UNIT -2 SOLUTIONS

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

Solvent: The component that is present in larger quantity in the solution is called solvent.
Solute: It is the component of a solution which is present in relatively small proportion.
Binary solution: A solution containing two components is called binary solution.
Types of solutions

SLNO: SOLUTE SOLVENT TYPE OF SOLUTION Examples

1 Solid solid Cu dissolved in Au,Brass,Bronze
Solid solutions
2 Liquid Solid Amalgam of Hg with sodium,
Hydrated salt
3 Gas solid Solution of H2 in Pd
4 Solid Liquid Sugar, salt in water
Liquid solutions
5 Liquid Liquid Ethanol in water
6 Gas Liquid O2 in water, aerated drinks
7 Solid Gas I2 vapours in air, camphor in N2
gas.
8 Liquid Gas Gaseous solutions CHCl3 mixed with N2 gas,
Humidity in air
9 Gas Gas Mixture of O2 and N2(air)

Expressing concentration of solutions: Composition of a solution can be described by expressing its

concentration. It is the amount of solute present in a given quantity of solvent or solution. It can be
expressed in the following ways.
1. Mass percentage (w/w): It is the amount of solute present in 100g of solution.

Mass % of solute= Mass of solute x100

Mass of solution

2. Volume percentage (v/v): It is the volume of solute present in 100ml of solution.

Volume% of solute= Volume of solute x100

Total volume of the solution

3. Mass by volume percentage (w/v): It is the mass of solute dissolved in 100ml of the solution.

1
 Mass by volume% of solute(w/v)= Mass of solute x100
volume of solution

3. Parts per million (ppm): It is the number of parts of component in million parts of the solution.

ppm= Number of parts of the component x106

Number of parts of all components of the solution

4. Mole fraction (x): It is the ratio of number of moles of one component to the total number of moles of
components of all components present in the solution.
Suppose a binary solution contains nA moles of a solvent and nB moles of a solute

XA = nA XB = nB
XA+XB=1
nA+nB nA+nB

5. Molarity (M): It is the number of moles of solute dissolved in 1L of the solution. Unit of molarity
is mol L-1 or M.

Molarity= Mass of soluteX1000

Molar mass of the solute x volume of solution (in ml)

WA=Mass of solvent
M= WBX1000 WB=Mass of solute
MBxV(in ml) MA=Molar mass of solvent
MB=Molar mass of solute
5. Molality (m): It is the number of moles of solute dissolved in 1Kg of the solvent. Unit of molality
is molKg-1 or molal (m)

Molality= Mass of soluteX1000

Molar mass of the solute x mass of solvent (in g)

m= WBX1000
MBx WA (in g)

Q No: 1. How does Molarity and Molality changes with temperature?

Molality does not change with temperature, because mass does not depend on temperature.
Molarity with temperature, because volume decrease with with temperature.

2
Relation between Molarity and mass %

Molarity= Mass% x 10 x d
Molar mass of solute

Relation between Molarity and Molality

Molality= 1000 x Molarity
(1000 xd)-(M x Molar mass)

Dilution formula
M1V1=M2V2

SOLUBILITY: It is the maximum amount of solute that can be dissolved in a specified amount of solvent
at a specified temperature.
It depends upon the nature of solute and solvent as well as temperature and pressure.
Solubility of solid in a iquid
Factors affecting solubility
a)Nature of solute:polar solutes dissolve in polarsolvents and non polar solutes in non polar solvents.i.e
lke dissolves like.
b)Temperature: We have, Solute+solvent solution
According to Le-Chateliers principle,If in a nearly saturated solution ,the dissolution process is
endothermic (∆sol H>0)the solubility should increase with rise in temperature ad if it is exothermic
(∆sol H<0), the solubility should decrease .
c)Pressure: It doesnot have any significant effect on solubility of solids in liquids.It is so because solids
and liquids are highly incompressible.
Solubility of gas in a iquid
Effect of Temperature:Solubility of gases in liquids decreases with rise in temperature.As dissolution is
an exothermic process,the solubility should decrease with increase in temperature.
Effect of pressure:The solubility of gases increase with increase of pressure.
HENRY’S LAW
It give quantitative relation between presssure and solubility of gas in a solvent.
STATEMENT: It states that at constant temperature,the solubility of gas in a liquid is directly
proportional to the pressure of the gas.
OR
The partial pressure of the gas in vapour phase(p) is proportional to the mole fraction of the gas
(x) in the solution. P α xgas
P=KHx
Where KH is the Henrys constant. xgas is the mole fraction of the gas.
Different gase have different values of KH.

