IGNITE ACADEMY

CHAPTER 2
SOLUTIONS
 Solution is a homogeneous mixture of two or more chemically non-reacting substances whose
composition can be changed within certain limits.
 A solution is regarded as a singular phase having more than one component. A solution which contains
two components is known as binary solution.
 The component which is present in smaller quantities is called the solute and the other which present in
larger amount is known as the solvent
 A solution which contains as much solute as it can dissolve at a given temperature is called a saturated
solution.
 A solution which contains lesser solute than the amount of solute if can dissolve is called unsaturated
solution.
 A solution which contains more solute than the amount of solute it can dissolve at a particular
temperature is called a super saturated solution.

1)TYPES OF SOLUTIONS
Solutions of Solids in Liquids : It is a solution which still in contact with excess of solute. y The solubility
of the solute is defined as the amount of solute dissolved per 100 g of solvent at a specific temperature
for a saturated solution. y For exothermic substances such as KOH, CaO, Ca(OH)2, M2CO3, M2SO4 etc.,
 2) EXPRESSING CONCENTRATION OF SOLUTIONS
Composition of a solution can be described by expressing its concentration.
The concentration can be expressed either qualitatively or quantitatively.

Quantitative Expressions
. (i) Mass percentage (w/w): The mass percentage of a component of a solution is defined as:

(ii) Volume percentage (V/V): The volume percentage is defined as:

Volume % of a component== Volume of the component x 100
Total volume of solution

(iii) Mass by volume percentage (w/V): Another unit which is commonly used in medicine and
pharmacy is mass by volume percentage. It is the mass of solute dissolved in 100 mL of the solution.

(iv) Parts per million: When a solute is present in trace quantities, it is convenient to express
concentration in parts per million (ppm) and is defined as:

Parts per million = Number of parts of the component x 106

Total number of parts of all components of the solution

v) Mole fraction: Commonly used symbol for mole fraction is x and subscript used on the right hand
side of x denotes the component. It is defined as:

Mole fraction of a component = Number of moles of the component

Total number of moles of all the components

(vii) Molality: Molality (m) is defined as the number of moles of the solute per kilogram (kg) of the solvent and
is expressed as

: Molality (m) = Moles of solute

Mass of solvent in kg
 3) SOLUBILITY
Solubility of a substance is its maximum amount 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.

i) Solubility of a Solid in a Liquid

Solution of sugar or salt dissolved is a common example of solubility of a solid in liquid. But it is not necessary
that all solids will dissolve in liquid.

 For instance, solids like naphthalene and anthracene do not dissolve in water but dissolves easily in
benzene but sugar and salt does not dissolves in benzene.
 This is because it is property of solution that polar solutes dissolve in polar solvents like Water, ethanol,
formaldehyde and chloroform whereas non polar solutes in nonpolar solvents like pyridine, toluene, and
hexane. This phenomenon can be easily defined as like dissolves like.
 The phenomenon of increase in the concentration of solution due to dissolving of solid solute to the
solvent is known as dissolution
 The phenomenon of collision of solute particles in a solution resulting in the separation of the solute
particles from the solution is known as crystallization.
 A phase when number of solute particles going into solution is equal to the solute particles separating
out of the solution is known as equilibrium. The concentration of solute remains constant at this stage.
 A solution in which no more solute can be dissolved into the solvent at the same temperature and
pressure is known as saturated solution.
 Whereas a solution in which more solute can be dissolved in the solvent at the same temperature and
pressure is known as unsaturated solution.
 According to Le Chateliers Principle in a saturated solution, if the dissolution process is endothermic
(Δsol H > 0), the solubility should increase with rise in temperature but if the dissolution process is
exothermic (Δsol H > 0) the solubility should decrease. Pressure does not have crucial effect on
solubility of solids in liquids because they remain unaffected to pressure due to the high
incompressibility of solids and liquids.

ii) Solubility of a Gas in a Liquid

Aerated drinks, Dissolved oxygen in water bodies that supports the aquatic life are natural instance of solubility
of gas in a liquid. Hydrogen chloride gas (HCl) is also highly soluble in water.
.
Increase in temperature reduces the solubility of gases in liquids because on dissolving gas molecules in liquid
the process of dissolution is similar to condensation leading to the evolution of heat. Therefore, dissolution is an
exothermic process, due to which the solubility decreases with increase of temperature.
Increase in pressure by compressing the gas to a smaller volume increase the number of
gaseous particles per unit volume over the solution and also the rate at which the gaseous particles are striking
the surface of solution to enter it leading to the increase in the solubility of gases.

