SOLUTIONS

Solution
(i) Homogeneous mixture of 2+ components. Composition and properties are uniform throughout.
(ii) Component that is present in largest quantity is known as solvent. It determines physical state in
which solution exists.
(iii) Solvent has lower boiling point
(iv) Component present in solution other than solvent is called solute.

Solvent Solute Examples

Gas Air
Gas
Liquid Chloroform in Nitrogen gas

Solid Camphor in Nitrogen gas

Gas Carbonated Drinks

Liquid
Liquid Ethanol in Water

Solid Glucose in Water

Hydrogen in Palladium
Solid Gas
(hydrogen storage)
Liquid Amalgam (Hg with a metal)
Brass (Cu, Zn)
Solid German silver (Cu, Zn, Ni)
Bronze (Cu, Sn)

*1 ppm fluoride prevents tooth decay, but 1.5 ppm causes tooth to become mottled. High concentrations
of fluoride can be poisonous (sodium fluoride- rat poison).
*1 L = 10-3 m3 = 1000 cm3

*A substance that vaporizes (liquid to gaseous phase) readily is termed ‘volatile’

*Vapor Pressure- Pressure exerted by the vapors of a substance which are in equilibrium with its solid/
liquid phase

*Colligative Properties- Properties that depend on number of solute particles, irrespective of nature,
relative to total number of particles of solutions
Composition
Described in 2 ways-
(i) Qualitatively: Dilute or concentrated

(ii) Quantitatively:

𝑤 𝑀𝑎𝑠𝑠 𝑜𝑓 𝐶𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡
a) 𝑀𝑎𝑠𝑠 % (𝑤) = 𝑇𝑜𝑡𝑎𝑙 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑥 100

Commonly used in industrial chemical applications like commercial bleaching solution

𝑉 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐶𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡
b) 𝑉𝑜𝑙𝑢𝑚𝑒 % (𝑉) = 𝑇𝑜𝑡𝑎𝑙 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑥 100

35% ethylene glycol (an antifreeze) is used in cars for cooling engine. It lowers freezing point of
water to -17.6 ℃

𝑤 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑆𝑜𝑙𝑢𝑡𝑒
c) 𝑀𝑎𝑠𝑠 𝑏𝑦 𝑉𝑜𝑙𝑢𝑚𝑒 % ( 𝑉 ) = 100 𝑚𝐿.𝑜𝑓 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛

Used in medicine and pharmacy

𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑝𝑎𝑟𝑡𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡

d) 𝑝𝑝𝑚/ 𝑝𝑝𝑏/ 𝑝𝑝𝑡 = 𝑇𝑜𝑡𝑎𝑙 𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑝𝑎𝑟𝑡𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑥 106/ 9/ 12

Concentration of pollutants in water or atmosphere

𝑛𝑖
e) Mole fraction 𝜒𝑖 = ∑𝑛
𝑖=0 𝑛𝑖

Calculations involving gas mixtures

𝑏 𝑛
f) 𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 (𝑀) = 𝑉 (𝐿)

𝑛𝑏
g) 𝑀𝑜𝑙𝑎𝑙𝑖𝑡𝑦 (𝑚) = 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑆𝑜𝑙𝑣𝑒𝑛𝑡 (𝑘𝑔)

*Independent of temperature- Mass %, ppm, mole fraction, molality

*Temperature dependent- Molarity
(Volume is a function of temperature, but mass is not)
Solubility
1) Maximum amount that can be dissolved in specific amount of solvent at a specific temperature
2) Depends on nature of solute and solvent, temperature and pressure

3) Solubility of Solid in Liquid

Solute dissolves in solvent if intermolecular interactions are similar (like dissolves like). When solid
solute is added to solvent, some solute dissolves and concentration increases; known as
dissolution. Some solute particles in solution collide with solid solute particles and get separated
out of solution; known as crystallization. When these processes occur at same rate, dynamic
equilibrium is reached, and at this stage concentration remains constant.

Saturated solution- Solution in which no more solute can be dissolved at a given temperature and
pressure. When solution is in dynamic equilibrium, it contains maximum amount of solute
dissolved in given amount of solvent, and concentration is solubility
Unsaturated solution- Solution in which more solute can be dissolved

Effect of Temperature- If in a nearly saturated solution, dissolution process is endothermic (ΔH > 0),
solubility increases with rise in temperature, and if exothermic (ΔH < 0), solubility decreases
Effect of Pressure- No significant effect because solids and liquids are highly incompressible and
practically remain unaffected by changes and pressure

4) Solubility of Gas in Liquid

Solubility increases with increase in pressure. Increase in pressure over solution increases number of
gaseous particles per unit volume over solution

Henry's Law- At constant temperature, solubility of gas in liquid is directly proportional to partial
pressure of gas present over surface of liquid/ solution. Thus, mole fraction of gas in solution is
proportional to partial pressure of gas over the solution
p = KH χ
Higher value of KH at given pressure, lower is solubility of gas.