3
Plot of Partialpressure vs Mole fraction

Slope=KH
• KH is a function of nature of gas.
• Greater the value of KH, lower is the solubility of the gas.
• The value of KH increases with increase in temperature indicates that solubility decreases with
increase of temperature at the same pressure.
Q.No:2 The aquatic species are more comfortable in cold water than in hot water.why?
Because KH value of O2 and N2 decreases with decrease in temperature.Therefore solubility of these
gases increases with decrease of temperture.
APPLICATIONS
➢ To increase the solubility of CO2 in soft drinks and soda water, the bottle is sealed under
high pressure.
➢ Scuba divers must cope with high concentrations of dissolved gases while breathing air at
high pressure underwater. Increased pressure increases the solubility of atmospheric gases
in blood. When the divers come towards surface, the pressure gradually decreases. This
releases the dissolved gases and leads to the formation of bubbles of nitrogen in the blood.
This blocks capillaries and creates a medical condition known as bends, which are painful
and dangerous to life. To avoid bends, as well as, the toxic effects of high concentrations of
nitrogen in the blood, the tanks used by scuba divers are filled with air diluted with helium.
(11.7% helium, 56.2% nitrogen and 32.1% oxygen).

➢ At high altitudes the partial pressure of oxygen is less than that at the ground level. This
leads to low concentrations of oxygen in the blood and tissues of people living at high
altitudes or climbers. Low blood oxygen causes climbers to become weak and unable to
think clearly, symptoms of a condition known as anoxia.
Vapour pressure (v.p)
It is the pressure exerted by the vapours above the liquid surface in equilibrium with the liquid at a
given temperature. It depends on
Nature of the liquid: The liquids which have weaker intermolecular forces have high v.p
Temperature: As temperature increases V.P increases because K.E of molecules increases.
Q. No:3. V.p of solution is less than that of the pure solvent. Why?
Evaporation is a surface phenomenon. V.p depends on the escape of solvent molecules from the
surface of the liquid. In case of solution, the non-volatile solute molecules also occupy in a certain

4
surface area. As a result, less number of solvent molecules can escape as vapours. Therefore v.p
decreases.
VapourPressure of Liquid-Liquid Solutions
Raoult’s law for a solution of volatile liquids
It states that for a solution of volatile liquids, the partial vapour pressure of each component in the
solution is directly proportional to its mole fraction.
Consider a binary solution having components A (solvent) and B (solute) respectively.

According to Raoult’s law pA α xA and pB α xB

pA = p0A xA
pB = p0BxB
Where pA and pB are the partial pressures and XA and XB are the mole fractions of the components A
and B respectively. p0A and p0B are the vapour pressures of the pure components A and B respectively.
According to Daltons law of partial pressures

P= pA+ pB

= p0A xA+ p0B xB

We have XA+XB=1 and XA=1- XB

Then P= p0A (1- XB )+ p0B xB

P= p0A -p0A xB+ p0B xB

P= p0A +(p0B - p0A) xB
The composition of the vapour phase in equilibrium with the solution

Let yA and yB are the mole fractions of the components A and B respectively in vapour phase. Then

PA=yA xPtotal

PB=yB xPtotal

Raoult’s law for a solution of non-volatile solute and volatile solvent

It states that relative lowering of vapour pressure is equal to the mole fraction of the solute at a
given temperature.

