MODULE-I

VAPOUR PRESSURE:
Consider a pure liquid in a beaker is covered with a jar. Some molecules on the liquid surface

evaporate and fill the vacant space available to them. The molecules in the vapour phase move

randomly in the vacant space, during this motion, they strike the surface of the liquid and

condensed. This process of evaporation and condensation go on and an equilibrium is

established between evaporation and condensation. The pressure exerted by vapours over the

liquid surface at equilibrium is called vapour pressure of the liquid.

If solute is non-volatile solid or liquid the vapour pressure of solution is equal to partial vapour

pressure of solvent in the solution and if the solute is volatile solid or liquid, then vapour

pressure will be equal to the sum of partial vapour pressure of solute and that of solvent.

RAOULT’S LAW:

In 1986, a French Chemist named Francois Marte Raoult proposed a quantitative relation

between partial pressure and mole fraction of volatile liquids. The law states that mole fraction

of the solute component is directly proportional to its partial pressure.

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Image 1: Types of Solutions

On the basis of Raoult’s Law, liquid-liquid solutions are classified into two types of solutions,

they are:

 Ideal Solutions

 Non-ideal Solutions

Ideal and Non – Ideal Solutions

The solutions which obey Raoult’s law at all compositions of solute in solvent at all

temperature are called ideal solutions.

Ideal solutions can be obtained by mixing two components with identical molecular size,

structure and they should have almost same inter molecular attraction e.g., two liquids A and

B form an ideal solution when A –A and B–B molecular attractions will be same and hence

A–B molecular atrraction will be almost same as A–A and B–B molecular attraction.

An ideal solution should have following characteristics

 It should obey Raoult’s law i.e., PA = XA and PB = XB

 Hmixing = 0, i.e. no heat should be absorbed or evolved during mixing

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 Vmixing = 0, i.e. no expansion or contraction on mixing ?

Examples of Ideal solutions

 Ethyl chloride and ethyl bromide

 n–hexane and n–heptane
 CCl4 and SiCl4

The solution which deviate from ideal behaviour are called non ideal solution or real

solutions and they do not obey Raoult’s law over entire range of composition.

It has been found that on increasing dilution, a non ideal solution tend to be ideal.

For non ideal solutions,

 PA XAP0A, PB ¹ XBP0B i.e, they do not obey Raoult’s law

 Hmixing 0,

 Vmixing = 0

Here we may have two cases

Case 1:

Such a solution shows positive deviation from Raoult’s Law and the observed boiling point

of such solutions is found to be less than the calculated value. e.g. cyclohexane and ethanol.

In ethanol the molecules are held together due to hydrogen bonding, when cyclohexane is

added to ethanol the molecules of cyclohexane tend to occupy the space between ethanol

molecules due to which some hydrogen bonds break due to which inter molecular attraction

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between cyclohexane and ethanol is reduced and hence show higher vapour pressure.

Examples of solutions showing positive deviation:

 Acetone + Ethanol

 Acetone- Benzene

 Water + Methanol

 Water + Ethyanol

Case 2:

Solutions of above type show negative deviation from Raoult’s law and their observed

boiling point is found to be higher than the calculated value eg. When acetone and chloroform

are mixed together a hydrogen bond is formed between them which increases inter molecular

attraction between them and hence decreases the vapour pressure

Examples of solutions showing negative deviation:

 Acetone + Aniline

 Chloroform + Diethyl ether

 Chloroform + Benzene

 Water + HCl

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Condition for forming non-ideal solution showing positive deviation

Two liquids A & B on mixing form this type of solutions when

 A-B attractive force should be weaker than A-A and B-B attractive force.

 “A” and “B” have different shape, size and character.

 “A” and “B” escape easily showing higher vapour pressure than the expected value.

Condition for forming non-ideal solution showing negative deviation

Two liquids A & B on mixing form this type of solutions when

 A-B attractive force should be greater than A-A and B-B attractive force.

 “A” and “B” have different shape, size and character.