Solubility of gases increases with decrease in temperature. Hence, aquatic species are more comfortable
in cold water

To increase solubility of CO2 in soft drinks, bottle is sealed under high pressure
Scuba divers must cope with high concentration of dissolved gases while breathing air at high pressure
under water. Increased pressure increases the solubility of gases in blood. When divers come to
surface, pressure gradually decreases, releasing dissolved gases and leading to formation of
bubbles of nitrogen in blood. This blocks capillaries and creates a condition known as bends. To
avoid toxic effects of high concentrations of nitrogen in blood, tanks used are filled with air
diluted with helium
At high altitudes, partial pressure of oxygen is less than at ground. This leads to low concentration of
oxygen in blood and tissues. This causes climbers to become weak and unable to think clearly;
condition called ‘anoxia’

Effect of Temperature- When dissolved, gas molecules are present in liquid phase and process of
dissolution can be considered similar to condensation and heat is evolved. As dissolution is an
exothermic process, solubility decreases with increase in temperature

Raoult’s Law
a) For a solution of volatile liquids, partial vapor pressure of each component of the solution is
directly proportional to its mole fraction present in the solution
pi = pi° χi

b) Dalton's law of partial pressures

ptotal = p1 + p2
= p1° χ1 + p2° χ2
= (1- χ2 ) p1° + p2° χ2
= p1° + (p2° - p1°) χ2

c) Total vapor pressure of a solution can be related to mole fraction of one component
d) Total vapor pressure of a solution varies linearly with mole fraction of component two
e) Depending on vapor pressure of pure components 1 and 2, total vapor pressure of a solution
decreases or increases with increase of mole fraction of component 1
 f) Minimum value of ptotal is p1° and maximum value is p2°, assuming that component 1 is less
volatile than component 2

g) If y1 and y2 are mole fractions of components 1 and 2 respectively in vapor phase, using Dalton's
law of partial pressures
pi = yi ptotal

h) In a solution of gas in liquid, one component is so volatile that it exists as gas. Thus, solubility is
p = KH χ
Partial pressure of volatile component (gas) is directly proportional to mole fraction in solution. Only
proportionality constant KH differs from p1°. Raoult’s law becomes a special case of Henry's law
in which,
K H = p1 °

Vapor Pressure of Solutions of Solids in Liquids

i. Vapor pressure of solution is only from solvent
ii. Vapor pressure of solution will be lower than vapor pressure of pure solvent
iii. In the solution, the surface has both solute and solvent molecules; thus, fraction of surface
covered by solvent molecules gets reduced. Hence, number of solvent molecules escaping from
surface is correspondingly reduced, and vapor pressure also reduces
iv. Decrease in vapor pressure depends on quantity of solute, irrespective of its nature
Ideal Solutions

● Solutions which obey Raoult's law over entire range of concentration

● Enthalpy of mixing of pure component to form solution is zero. No heat is absorbed or evolved
when components are mixed
ΔHmix = 0
● Volume of mixing is also zero. Volume will be equal to sum of volumes of the two components
ΔVmix = 0

● Intermolecular attractive forces between AA and BB are nearly equal to those between AB,
leading to formation of ideal solution
● n-hexane and n-heptane, bromoethane and chloroethane, benzene and toluene

Non- Ideal Solution

● Does not obey Raoult's law over entire range of concentration

● Positive Deviation- AB interactions are weaker than AA or BB. Hence, solute/ solvent molecules
will find it easier to escape than in pure state. This increases vapor pressure

In pure ethanol, molecules are hydrogen-bonded. On adding acetone, its molecules get in between host
molecules and break the hydrogen bonds. This weakens interactions

In a solution formed by adding carbon disulphide to acetone, dipole interactions between solute- solvent
molecules are weaker than respective interactions between solute- solute/ solvent- solvent
molecules

● Negative Deviation- Intermolecular forces between AA and BB are weaker than AB. This leads
to a decrease in vapor pressure
In a mixture of phenol and aniline, hydrogen bond between phenolic proton and lone pair on nitrogen
atom of aniline is stronger than respective intermolecular hydrogen bonding.

Mixture of chloroform and acetone

Azeotrope
● Binary mixtures which have the same composition in liquid and vapor phase, and boil at constant
temperature. It is not possible to separate them by fractional distillation

● Minimum Boiling Azeotrope- Show positive deviation like 95% by volume of ethanol- water
mixture (fermentation of sugars)

● Maximum Boiling Azeotrope- Shows negative deviation like mixture of 68% HNO3 and 32%
water by mass
Relative Lowering of Vapor Pressure
Δp1 = p1° - p1
= p1° - p1° χ1
= p1° (1 - χ1)
= χ2 p1°
𝛥𝑝1
⇨ 𝑝1°
= 𝜒2