We have pA = p0A xA or pA = xA
p0A
Subtract each side of the above equation from 1

5
 PA
1− = 1- XA 𝟎
PB 𝐏𝐒𝐨𝐥𝐯𝐞𝐧𝐭 −𝐏𝐬𝐨𝐥𝐮𝐭𝐢𝐨𝐧
𝟎 =Xsolute
P0A −PA 𝐏𝐬𝐨𝐥𝐯𝐞𝐧𝐭
= XB
P0A

P0Solvent −Psolution
Relative lowering of v.p=
P0solvent

Raoult’sLaw as a special caseof Henry’Law

According to Raoult’s law, the vapour pressure of a volatile component in a given solution is given by
pA = p0A xA
According to Henry’s law P = KH x
If we compare the equations for Raoult’s law and Henry’s law, it can be seen that the partial pressure of
the volatile component or gas is directly proportional to its mole fraction in solution. Only the
proportionality constant KH differs from p0A.
Thus, Raoult’s law becomes a special case of Henry’s law in which KH becomes equal to p0A.
IDEAL SOLUTIONS
The solutions which obey Raoult’s law over the entire range of concentration are known as ideal
solutions.
Criteria for an ideal solution
• The enthalpy of mixing of the pure components to form the solution is zero and the volume of
mixing is
also, zero, i.e.
∆mixH = 0 and ∆mixV = 0
• The intermolecular attractive forces between the A-A and B-B are nearly equal to those between
A-B.
i.e. FA-A=FB-B=FA-B
• pA = p0A xA and pB = p0BxB
• E.g Solution of n-hexane and n-heptane, bromoethane and chloroethane, benzene and toluene,
etc.

NON-IDEAL SOLUTIONS
The solutions which do not obey Raoult’s law over the entire range of concentration are known as non-
ideal solutions.
Criteria for non- ideal solution
• The enthalpy of mixing of the pure components to form the solution is not zero and the volume
of mixing is also not zero, i.e.
∆mixH =≠ 0 and ∆mixV =≠0
6
 • The intermolecular attractive forces between the A-A and B-B are not equal to those between
A-B.
i.e. FA-A≠FB-B≠FA-B
• pA ≠ p0A xA and pB ≠ p0BxB
Types of non-ideal solutions
These are of 2 types.
1. Solutions showing positive deviation
2. Solutions showing negative deviation
Solutions showing positive deviation
• The vapour pressure of a solution is higher than that predicted by Raoult’s law, then the solution
exhibits positive deviation. In case of positive deviation from Raoult’s law, A-B interactions are
weaker than those between A-A or B-B. This means that in such solutions, molecules of A (or
B) will find it easier to escape than in pure state. This will increase the vapour pressure and result
in positive deviation.
• ∆mixH >0 and ∆mixV >0
• pA >p0A xA and pB > p0BxB
• FA-A and FB-B>FA-B
• E.g. Mixture of ethanol and acetone, mixture of CS2 and acetone etc.
Solutions showing negative deviation
• The vapour pressure of a solution is lower than that predicted by Raoult’s law, then the solution
exhibits negative deviation. In case of negative deviation from Raoult’s law, A-B interactions are
stronger than those between A-A or B-B and leads to decrease in vapour pressure and result in
negative deviation.
• ∆mixH <0 and ∆mixV <0
• pA <p0A xA and pB < p0BxB
• FA-A and FB-B <FA-B
• E.g. Mixture of phenol and aniline, mixture of chloroform and acetone etc.

7
QN0 4: Mixtures of ethanol and acetone shows + ve deviation from Raoult’s law. Why?
In pure ethanol, molecules are hydrogen bonded. On adding acetone, its molecules get in
between the ethanol molecules and break some of the hydrogen bonds between them. Due to weakening
of Interactions, the solution shows positive deviation from Raoult’s law.
QN0 5: Mixtures of CS2 and acetone shows +ve deviation from Raoult’s law. Why?
The dipolar interactions between solute-solvent molecules are weaker than the respective
interactions among the solute-solute and solvent-solvent molecules. Therefore, this solution shows
positive deviation from Raoult’s law.
QN0 6: Mixtures of phenol and aniline shows –ve deviation from Raoult’s law. Why?
The intermolecular hydrogen bonding between phenolic proton and lone pair on nitrogen atom of
aniline is stronger than the respective intermolecular hydrogen bonding between similar molecules.
QN0 7: Mixtures of chloroform and acetone shows –ve deviation from Raoult’s law. Why?
Chloroform molecule is able to form hydrogen bond with acetone molecule. This decreases the
escaping tendency of molecules for each component and consequently the vapour pressure decreases
resulting in negative deviation from Raoult’s law.

