: When a solute like an electrolyte is dissolved in a
point of the solution. Hence, 𝑖 =𝑂𝑏𝑠𝑒𝑟𝑣𝑒𝑑 𝑙𝑜𝑤𝑒𝑟𝑖𝑛𝑔 𝑜𝑓 𝑣𝑎𝑝𝑜𝑢𝑟 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙
polar solvent like water, it undergoes dissociation, which results in the increase in the
𝑙𝑜𝑤𝑒𝑟𝑖𝑛𝑔 𝑜𝑓 𝑣𝑎𝑝𝑜𝑢𝑟 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒
number of particles in the solution.
= P(ob)/ P(th) 𝑖 =𝑂𝑏𝑠𝑒𝑟𝑣𝑒𝑑 𝑒𝑙𝑒𝑣𝑎𝑡𝑖𝑜𝑛 𝑖𝑛 𝑏𝑜𝑖𝑙𝑖𝑛𝑔 𝑝𝑜𝑖𝑛𝑡𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑒𝑙𝑒𝑣𝑎𝑡𝑖𝑜𝑛 𝑖𝑛
Hence, the observed value of the colligative property becomes higher than the
𝑏𝑜𝑖𝑙𝑖𝑛𝑔 𝑝𝑜𝑖𝑛𝑡
theoretical value, e. g. when one mole of KCI is dissolved in the solution then due to
dissociation, KCl —> K+ + Cl-, the number of particles increases, hence, the colligative = Tb(ob)/ Tb(th) 𝑖 =𝑂𝑏𝑠𝑒𝑟𝑣𝑒𝑑 𝑑𝑒𝑝𝑟𝑒𝑠𝑠𝑖𝑜𝑛 𝑖𝑛 𝑓𝑟𝑒𝑒𝑧𝑖𝑛𝑔 𝑝𝑜𝑖𝑛𝑡𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙
properties like osmotic pressure, elevation in the boiling point, etc. increase. 𝑑𝑒𝑝𝑟𝑒𝑠𝑠𝑖𝑜𝑛 𝑖𝑛 𝑓𝑟𝑒𝑒𝑧𝑖𝑛𝑔 𝑝𝑜𝑖𝑛𝑡

Association of the solute molecules: When a solute like a nonelectrolyte is dissolved in = Tf(ob)/ Tf(th) 𝑖 =𝑂𝑏𝑠𝑒𝑟𝑣𝑒𝑑 𝑜𝑠𝑚𝑜𝑡𝑖𝑐 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑜𝑠𝑚𝑜𝑡𝑖𝑐 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒
a nonpolar solvent like benzene, it undergoes association forming molecules of higher
= (ob)/ (th) Solutions and colligative properties.
molecular mass. Hence, the number of particles in the solution decreases. Therefore
the colligative properties like osmotic pressure, elevation in the boiling point, etc., are
lower than the theoretical value.

e.g. nA —> An. 2CH3COOH -> (CH3COOH)2 Solutions and colligative properties.
When the solute neither undergoes dissociation or association in the solution, then, i
=1

Abnormal osmotic pressure : When the experimentally observed osmotic pressure is When the solute undergoes dissociation in the solution, then, i > l
different than theoretically calculated value by van’t Hoff’s equation, then it is called
When the solute undergoes association in the solution, then i < 1
abnormal osmotic pressure.

This arises when the dissolved solute undergoes a molecular change like association or
dissociation. From the value of the van’t Hoff factor, the degree of dissociation of electrolytes,
degree of association of nonelectrolytes can be obtained.
Abnormal molecular masses : When the observed molecular masses obtained from
their colligative properties of the substances are different (higher or lower) than the van’t Hoff factor gives the important information about the solute molecules in the
theoretical or normal values calculated from their molecular formulae, then they are solution and chemical bonding in them.
called abnormal molecular masses.
van’t Hoff factor related to molecular mass of the substance :
Van’t Hoff factor : To obtain the colligative properties of electrolyte solutions by using
The van’t Hoff factor is also defined as, 𝑖 =𝑎𝑐𝑡𝑢𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 𝑖𝑛 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
relations for nonelectrolytes, van’t Hoff suggested a factor i.
𝑎𝑓𝑡𝑒𝑟 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑓𝑜𝑟𝑚𝑢𝑙𝑎 𝑢𝑛𝑖𝑡𝑠 𝑑𝑖𝑠𝑠𝑜𝑙𝑣𝑒𝑑 𝑖𝑛 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛=𝑀𝑡ℎ𝑀𝑜𝑏

In case of nonelectrolytes, i < 1.