 Escaping tendency of both “A” and “B” is lower showing lower vapour pressure than

expected ideally.

Comparison between Ideal and Non-ideal solution

Non-ideal solutions
Ideal solutions Positive deviation from Negative deviation from
Raoult’s law Raoult’s law
Obey Raoult’s law at every Do not obey Raoult’s law. Do not obey Raoult’s law
range of concentration.
Hmix = 0; neither is Hmix>0. Endothermic Hmix<0. Exothermic
evolved nor absorbed dissolution; heat is dissolution; heat is evolved.
during dissolution. absorbed.

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 Vmix = 0; total volume of Vmix > 0. Volume is Vmix <0. Volume is
solution is equal to sum of increased after dissolution. decreased during
volumes of the dissolution.
components.
P = pA + pB = pA0XA + pA > pA0XA; pB > pB0XB pA < pA0XA; pB < pB0XB
pB0XB ∴ pA + pB > pA0XA + pB0XB ∴ pA + pB < pA0XA + pB0XB
A—A, A—B, B—B A—B attractive force should A—B attractive force should
interactions should be same, be weaker than A—A and be greater than A—A and
i.e., ‘A’ and ‘B’ are B—B attractive forces. ‘A’ B—B attractive forces. ‘A’
identical in shape, size and and ‘B’ have different shape, and ‘B’ have different shape,
character. size and character. size and character.
Escaping tendency of ‘A’ ‘A’ and B’ escape easily Escaping tendency of both
and ‘B’ should be same in showing higher vapour components ‘A’ and ‘B’ is
pure liquids and in the pressure than the expected lowered showing lower
solution. value. vapour pressure than
expected ideally.

AZEOTROPES:

Azeotropes are defined as a mixture of two liquids which has a constant composition in liquid

and vapour phase at all temperatures. Azeotropes can’t be separated by fractional distillation,

as the composition of vapour phase remains same after boiling. Because of uniform

composition azeotropes are also known as Constant Boiling Mixtures.

There are two types of Azeotropes:

 Maximum Boiling Azeotrope

 MinimumBoilingAzeotrope

Maximum Boiling Azeotrope

Maximum Boiling Azeotrope is formed when we mix two non-ideal solutions at some specific

composition, showing large negative deviation from Raoult’s law.

Examples:

 Nitric Acid (HNO3) (68%) and water (32%) form maximum boiling azeotrope at boiling

temperature of 393.5 K

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 Hydrochloric Acid (HCl) (20.24%) and water form maximum boiling azeotrope at

boiling temperature of 373 K

Minimum Boiling Azeotrope

Minimum Boiling Azeotrope is formed when we mix two non-ideal solutions at some specific

composition, which shows large positive deviation from Raoult’s Law.

Example:

 Ethanol (95.5 %) and water (4.5 %) form minimum boiling azeotrope at boiling

temperature of 351.5 K

COLLIGATIVE PROPERTIES:

A dilute solution is one in which the amount of the solute is very small in comparison to the

amount of the solvent.The dilute solutions show more or less ideal behavior as the heat and

volume changes, accompanying the mixing of solute and solvent, are negligible for all

practical purposes. Dilute solutions obey Raoult’s law. The properties of dilute solutions

which depend only on number particles of solute present in the solution and not on their

identity are called colligative properties (denoting depending upon collection).

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We shall assume here that the solute is non-volatile, so it does not contribute to the vapour.

We shall also assume that the solute does not dissolve in solid solvent, that is, the pure solid

solvent separates when the solution is frozen, the latter assumption is quite drastic, although

it is true for many mixtures, it can be avoided.

Colligative properties are the properties of only dilute solution which are supposed to behave

as ideal solutions. The various colligative properties are:

 Depression of freezing point

 Lowering of vapour pressure

 Osmotic pressure

 Elevation of boiling point

LOWERING OF VAPOUR PRESSURE BY NON VOLATILE SOLUTE:

It has been known for a long time that when a non-volatile solute is dissolved in a liquid, the

vapour pressure of the solution becomes lower than the vapour pressure of the pure solvent.