QNO 8. Why is an increase in temperature observed on mixing chloroform and acetone?

The bonds between chloroform and acetone molecules are dipole-dipole interactions. On mixing, they
start forming H-bonds which are stronger bonds results in the release of energy. This gives to an
increase in temperature.
Azeotropes
Liquid mixtures which boil at constant temperature and distil over without change in
composition are called constant boiling mixtures or azeotropes. There are two types of azeotropes.
1. Minimum boiling azeotrope
2. Maximum boiling azeotrope.
1. Minimum boiling azeotrope
Non-ideal solutions showing large positive deviation from Raoult’s law form Minimum boiling
azeotrope. These azeotropes boil at a temperature lower than the boiling point of its components.
.E.g. ethanol water mixture.
2. Maximum boiling azeotrope
Non-ideal solutions showing large negative deviation from Raoult’s law form Maximum boiling
azeotrope. These azeotropes boil at a temperature higher than the boiling point of its components.
E.g. Nitric acid and water mixture.
Colligative properties
Properties of the solution which depend only on the number of solute particles and do not depend on
their nature are called colligative properties.
The four colligative properties are
1. Relative lowering of vapour pressure
2. Elevation in boiling point
3. Depression in freezing point
4. Osmotic pressure
8
1. Relative lowering of vapour pressure
When a non-volatile solute is added to a pure solvent, V.P decreases.
𝐏𝐀𝟎 −𝐏𝐀
= 𝐱𝐁
𝐏𝐀𝟎
This equation shows that relative lowering of V.P depends only on the number of solute particles and
independent of its nature.
Determination of molar mass of the solute (MB)
P0A −PA
We have = xB
P0A
P0A −PA 𝑛𝐵
=
P0A 𝑛𝐴 +𝑛𝐵
For dilute solutions, nB <<< nA

wB
P0A −PA 𝑛𝐵 ⁄M
B
= = wA
P0A 𝑛𝐴 ⁄M
A
wB xMA xp0A
PA0 − PA wB xMA MB =
= OR (p0A −pA) xwA
PA0 MB xwA

2.Elevation in boiling point

• Boiling point is the temperature at which vapour pressure of al liquid becomes to the
atmospheric pressure.
• When a non-volatile solute is added to a volatile solvent, the V.P of solution decreases. So, the
boiling point of a solution is always higher than that of the boiling point of the pure solvent.
• Elevation in boiling point: It is the difference between the boiling point (B.P) of the solution (Tb)
and the boiling point of the solvent (Tb0).

∆Tb= Tb- 𝑇𝑏0

For a dilute solution
∆Tb=kbxm
∆Tbα m (molality)

Where kb is known as Boiling Point elevation constant or Molal Elevation Constant or

EbullioscopicConstant. The unit of Kb is K kg mol-1.
It is defined as elevation in B.P, when 1 mole of non-volatile solute is dissolved in 1kg of solvent.
Determination of molar mass of the solute (MB)
We have ∆Tb=kbxm