Henry’s law

 Henry’s Law establishes aquantitative relation between pressure and solubility of a gas in a solvent.
 This law is for gas-liquid solution.
  According to the law at a constant temperature, thesolubility of a gas in a liquid is directly proportional
to thepressure of the gas.
 It can also be stated as - The partial pressure of the gas in vapour phase (p) is proportional to the mole
fraction of the gas (x) in the solution.
 Mathematically,

p = KH x where KH = Henry’s law constant.

 At same temperature different gasses have different KH

 It is a function of the nature of the gas. At a given pressure increasing value of KH implies lower
solubility of the gas in the liquid.
 Value of KH increases with the increase in temperature therefore solubility of gases increases with
decreasing temperature. Due to this reason cold water is more sustainable for aquatic life than warm
water.

Raoult’s law

 Raoult’s law establishes a quantitative relationship between the partial vapour pressure and mole
fraction of a solution.
 This law is only for liquid-liquid solution.
 The law states that for a solution of volatile liquids, the partial vapour pressure (p) of each component in
the solution is directly proportional to its mole fraction (x).
 Mathematically, p ∝ x

Or p = p 0x

Where p0 is the vapour pressure of pure component at the same temperature.

Thus, for component 1, p1 = p1 0 x1 and for component 2 p2 = p20 x

Let the solvent be represented by 1 and solute be represented by 2. At the point when the solute is non-volatile,
just the solvent molecules are present in vapour phase and
add to vapour pressure.

Let p1 = vapour pressure of the solvent,

x1 = mole fraction,

pi0 = vapour pressure in the pure state.

According to Raoult’s law

p1 ∝ x1

And p1 = p1 0 x1

Fig. a plot between the vapour pressure and the

mole fraction of the solvent is linear
 Raoult’s law as special case of Henry’s law

 At a given temperature liquids vaporize. At equilibrium the pressure exertedby the vapour of the liquid
over the liquidphase is referred to as vapour pressure.
 According to Raoult’s law, vapour pressure of a volatile component in a given solution ca be defined by
pi = pi 0 xi
 In an answer of a gas in a fluid one of the segments is volatile to the point that it exists as a gas and
solvency is given by Henry's law which expresses that p = KH x
 Comparing both the equations we get that partial pressure of the volatile component or gas is directly
proportional to its mole fraction in solution. Proportionality constant KH differs from p10
 Therefore, Raoult's law turns into a unique instance of Henry’s law in which KH get to be equivalent to
p10.

4) VAPOUR PRESSURE OF LIQIUD SOLUTIONS

i) Vapour pressure of a liquid-liquid solution

 Acetic acid in water is a liquid-liquid solution. Similarly lemon juice added to water for making
lemonade is a liquid-liquid solution.
 Let two volatile components of a binary solution be expressed as 1 and 2.
 In a closed vessel both the components of the solution would evaporate and establish an equilibrium
state between the vapour phase and the liquid phase.
 Let p total = Total vapour pressure
p1 = Partial vapour pressures of component 1
p2= Partial vapour pressures of component 2
x1 = Mole fractions of component 1.
x2 = Mole fractions of component 2

 Dalton’s law of partial pressures states that the total pressure (ptotal) of the solution is the sum of the
partial pressures of the components of the solution.
 Mathematically, P total = P1 + P2
 Substituting the values of p1 and p2 we get

 The minimum value of ptotal is p10 and the maximum value is p20, assuming that p10 < p20.
 Let y1 = Mole fractions of the component 1

y2 = Mole fractions of the component 2

According to Dalton’s law of partial pressures:
P1 = y1 Ptotal
P2 = y2 Ptotal

ii)Vapour pressure of solution of solids in liquids

 Solution of salt, sugar or glucose dissolved in water is solutions of solids in liquids.

  Similarly iodine and sulphur dissolved in carbon disulphide are also solutions of solids in liquids
 Addition of anon-volatile solute to a solvent to give a solution results in the exertion of the vapour
pressure of the solution uniquely from the solvent.

 This vapour pressure is lower than the vapour pressure of the pure solvent at a given temperature.
 The surface of the solution is occupied by both solute and solvent molecules which results in the
reduction of the surface for the solvent molecules. As a result the apparent number of solvent molecules
escaping from the surface is reduced. This in turn reduces the vapour pressure.
 The reduction of vapour pressure of solvent depends on the quantity of non-volatile solute present in the
solution not on its nature.