In 1886, the French chemist, Francois Raoult, after a series of experiments on a number of

solvents including water, benzene and ether, succeeded in establishing a relationship between

the lowering of vapour pressure of a solution and the mole fraction of the non-volatile solute.

Let us consider a solution obtained by dissolving n moles of a non-volatile solute in N moles

of a volatile solvent. Then mole fraction of the solvent, X 1 = N/(n+N) and mole fraction of

the solute, X2 = n /(N +n). Since the solute is non-volatile, it would have negligible vapour

pressure. The vapour pressure of the solution is, therefore merely the vapour pressure of the

solvent. According to Raoult's law, the vapour pressure of a solvent (P1) in an ideal solution

is given by the expression;

P1 = X1 P10 ................(1)

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where P10 is the vapour pressure of the pure solvent. Since X1 + X 2 = 1, Eq. 1 may be written

as

The expression on the left hand side of Equation (3) is usually called the relative lowering of

vapour pressure. Equation (3) may thus be stated as: `The relative lowering of vapour

pressure of a solution containing a non-volatile solute is equal to the mole fraction of the

solute present in the solution.'

This is one of the statements of the Raoult's law.

Since mole fraction of the solute, X 2 is given by n/(N+n), Equation (3) may be expressed as

It is evident from Equation (4) that the lowering of vapour pressure of a solution depends

upon the number of moles (and hence on the number of molecules) of the solute and not upon

the nature of the solute dissolved in a given amount of the solvent. Hence, lowering of vapour

pressure is a colligative property.

Determination of Molar Masses from Lowering of Vapour Pressure

It is possible to calculate molar masses of non-volatile non-electrolytic solutes by measuring

vapour pressures of their dilute solutions.

Suppose, a given mass, w gram, of a solute of molar mass m, dissolved in

W gram of solvent of molar mass M, lowers the vapour pressure from P10 to P1.

Then , by Equation (4)

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Since in dilute solutions, n is very small as compared to N, Equation (5) may be put in the

approximate form as

Limitations of Raoult’s Law

 Raoult’s law is applicable only to very dilute solutions.

 It is applicable to solutions containing non-volatile solute only.

 It is not applicable to solutes which dissociate or associate in a particular solution.

Question

The density of a 0.438 M solution of potassium chromate at 298 K is 1.063 g cm-3. Calculate

the vapour pressure of water above this solution. Given : P0 (water) = 23.79 mm Hg.

Solution

A solution of 0.438 M means 0.438 mol of K2CrO4 is present in 1L of the solution. Now,

Mass of K2CrO4 dissolved per litre of the solution = 0.438 194 = 84.972 g

Mass of 1L of solution = 1000 1.063 = 1063 g

Amount of water in 1L of solution = 978.028/18 = 54.255 mol

Assuming K2CrO4 to be completely dissociated in the solution, we will have;

Amount of total solute species in the solution = 3 0.438 = 1.314 mol.

Mole fraction of water solution = 54.335/(54.335+1.314) = 0.976

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Finally, Vapour pressure of water above solution = 0.976 23.79 = 23.22 mm Hg

BOILING POINT ELEVATION BY A NON-VOLATILE SOLUTE:

The boiling point of a liquid is the temperature at which its vapour pressure becomes equal to

760 mm (i.e. 1 atmospheric pressure). Since the addition of a non-volatile solute lowers the

vapour pressure of the solvent, the vapour pressure of a solution is always lower than that of

the pure solvent, and hence it must be heated to a higher temperature to make its vapour

pressure equal to atmospheric pressure. Thus the solution boils at a higher temperature than

the pure solvent. If Tb0 is the boiling point of the solvent and Tb is the boiling point of the

solution, the difference in boiling points ( Tb) is called the elevation of boiling point.

Thus, Tb –Tb0 = Tb.

