SCIENTIA TUITION CENTRE

Gandhi Nagar Avadi

[Link]
Solution:
Homogeneous mixtures of two or more than two components
Expressing Concentration of Solutions
i. Mass percentage (w/w):
Mass by mas % = Mass of solute X 100
Total mass of the solution
WA
Mass % of A = X100
WA+WB
ii. Volume percentage (V/V)
Volume by volume % = Volume of solute X 100
Total volume of solution
VA
Volume % of A = X100
VA +VB
(iii) Mass by volume percentage (w/V):
Mass by volume % = Mass of solute X 100
Total volume of solution
(iv) Parts per million:
Parts per million = Mass of solute × 106
Total mass of the solution
v) Mole fraction:
Mole fraction of a component = Number of moles of the component
Total number of moles of all the components
nA nB
Mole fraction of A XA = Mole fraction of B XB =
n A +¿ n ¿
B B
n A +¿ n ¿
mass∈ gram
No. moles of = Total mole fraction of a solution ( XA + XB ) = 1
molar mass
vi) Molarity: Number of moles of solute dissolved in one litre of solution,
Molarity = No. of Moles of solute
Volume of solution in litre
Vii) Molality (m): Number of moles of the solute dissolved in one kilogram of the solvent
Molality (m) = No. of Moles of solute
Mass of solvent in kg
i) Normality:-[Link] gram equivalents of solute dissolved in one litre of the solution
Normality = [Link] gram equivalents of the solute
Volume of the solution in litre
Molarity, Normality change with temperature due to the change in volume
Inter relationship between concentration terms

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 Molality (m) = 1000 X Molarity
Molarity X mass of solute – 1000X density

Molality = 1000 X mole fraction of solute

Mole fraction of solvent X molar mass of solvent

1 density of the solution molar mass of solute

= -
molality Molarity 1000

molefractionof solute X 1000 X density of the solution

Molarity =
mole fractionof solvent X molar mass of solvent +mole fraction of solute X molar mass of solute
Solubility:
Maximum amount of solute dissolved in a specified amount of solvent at a specified temperature.
Solubility of a Solid in a Liquid
Saturated solution : No more solute can be dissolved at the same temperature and pressure Under these
condition, number of solute particles going into solution( dissolution ) will be equal to the solute particles
separating out(Crystallisation) and a state of dynamic equilibrium is reached.
dissolution
Solute + Solvent Solution
(solid) (liquid) Crystallisation
Factors affecting Solubility of a solid in a Liquid
a) Nature of solute and solvent b) temperature
c) Pressure has insignificant because solids and liquids are incompressible
a) Nature of solute and solvent
Polar solutes dissolve in polar solvents and non polar solutes dissolves in nonpolar solvents.
In general, a solute dissolves in a solvent if the intermolecular interactions are similar in the two
ie. Like dissolves like
b) Temperature
Solubility may increase or decrease with increase in temperature
Case i) Dissolution is endothermic
For a saturated solution ( which follows Le Chateliers Principle), if the dissolution process is
endothermic (∆sol H > 0), the solubility should increase with rise in temperature
dissolution
Solute + Solvent + heat Solution ∆sol H = +ive
Crystallization
E.g. Aqueous solution of solutes such as NaNO3, KNO3,NH4Cl, [Link] ,AgNO3,KI etc
Case ii) Dissolution is exothermic
For a saturated solution ( which follows Le Chateliers Principle), if the dissolution process is
enexothermic (∆sol H < 0), the solubility should increase with rise in temperature
dissolution
Solute + Solvent Solution + heat ∆solH = -ive
Crystallization
E.g. Aqueous solution of solutes such as Lithium sulphate, cerium sulphate etc.

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Solubility of a Gas in a Liquid
Factors affecting Solubility of a solid in a Liquid
a) Nature of a gas and the solvent b) temperature c) pressure
a) Nature of a gas and the solvent : Easily liquefiable gases NH3, SO2, HCl, etc. are more soluble
in water than non-liquefiable gases like O2,H2,N2,He etc.
b) Temperature: Solubility of a gas decreases with increase in temperature because dissolution of
gases in a liquid is exothermic
solute + Solvent Solution + heat ∆solH = -ive
(gas) (liquid)
c) Pressure: Solubility of a gas increases with increase in pressure. This is because on increase in
pressure, more molecules will strike on the surface of liquid and more molecules will dissolve.
Henry’s law:
“The partial pressure of the gas in vapour phase (p) is proportional to the mole fraction of the gas (x) in the
solution”
: p = KH X Where KH is the Henry’s law constant.
p- partial pressure of the gas in vapour phase KH – Henry’s constant
X- mole fraction of the gas (x) in the solution or solubility of gas
Characteristics of Henry’s constant KH:
[Link] gases have different KH values at the same temperature (KH is a function of the nature of the gas)
2. Higher the value of KH at a given pressure, the lower is the solubility of the gas in the liquid
3. KH increases with increase in temperature ( solubility of a gas decreases with increase in temperature)
[Link] slope of the graph [mole fraction Vs partial pressure) gives KH value
Applications of Henry’s law
[Link] increase the solubility of CO2 in soft drinks and soda water, the bottle is sealed under high pressure
[Link] 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)
3At 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. Low blood oxygen causes climbers to become weak and
unable to think clearly, symptoms of a condition known as anoxia
Limitations of Henry’s law
i) Henry’s law is applicable at moderate temperature and pressure only.
ii) Only the less soluble gases obeys Henry’s law
iii) The gases reacting with the solvent do not obey Henry’s law.
Vapour Pressure
When a liquid is taken in a closed vessel, a part of liquid goes to vapour state (called evaporation )
Some of these vapour state molecules strike the surface of liquid and goes to liquid state( condensation)
Evaporation and condensation are continuous processes. If the process is carried out in a closed system, a stage is
reached when the rate of evaporation becomes equal to the rate of condensation.(called equilibrium)
The pressure of the vapour in equilibrium is called vapour pressure of the liquid
The vapour pressure of a liquid depends on its nature, temperature and the surface area.
Boling Point : The boiling point of a liquid is the temperature at which its vapour pressure becomes equal to
the atmospheric pressure (1 atm).