5) IDEAL SOLUTIONS AND NON- IDEAL SOLUTIONS

 The solutions that obey Raoult’s law over the whole collection of concentration are known as ideal
solutions.

 The enthalpy of mixing of the pure components for the formation of the solution is zero.
Mathematically, Δmix H = 0.
 This implies that heat is neither absorbed nor evolved during the mixing of components in a solution.
 The volume of mixing of the pure components for the formation of the solution is also zero.
Mathematically, Δmix V = 0

Volume of the entire solution = Sum of volumes of the components.

 In case of pure components the intermolecular attractive interactions is of A-A and B-B type.
 In case of binary solutions the intermolecular attractive interactions is of A-A, B-B and A-B type.
 When the intermolecular attractive forces between the A-A and B-B type arenearly equivalent to the
intermolecular attractive forces between A-B it results in the formation of ideal
 No solution is perfectly ideal but some solutions are nearly ideal in behaviour. For instance, solution of
n-hexane and n-heptane, Bromoethaneand chloroethane, benzene and toluene, etc. exhibits ideal
behavior.

 The solutions that do not obey Raoult’s law over the whole collection of concentration are known as
non-ideal solutions.
 The vapour pressure of a non-ideal solution is either higher or lower than predicted by Raoult’s law.

 Positive deviation from Raoult’s Law

 The solute- solute and solvent-solvent interaction are stronger than solute-solvent interaction.
 Let pA = Partial vapour pressures of component A

PB = Partial vapour pressures of component B

Hmix = Change in enthalpy of mixing.
Vmix =Change in volume of mixing.

 pA > pAoxA
 pB > pBoxB
 ΔHmix > 0
  ΔVmix > 0
 Total vapor pressure is more than as expected from Raoult’s law.
 Solution of ethanol and acetonebehaves in the same manner. Molecules of pure ethanol are hydrogen
bonded. The molecules of acetone get in between the molecules of ethanol on addition of acetone and
break some of the hydrogen bonds between them.

Negative deviation from Raoult’s Law

 The solute-solute and solvent –solvent interactions are weaker than solute-solvent
interaction.
 Let pA = Partial vapour pressures of component A
PB = Partial vapour pressures of component B
Hmix = Change in enthalpy of mixing.
Vmix =Change in volume of mixing.
o
 pA< pA xA
o
 pB < pB xB
 ΔHmix < 0
 Total vapor pressure is less than as expected from Raoult’s law.
 Solution of phenol and aniline. It has strong intermolecular hydrogen bonding between phenolicproton
and lone pair of nitrogen atom of aniline than the intermolecular hydrogen bonding between similar
molecules.
 A solution of chloroform and acetone shows negative deviation from Raoult’s law due to the formation
of hydrogen bond with acetone molecule by chloroform molecule. This decreases the chances of
molecules of component to escape leading to the decrease in vapour pressure. And hence the solution
exhibits negative deviation from Raoult’s law
Azeotropes

 Azeotropes are binary mixturespossessing the same synthesis in fluid, vapor stage and boiling stage at a
steady temperature.
 The components of azeotropic mixtures are separated by fractional distillation.
 Azeotropes can be broadly categorized into two types-

1. Minimum boiling azeotrope :The solutions showing positive deviation from Raoult’s law. For instance,
solution of ethanol and water on fractional distillation results in a solution containing approximately
95% by volume of ethanol.

2. Maximum boiling azeotrope.: The solutions showing negative deviation from Raoult’s law. For
instance, solution of nitric acid and water has the approximate arrangement, 68% nitric corrosive and
32% water by mass, with a breaking point of 393.5 K

Properties of solution affected by vapour pressure

 Vapour pressure of solution decreases on addition of a non-volatile solute to a volatile solvent.

 Properties of solutions affected by the decrease of vapour pressure includes-

1. Relative lowering of vapour pressure of the solvent

2. Depression of freezing point of the solvent
3. Elevation of boiling point of the solvent and
4. Osmotic pressure of the solution.

 These properties of solution depend on the number of solute particles present in the solution regardless
of their nature relative to the total number of particles present in the solution. These properties are
termed as colligative properties derived from a Latin word with co meaning together ligare meaning to
bind.