Tb a molality where Tb = elevation of boiling point

n= no. of moles of non-volatile solute

N= Total no. of moles in the solution

This implies that the boiling point elevation in a dilute solution is directly proportional to the

number of moles of the solute dissolved in a given amount of the solvent and is quite

independent of the nature of the solute. Hence, boiling point elevation is a colligative property

Tb = Kb m

kb : molal elevation constant or Ebullioscopic constant

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m : molality of the solution

Molal boiling point elevation constant or ebullioscopic constant of the solvent, is defined

as the elevation in boiling point which may theoretically be produced by dissolving one mole

of any solute in 1000 g of the solvent.

or

where m1 = molecular weight of solute and w and W are weights of solute and solvent.

DEPRESSION OF FREEZING POINT BY A NON-VOLATILE SOLUTE:

Freezing point is the temperature at which solid and liquid states of a substance have the

same vapour pressure. It is observed that the freezing point of the solution (Tf) containing

non volatile solute is always less than the freezing

point of the pure solvent (Tf0). Thus, Tf0 - Tf = Tf

It can be seen that

Tf molality

that, is freezing point depression of a dilute

solution is directly proportional to the number of

moles of the solute dissolved in a given amount of

the solvent and is independent of the nature of

solute

or Tf = Kfm

kf : molal freezing point depression constant of the solvent or cryoscopic constant

m : molality of the solution

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Molal freezing point depression constant of the solvent or cryoscopic constant, is defined as

the depression in freezing point which may theoretically be produced by dissolving 1 mole of

any solute in 1000g of the solvent.

where m1 = molecular weight of solute and w and W are weights of solute and solvent.

OSMOSIS AND OSMOTIC PRESSURE:

The phenomenon of the passage of pure solvent from a region of lower concentration (of the

solution) to a region of its higher concentration through a semi-permeable membrane is

called osmosis.

The driving force of osmosis is what is known as osmotic pressure. It is the difference in the

pressure between the solution and the solvent system or it is the excess pressure which must

be applied to a solution in order to prevent flow of solvent into the solution through the semi-

permeable membrane. Once osmosis is complete the pressure exerted by the solution and the

solvent on the semi-permeable membrane is same.

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Van't Hoff equation for dilute solutions is (parallel to ideal gas equation)

V = nRT

where = Osmotic pressure

V= volume of solution

n= no. of moles of solute that is dissolved

R = Gas constant

T= Absolute temperature

Isotonic Solutions: A pair of solutions having same osomotic pressure is called isotonic

solutions.

Reverse Osmosis

When a solution is separated from pure water by a semipermeable membrane, water moves

towards solution on account of osmosis. This process continues till osmotic pressure becomes

equal to hydrostatic pressure or osmosis can be stopped by applying external pressure equal

to osmotic pressure on solution. If external pressure greater than osmotic pressure is applied,

the flow of solvent molecules can be made to proceed from solution towards pure solvent,

i.e., in reverse direction of the ordinary osmosis. This type of osmosis is termed reverse

osmosis. Reverse osmosis is used for the desalination of sea water for getting fresh drinking

water.

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Determination of osmotic pressure: Berkeley and Hartley’s method

Various methods are employed for the measurement of osmotic pressure but the best known

method was suggested by Berkeley and Hartley. The apparatus used is shown in Fig. 5.11. A

porcelain tube having copper ferrocyanide membrane in its walls in enclosed in a metallic

jacket. The porcelain tube is fitted with a reservoir of pure solvent at one end and a capillary

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tube at the other end. In a metallic jacket is an arrangement for applying external pressure

which is measured with the help of pressure eggs.

Procedure:

The porcelain tube is filled with pure solvent and the metallic jacket with solution. The level

in the capillary tube will tend to move down as the solvent flows towards solution due to

osmosis. External pressure is now applied on the solution by the piston so that level in

capillary remain stationary. The reading of pressure gauge is recorded. This is the osmotic

pressure of the solution.

Advantages:

 It is a quick and accurate method.