𝒌𝒃 𝐱 𝒘𝑩𝐱𝟏𝟎𝟎𝟎 OR 𝒌𝒃 𝐱 𝒘𝑩𝐱𝟏𝟎𝟎𝟎
∆Tb= MB=
∆𝐓𝐛 𝐱𝐰𝐀
𝐌𝐁 𝐱𝐰𝐀

9
Vapour pressure vs Temperature curve

3. Depression in freezing point

• Freezing point is defined as the temperature at which the V.P of a substance in its liquid phase is
equal to its V.P in the solid state.
• A solution freezes when its V.P is equal to the V.P of the solid solvent.
• When a non-volatile solute is added to the solvent, its V.P decreases and it would come equal to
that of the solid solvent at a lower temperature.
• Depression in freezing point: It is the difference between the freezing point (F.P) of the pure
solvent (Tf0) and the freezing point of the solution (Tf).
∆Tf = 𝑻𝟎𝒇 − 𝑻𝒇
• For a dilute solution
• ∆Tfα m (molality)
∆Tf =kf x m

Where Kf is known as Freezing point depression constant or Molal depression Constant or

cryoscopic constant. The unit of Kf is K kg mol-1..
• It is defined as depression in F.P, when 1 mole of non-volatile solute is dissolved in 1kg of
solvent.
Determination of molar mass of the solute (MB)
• We have ∆Tf =kf x m

𝒌𝒇 𝐱 𝒘𝑩𝐱𝟏𝟎𝟎𝟎 𝒌𝒇 𝐱 𝒘𝑩𝐱𝟏𝟎𝟎𝟎
∆Tf= OR M B=
𝐌𝐁 𝐱𝐰𝐀 ∆𝐓𝐟 𝐱𝐰𝐀
Vapour pressure vs Temperature curve

10
OSMOSIS: The spontaneous flow of solvent molecules through a semi permeable membrane from pure
solvent to the solution is called osmosis.
Semi permeable membrane (SPM): A membrane which allows the solvent molecules to pass through
but not the solute molecules is called SPM. E.g. Cellophane, parchment paper, walls of living cells etc.
4. OSMOTIC PRESSURE: It is the excess pressure that must be applied to solution side to prevent
osmosis.
It is a colligative property as it depends on the no: of solute particles and not on their nature.
For dilute solutions, osmotic pressure is directly proportional to molarity ‘C’ of the solution at a given
temperature T.
∏=CRT

C=Molarity R=Universal gas constant,

For a solution at a given temperature, both R and T are constants. Then

∏α C

Since ∏ depends up on the molar concentration of solution, it is colligative property.

Determination of molar mass of the solute (MB)

We have ∏=CRT C=n/V n=wB/MB

𝒏𝑹𝑻
∏=
𝑽
𝒘𝑩 𝐱𝑹𝐱𝑻 OR
∏V= 𝒘𝑩 𝐱𝑹𝐱𝑻
𝑴𝑩 𝑴𝑩 =
∏𝐕

Reverse Osmosis and Water Purification

If pressure larger than osmotic pressure is applied to the solution side, the pure solvent flows out of the
solution through the semi permeable membrane. This process is called reverse osmosis.
Application

Reverse osmosis is used in desalination of seawater. A schematic set up for the process is shown in Fig.
When pressure more than osmotic pressure is applied, pure water is squeezed out of the seawater
through the membrane.

11
Qno: 8. How is that measurement of osmotic pressure widely used for determining molar masses
of macromolecules than elevation in B.P or depression in F.P of their solution?
• Osmotic pressure measurement is around the room temperature and the molarity of the solution
is used instead of molality.
• As compared to other colligative properties, its magnitude is large even for very dilute solutions.
Isotonic solutions: Two solutions having same osmotic pressure at a given temperature are called
isotonic solutions. i.e. they have same molar concentration.
Hypertonic solutions: A solution having higher osmotic pressure than the other solution is said to
be hypertonic with respect to the other solution.
Hypotonic solutions: A solution having lower osmotic pressure than the other solution is said to be
hypotonic with respect to the other solution.
Importance of osmosis
• A 0.9% solution of NaCl (saline water) is isotonic with the fluids inside human RBC.In this
solution, the cell neither swell nor shrink. Therefore, the medicines are mixed with saline
water before injecting in to veins.
• A pure NaCl solution with concentration more than 0.9% is called hypertonic solution. On
placing RBC in this solution, they shrink due to plasmolysis.
• A pure NaCl solution with concentration less than 0.9% is called hypotonic solution. On
placing RBC in this solution, they swell and burst.
• A raw mango placed in concentrated salt solution loses water by osmosis and shrivel into pickle.
• People taking a lot of salt or salty food experience water retention in tissue cells and intercellular
spaces because of osmosis. The resulting puffiness or swelling is called edema.
• The preservation of meat by salting and of fruits by adding sugar protects against bacterial
action. Through the process of osmosis, a bacterium on salted meat or candid fruit loses water,
shrivels and dies.
• A carrot that has become limp because of water loss into the atmosphere can be placed into the
water making it firm once again. Water will move into them through osmosis.