6) COLLIGATIVE PROPERTIES & DETERMINATION OF MOLAR

MASSES

i) Relative lowering of vapour pressure

 Vapour pressure of a solvent present insolution is less than the vapour pressure of the pure
solvent.
 According to Raoult lowering of vapour pressure of a solution depends only on the concentration of
thesolute particles and remains independent of their identity.
 p1 =x1 p10
 The reduction in the vapour pressure of solvent (p1) is given as:

As x2=1-x1 the above equation reduces to Δp1= x2p10

 Lowering of the vapour pressure of a solution with several non-volatile solutes depends upon the sum of
the mole fraction of different solutes which makes the above equation as-
Where n1 and n2 are the number of moles of solvent and solute respectively present in the solution.
 The above equation can be written as:

 For dilute solutions n2 << n1, hence ignoring n2 in the denominator we get

w1 and M1 = Masses and molar masses of solvent.

w2 and M2 = Masses and molar masses of solute.

ii)Elevation of boiling point

 Increase in temperature increases the vapour pressure of a liquid .
 A liquid boils at a temperature where the vapour pressure is equal to the atmospheric
 Vapour pressure of the solvent decreases in the presence of non-volatile solute.
 The boiling point of a solution is always higher than that ofthe boiling point of the pure solvent in which
the solution is prepared as.
 The elevation of boiling point also depends on the number ofsolute molecules rather than their nature.
0
 The increase in the boiling point = ΔTb = Tb – Tb . This is known as elevation of boiling point.
0
Tb = boiling point of pure solvent
Tb0 = boiling point of solution
 In dilute solutions the elevation of boiling point Tb is directly proportional to the molal
concentration of the solute in a solution. Mathematically,
ΔTb ∝ m
ΔTb = kb m
m = Molality = number of moles of solute dissolved in 1 kg of solvent
Kb = constant of proportionality. It is also known as Boiling Point Elevation Constant or Molal
Elevation Constant (Ebullioscopic Constant). The unit of Kb is K kg mol-1.

 Let w2 and M2 = Masses and molar masses of solute

w1= Mass of solvent

iii) Depression of freezing point

 Freezing point of a substance is the temperature at which the vapour pressure

of the substance in its liquid phase is equal to the vapour pressure in the solid phase.
 If the vapour pressure of the solution is equal to the vapour pressure of the pure solid solvent then the
solution freezes.

 According to Raoult’s law, addition of non-

volatile solute decreases the vapour pressure of
the solvent and would be equal to that of solid
solvent at lower This decreases the freezing point
of thesolvent.
0
 The decrease in the freezing point = ΔTf = Tf – Tf .
This is known as depression in freezing point.
Tf0 = freezing point of pure solvent
Tf0 = freezing point when non-volatile solute is
dissolved
 In a dilute solution the depression of freezing
point Tf is directly proportional to
molality of the solution.
 Mathematically,
ΔTf ∝m Diagram showing, depression of the
ΔTf = Kf m freezing point of a solvent in a solution.
Kf = Proportionality constant depending upon the nature
of the solvent. This is known as Freezing Point Depression Constant or Molal Depression Constant or
Cryoscopic Constant. The unit of Kf is K kg mol-1.
 Let w2 and M2 = Masses and molar masses of solute
w1= Mass of solvent

Putting this value of molality in the equation ΔTf = Kf m

 M2 can be determined by the equation

 The values of Kf and Kb can be determined from the following relations.

R= gas constant
M1 = molar mass of the solvent
Δfus H= enthalpies for the fusion of the solvent.
Δvap H= enthalpies for the vaporization of the solvent.

iv) Osmosis and Osmotic pressure

 We have often observed that raw mangoes shrink when kept in salt water (brine solution),
flowers remain fresh for longer time when kept in water.
 This is due to the fact that small solvent molecules such as water are capable of passing through the
pores present in every cell. These pores allows small solvents like water to pass through but hinders the
passing of larger molecules. This membrane possessing such pore is known as semipermeable
membranes.
 The process of flow of solvents from the pure solvent to the solution through a semipermeable
membrane is termed as osmosis.
 This flow of solvents to the solution continues until the stage of equilibrium is reached.
 Application of extra pressure on the solution can terminate the flow of solvents from the pure solvent to
the solution. This pressure is called osmotic pressure of the solution. It is a colligative property that
depends upon the concentration of the solution and is basically meant to stop the passage of solvent
molecules through a semipermeable membrane into the solution.
  Solvent molecules generally flows from lower concentration to higher concentration. This flow of
solvent from dilute solution to the concentrated solution through a semipermeable membrane is due to
the phenomenon of osmosis.