In case of electrolytes, i > 1. For example for KNO3 and NaCl, i = 2, for Na2SO4, CaCl2, i = m[1 + x + y — ]
= 3, etc.
= m[1 + (x + y — 1)]
Modification of expressions of colligative properties : The expressions of colligative
The van’t Hoff factor i will be, 𝑖=𝑂𝑏𝑠𝑒𝑟𝑣𝑒𝑑 𝑐𝑜𝑙𝑙𝑖𝑔𝑎𝑡𝑖𝑣𝑒 𝑝𝑟𝑜𝑝𝑒𝑟𝑡𝑦𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙
properties mentioned earlier for nonelectrolytes are to be modified so as to make them
𝑐𝑜𝑙𝑙𝑖𝑔𝑎𝑡𝑖𝑣𝑒 𝑝𝑟𝑜𝑝𝑒𝑟𝑡𝑦=m[1 + (x + y — 1)]m
applicable for electrolyte solutions.
i = 1 + (x + y — 1)
The modified equations are:
If total number of ions from one mole of electrolyte is denoted by n, then (x + y) = n
By Raoult’s law : 𝑃0−𝑃𝑃=𝑖𝑥2=𝑖 ×𝑊2×𝑀1𝑊1×𝑀2
i = 1 + (n — 1)
For elevation in boiling point :
(n — 1) = i - 1
Tb = i x Kb x m = 𝑖 ×𝐾𝑏×𝑊2×1000𝑊1×𝑀2
= 𝑖−1𝑛−1 …..(1)
Tb = 𝑖 ×𝐾𝑏×𝑊2𝑊1×𝑀2
This is a relation between van’t Hoff factor i and degree of dissociation of an
For depression in freezing point
electrolyte. Solutions and colligative properties.
Tf = i x Kf x m = 𝑖 ×𝐾𝑓×𝑊2×1000𝑊1×𝑀2

Tf = 𝑖 ×𝐾𝑓×𝑊2𝑊1×𝑀2 Solutions and colligative properties.

Relation between van’t Hoff factor and molar mass of electrolyte :

Consider an elctrolyte AxBy that dissociates in aqueous solution as

For Osmotic pressure :
AxBy xAy+ + yBx-
= iCRT = 𝑖×𝑛𝑅𝑇𝑉 =𝑖×𝑊𝑅𝑇𝑀𝑉
Initially : 1 0 0
Relationship between degree of dissociation of an electrolyte and van’t Hoff factor :
At equilibrium : (1-∝) (x∝) (y ∝)
Consider 1 dm3 of a solution containing m moles of an electrolyte AxBy. The electrolyte
If i is van’t Hoff factor and n is total number of ions produced from dissociation of one
on dissociation gives x number of Ay+ ions and y number of Bx- ions.
mole of electrolyte then, the degree of dissociation ∝ is given by,
Let be the degree of dissociation.
= 𝑖−1𝑛−1
At equilibrium,
Now if Mth and Mob are theoretical and observed molecular (or molar) masses
AxBy x Ay+ + y Bx- respectively, then, 𝑖 =𝑀𝑡ℎ𝑀𝑜𝑏

For 1 mole of electrolyte : 1 — , x , y (n — 1) = i – 1 = 𝑀𝑡ℎ𝑀𝑜𝑏−1

and For ‘m’ moles of an electrolyte : m(1 — ), mx , my are the number of particles. (n — 1) = 𝑀𝑡ℎ−𝑀𝑜𝑏𝑀𝑜𝑏

Total number of moles at equilibrium, will be, = 1n — 1[ 𝑀𝑡ℎ−𝑀𝑜𝑏𝑀𝑜𝑏 ] ….. (2)

Total moles = m(1 — ) + mx + my This is a relation between degree of dissociation and molecular masses of the dissolved
electrolyte AxBy
= m[(1 — ) + x + y ]
Q. Arrange the following solutions in order of increasing osmotic pressure. Assume
complete ionization. a) 0.5m Li2SO4 b) 0.5m KCl c) 0.5m Al2(SO4)3 d) 0.1m BaCl2.

Ans.

Consider 1 dm3 of each solution.

a) 0.5m Li2SO4

(a) Li2SO4 --> 2Li+ + SO42- (Total particles =2x0.5+0.5=1.5m)

b) 0.5m KCl

KCl --> K+ + Cl- (Total particles =0.5+0.5=1m)

c) 0.5m Al2(SO4)3

Al2(SO4)3 2Al3+ + 3SO42- (Total particles =2x0.5+3x0.5=1+1.5=2.5m) Solutions and

colligative properties.

d) 0.1m BaCl2.

BaCl2 --> Ba2+ + 2Cl- (Total particles =0.1+2x0.1=0.1+0.2=0.3m)

Osmotic pressure being a colligative properly, it depends on number of particles in the

solution.

Therefore, increasing order of osmotic pressure is,

BaCl2 < KCl < Li2SO4 < Al2(SO4)3

03m 1m 1.5m 2.5m