ABNORMAL MOLAR MASS

The molar mass calculated from the observed colligative properties is different from the theoretical
value; it is called abnormal molar mass.
It is due to association or dissociation of molecules.
1. Association: It decreases the no: of particles in the solution and as result the value of colligative
property also decreases. Therefore, higher value is obtained for molar mass than the normal values.
Colligative property α no: of particles
1
Colligative property α
Molar mass

E.g.Acetic acid is dissolved in benzene undergoes dimerization and shows a molar mass of 120.(Normal
value-60)
12
2. Dissociation

It increases the no: of particles in the solution and as result the value of colligative property also
increases. Therefore, lower value is obtained for molar mass than the normal values.
Colligative property α no: of particles
1
Colligative property α
Molar mass

E.g. KCl dissolved in water dissociates to give K+ and Cl- ions.

KCl K+ +Cl-
The no: of particles increases and shows a molar mass of 37.25(normal value-74.5)
Van’t Hoff factor (i)
Van’t Hoff introduced a factor i, known as the van’t Hoff factor, to account for the extent of dissociation
or association of solute particles in the solution. i is defined as:

Normal molar mass

i=
observed molar mass

Observed colligative property

i=
calculated colligative property

Total number of moles of particles after association/dissociation

i=
Number of molesof particles beforeassociation/dissociation

For association i<1

For dissociation i>1

Modified form of colligative properties

1. Relative lowering of V.P
P0A −PA
= i xB
P0A
2. Elevation in B.P
∆Tb=i kbxm

3. Depression in F.P
∆Tf=i kfxm

13
4. Osmotic pressure
𝒊𝒏𝑹𝑻
∏=
𝑽

NOTE
𝒊−𝟏
α=
𝒏−𝟏
α=Degree of dissociation, n= no: of ions produced after dissociation
𝟏−𝒊
α= 𝟏
𝟏−
𝒏
α=Degree of association, n=no: of moles of solute associated to form a molecule.
Qno:9. Out of 0.1molal solutions of glucose and KCl,which one will have a higher B.P and why?
0.1molal solutions of KCl will have a higher B.P as KCl dissociates in the solution.
Qno: 10. The dissolution of NH4Cl in water is an endothermic process but still it dissolves in water
readily?
Because in this case ∆S is positive. Therefore ∆G is negative.
Qno: 11. What will happen to F.P of KI solution when mercuric iodide is added to this solution?
Mercuric iodide forms a complex with KI, therefore the no: of solute particles (KI) in the solution
decreases and ∆Tf also decreases. As a result, F.P of the solution will increase.
Qno: 12. Cooking is faster in pressure cooker than in cooking pan. Give reason.
Pressure inside the pressure cooker is high. Higher the pressure higher is the B.P and faster is the
cooki ng.
Qno: 13. Why is glycol and water mixture used in car radiators in cold countries?
Ethylene glycol lowers the F.P of water. Due to this, coolant in radiators will not freeze. Otherwise,
radiator will burst due to freezing of coolant. (Water)
Qno:14. Identify which h liquid will have higher vapour pressure at 900C if the boiling point of 2
liquids A and B are 1400C and 1800C respectively.
Liquid A
Qno: 15. Predict the state of the solute in the solutions in the following situations.
(i) When i is found to be 0.3 (ii) When i is found to be 4
Ans (i) Associated (ii) Dissociated

14