Calculation of Molar Mass from Osmotic Pressure

In dilute solutions the osmotic pressure is proportional to the molarity, C of the solution at a given temperature
T. Mathematically,
π= C R T
R= gas constant
π = osmotic pressure = (n2/V) RT
V = Volume of a solution in litres
n2 = Moles of solute.
w2 = Grams of solute
M2 = Molar mass
Now, n2 = w2/M2

Classification of solutions on the basis of osmotic pressure

On the basis of osmotic pressure solution can be classified into three broad categories.
1. Isotonic solutions : Two solutions possessing same osmotic pressure at a given temperature are termed
as isotonic solution. No osmosis occurs on isolation of these solutions when isolated through a
semipermeable membrane.

2. Hypertonic solutions : In the event that the medium has a lower convergence of water than the cell,
implying that it is a concentrated solution, the cell will lose water by osmosis. . Such a solution is known
as a hypertonic solution. Once more, water crosses the cell layer in both directions, yet this time more
water leaves the cell than enters it. In this manner the cell will shrink.

3. Hypotonic solutions : In the event that the medium encompassing the cell has a higher water
concentration than the cell, implying that the outside solution is extremely weaken, the cell will pick up
water by osmosis. Such a solution is known as a hypotonic solution. Water particles are allowed to go
over the cell layer in both directions, yet more water will come into the cell than will clear out. The net
(general) result is that water enters the cell. The cell is prone to swell up.

 In case of cells with vacuoles

 Due to this reason people consuming more salty food suffer from water retention in their cell tissues and
intercellular spaces resulting in swelling. This is known as edema.
 Movement of water from soil to the top of the tree is also due to the phenomenon of osmosis.
 Adding salt preserves the food from getting spoilt. Due to osmosis bacterium germinating
on the food loses water and shrinks down. This kills the bacteria.
 v) Reverse osmosis

 Reverse Osmosis is just the reverse process of Osmosis. Osmosis can occur naturally
whenever there is a difference in concentration between the two solutions. But reverse
osmosis takes place only when external energy is applied to the more saline solution.
 Application of larger osmotic pressure to the solution side reverses the direction of
osmosis.
 This phenomenon makes the pure solvent flow out of the solution through the semi
permeable
 Reverse osmosis is extensively used in desalination of sea

Use of Reverse osmosis in water purification

 Reverse osmosis is extensively used in the desalination of sea water.

 A porous film of cellulose acetate is used as a membrane which is permeable to water but impermeable
to impurities and ions is placed over a support.
 Pressure larger than the osmotic pressure is applied on the sea water solution which allows the passing
out of the pure water holding back the bulk of contaminants through the membrane made of polymer.
 The measure of pressure required relies upon the salt grouping of the food water. Greater concentration
of feed water requires more pressure to defeat the osmotic pressure.
 As the water enters the RO membrane under great pressure the water molecules pass through the semi-
permeable membrane.
 The membrane is impermeable to salts and other contaminants and hence is not allowed to pass through
it.
 These leftover contaminated water is then discharged through the reject stream and finally drained out or
is fed back into the feed water supply. This water will again undergo same procedure and will be
purified in some way.

7)Abnormal molar mass

 Some molecules of solvents with low dielectric constant like molecules of ethanoic acid dimerize into
benzene due to the presence of hydrogen bond.
 Association of all the molecules of ethanoic acid into benzene means Tb or Tf for ethanoic acid will be
half of the normal value.
 The molar mass calculated on the basis of this ΔTb or ΔTf will be twice the expected molar mass.
 This value of molar mass is either lower or higher compared to expected or normal value and is known
as abnormal molar mass.
 In 1880 van’t Hoff introduced a factor i and was named as the van’t Hoff factor.
 The van’t Hoff factor account for the degree of dissociation or association.
 The van’t Hoff factor i can be defined as the ratio of Normal molar mass to the abnormal molar mass.
In case of association, value of i is less than unity.

 In case of dissociation value of i is greater than unity.

 Relative lowering of vapour pressure of solvent =

 Elevation of Boiling point, ΔTb = i Kb m

Depression of Freezing point, ΔTf = i Kf m
Osmotic pressure of solution, ð = i n2RT/V