For dilute solutions, n2 « n1,

𝛥𝑝1 𝑛2
⇨ 𝑝1°
= 𝑛1

Elevation of Boiling Point

Vapor pressure of liquid increases with increase in temperature. It boils at temperature at which its vapor
pressure is equal to atmospheric pressure. Vapor pressure of solvent decreases in presence of non-volatile
solute. Thus, boiling point of solution is always higher than that of boiling point of pure solvent. It
depends on number, rather than nature.
𝑇𝑏 − 𝑇𝑏 ° = 𝛥 𝑇𝑏 = 𝐾𝑏 𝑚

𝛥 𝑇𝑏 - Elevation of boiling point

Kb - Boiling point elevation constant/ Molal elevation constant/ Ebullioscopic constant (K kg mol-1)

Depression of Freezing Point

At freezing point of substance, solid phase is in dynamic equilibrium with liquid phase. Thus, it is the
temperature at which vapor pressure of substance in liquid phase is equal to vapor pressure and solid
phase. When solid is added to solvent, vapor pressure decreases and would become equal to that of solid
solvent at lower temperature. Thus, freezing point of solvent decreases.
𝑇𝑓 ° − 𝑇𝑓 = ∆𝑇𝑓 = 𝐾𝑓 𝑚

∆𝑇𝑓 - Depression in freezing point

Kf - Freezing point depression constant/ Molal depression constant/ Cryoscopic constant. Depends on
nature of solvent.
 𝑅 × 𝑀1 × 𝑇𝑓2 𝑅 × 𝑀1 × 𝑇𝑏2
𝐾𝑓 = 𝐾𝑏 =
1000 × ∆𝑓𝑢𝑠𝐻 1000 × ∆𝑣𝑎𝑝𝐻

Solvent Kb Kf
Water 0.52 1.86
Ethanol 1.20 1.99
Benzene 2.53 5.12
Acetic Acid 2.93 3.90

Osmotic Pressure

a) Semi- permeable membrane- Continuous sheets/ films containing a network of submicroscopic

holes through which passage of bigger molecules like solute is hindered. E.g.- Pig’s bladder,
parchment, cellophane
b) Process of flow of solvent molecules from dilute solution to concentrated solution through SPM
till is called osmosis. It continues till equilibrium is attained
c) It can be stopped if extra pressure is applied on concentrated solution. This pressure that just
stops flow of solvent called osmotic pressure
𝛱=𝐶𝑅𝑇

d) Widely used to determine molar mass of proteins, polymers and other macromolecules. Pressure
measurement is around room temperature and molarity is used instead of molality. Magnitude is
large even for very dilute solutions. Useful for biomolecules as they are generally not stable at
higher temperatures and polymers have poor solubility

e) Isotonic- Same osmotic pressure. E.g.- Blood cells and 0.9% sodium chloride solution (normal
saline solution)
f) Hypertonic- Water flows out and shrinks
g) Hypotonic- Water flows in and swells
 h) People taking a lot of salty food experience water retention in tissue cells and intercellular spaces
because of osmosis, resulting in puffiness or swelling, called edema Water movement from soil
into plant roots is also due to osmosis
Preservation of meat by salting and of fruits by adding sugar protects against bacterial action as bacterium
loses water, shrivels and dies

i) Reverse Osmosis- Direction of osmosis can be reversed if pressure larger than osmotic pressure is
applied to solution side. Pure solvent flows out of solution through SPM. E.g.- Desalination of
seawater. SPM used is cellulose acetate, which is permeable to water but impermeable to
impurities and ions present

Van’t Hoff Factor

i. When there is dissociation of solute into ions, experimentally determined molar mass is always
lower than true value
ii. Molar mass that is lower or higher than expected or normal value is called abnormal molar mass
iii. Van't Hoff factor accounts for extent of dissociation and association

𝑛𝑜𝑟𝑚𝑎𝑙 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑏𝑠𝑒𝑟𝑣𝑒𝑑 𝑐𝑜𝑙𝑙𝑖𝑔𝑎𝑡𝑖𝑣𝑒 𝑝𝑟𝑜𝑝𝑒𝑟𝑡𝑦

𝑖 = =
𝑎𝑏𝑛𝑜𝑟𝑚𝑎𝑙 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑐𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑒𝑑 𝑐𝑜𝑙𝑙𝑖𝑔𝑎𝑡𝑖𝑣𝑒 𝑝𝑟𝑜𝑝𝑒𝑟𝑡𝑦
𝑡𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑎𝑓𝑡𝑒𝑟 (𝑑𝑖𝑠)𝑎𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛
=
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 𝑏𝑒𝑓𝑜𝑟𝑒 (𝑑𝑖𝑠)𝑎𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛

iv. Abnormal molar mass is the experimentally determined molar mass and calculated colligative
properties are obtained by assuming that non-volatile solute is neither associated nor dissociated.
v. Association- i < 1; Dissociation- i > 1
𝛥𝑝1 𝑛
vi. 𝑝1°
= 𝑖 𝑛2
1
vii. 𝛥 𝑇𝑏 = 𝑖 𝐾𝑏 𝑚
viii. ∆𝑇𝑓 = 𝑖 𝐾𝑓 𝑚
ix. 𝛱=𝑖𝐶𝑅𝑇