 The concentration of the solution does not change because flow of solvent is not permitted

into solution; so the results obtained by this method are reliable.

 As the osmotic pressure is balanced by external pressure, there is no strain on membrane

and the danger of its bursting is eliminated. So, this method can be used to measure high

osmotic pressure also.

Comparison of osmotic pressures:

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de-Vries developed an approximate method for comparing the relative osmotic pressures of

aqueous solutions. A solution of low osmotic pressure is termed hypotonic and solution of

high osmotic pressure is termed hypotonic. The protoplasmic layer, lining the cell walls of

plant cells is easily penetrated by water but us almost impermeable to the substances dissolved

in the cellular fluid. When a plant cell is placed in hypotonic solution, the water is drawn in

and the cell swells. If the cell is placed in a hypertonic solution, water will diffuse out of the

cell fluid and partial collapse of the cell will take place when potonic solution is separated

from hypertonic solution using semipermeable membrane then osmosis takes place from

hypotonic to hypertonic because solvent concentration is greater in hypotonic solution. this

phenomenon is known as plasmolysis.

The change in cell can be placed in the solution of same osmotic pressure as that of the cell

fluid, no change in the structure of the cell is observed. Such solutions having some osmotic

pressures are termed isotonic. By putting, therefore, cells of the same kind into solutions of

different concentrations, it can be ascertained whether the solution is hypertonic or hypotonic

or isotonic.

Relation between osmotic pressure and vapour pressure

Let an aqueous dilute solution filled in a capillary tube is closed at one end by semipermeable

membrane. The tube is placed in pure solvent (water). Entire apparatus is closed by a belljar.

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At osmotic equilibrium, the belljar is saturated with water vapour. At equilibrium osmotic

pressure (π) becomes equal to hydrostatic pressure.

π=h×d …(i)

where ‘h’ is height in the column, π is osmotic pressure

Let p0 = Vapour pressure of pure solvent

p = Vapour pressure of solution

Pressure at level L1 = p0; Pressure at level L2 = p. Pressure at L1 will be greater than pressure

at L2. Then

P0 – p = hD …(ii)

where ‘d’ is density of solvent vapour of pressure p0.

Dividing Eq. (i) by (ii), we have,

at a fixed temperature d/D is constant.

∴ π = constant (p0 − p) …(iii)

i.e., π ∝ (p0 – p) or p …(iv)

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Thus, osmotic pressure is directly proportional to the lowering of vapour pressure.

We know that p0V = nRT

i.e.

….............(v)

Dividing Eq. (iii) by (v), we get

At a fixed temperature, π and M/dRT are constant.

Thus, p/p0 ∝ π, i.e., Osmotic pressure is proportional to relative lowering of vapour pressure.

ABNORMAL COLLIGATIVE PROPERTIES AND VAN’T HOFF FACTOR:

Since colligative properties depend upon the number of particles of the solute, in some cases

where the solute associates or dissociates in solution, abnormal results for molecular masses

are obtained.

Van't Hoff Factor:

Van't Hoff, in order to account for all abnormal cases introduced a factor i known as the Van't

Hoff factor, such that

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ASSOCIATION:

There are many organic solutes which in non-aqueous solutions undergo association, that is,

two or more molecules of the solute associate to form a bigger molecule. Thus, the number

of effective molecules decreases and, consequently the osmotic pressure, the elevation of

boiling point or depression of freezing point, is less than that calculated on the basis of a single

molecule. Two examples are : acetic acid in benzene and chloroacetic acid in naphthalene.

Association of Acetic acid in benzene through hydrogen bonding

Degree of Association:

The fraction of the total number of molecules which combine to form bigger molecule.

Consider one mole of solute dissolved in a given volume of solvent. Suppose n simple

molecules combine to form an associated molecule,

i.e. nA (A)n

Let a be the degree of association, then,

The number of unassociated moles = 1-a

The number of associated moles = a/n

Total number of effective moles = 1-a+a/n

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