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Boiling point α atmospheric pressure , Boiling point α 1
Vapour pressure
Vapour pressure solution of liquid in liquids
Raoult’s law: For a solution of volatile liquids the partial vapour pressure of each component of the solution is
directly proportional to its mole fraction present in solution
PA α XA PA = P0A XA where P°A is the vapour pressure of pure component ‘A’
For the component ‘B
PB α XB PB = P0B XB where P°B is the vapour pressure of pure component ‘B’
PTotal = pA + pB
PTotal = P0A XA + P0B XB We know that XA + XB = 1 or XA = 1 - XB
0 0
Therefore, PTotal = (1 - XB) P A + P B XB
, PTotal = P0A - P0A XB + P0BXB PTotal= P0A + (P0B - P0A) XB
The above equation is of the straight-line equation form y = mx+c.
The plot of , PTotal l versus XB will give a straight line with (P0B - P0A) as slope and P0A as the y intercept.
Assuming component “B ” is more volatile (less boiling point) than “A” (P0B > P0A)

If yA and yB are the mole fractions of the components A and B respectively in the vapour phase
then, using Dalton’s law of partial pressures:
PA = yA Ptotal and PB = yB Ptotal
Difference between ideal and non-ideal solution
[Link] Ideal solution Non ideal solution
1. Solute as well as the solvent obeys Solution does not obeys the Raoult’s law over
the Raoult’s law over the entire the entire range of concentration.
range of concentration.
2 No change in the volume on mixing change in the volume on mixing ∆Vmix ≠ 0
∆Vmix = 0
3. no exchange of heat when the solute exchange of heat when the solute is dissolved in
is dissolved in solvent ∆Hmix = 0 solvent ∆Hmix≠ 0
4. Escaping tendency of the solute and Escaping tendency of the solute and the solvent
the solvent present in it should be present in it should be different from pure liquids
same as in pure liquids.

Examples for ideal solutions:

(Benzene & Toluene) ; (n-hexane & n-heptane) ; (Ethyl bromide & Ethyl iodide) ; (Chlorobenzene &
Bromobenzene).
Non-ideal solutions - positive deviation from Rauolt's Law:
i)Intermolecular attractive forces between A and B are weaker than those between the molecules of A (A-A)
and molecules of B (B-B).
ii)Escaping tendency of A and B in solution will be easier when compared with A and B in their pure state.
iii)The vapour pressure of such non-ideal solution increases and it is greater than the sum of the
vapour pressure of A and B as predicted by the Raoult’s law
PA > P0A XA PB > P0B XB , PTotal > P0A XA + P0B XB
iv)There is a slight increase in volume (ΔVmixing >0) on mixing
v)During this process heat is absorbed ∆Hmixing = positive ( endothermic)

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vi)Increase in temperature increases the soluility
Examples for non-ideal solutions showing positive deviations:
(Ethyl alcohol & cyclohexane), (Ethyl alcohol & water.) (ethyl alcohol & Acetone)
(Benzene & acetone), (Carbon tetrachloride & chloroform),
Non-ideal solutions - negative deviation from Rauolt's Law
i)Inter molecular attractive forces between A and B are stronger than those between the individual
components (A-A & B-B)
ii)Escaping tendency of A and B in solution will be lower when compared with an ideal solution formed
by A and B
iii)Hence, the vapour pressure of such solutions will be lower than the sum of the vapour pressure of A and B
PA < P0A XA PB < P0B XB , PTotal < P0A XA + P0B XB
iv)There is a slight decrease in volume (ΔVmixing< 0) on mixing
v)During this process heat is evolved ∆Hmixing = negative ( exothermic)
vi)Increase in temperature decreases the solubility
Examples for non-ideal solutions showing negative deviation: (chloroform + Acetone ), (Chloroform + diethyl
ether), (Chloroform + Benzene ), (Chloroform + nitric acid) (nitric acid + water) , (Acetone + aniline).

Azeotropes
Binary mixtures having the same composition in liquid and vapour phase and boil at
a constant temperature
It is not possible to separate the components by fractional distillation.
Minimum boiling azeotrope
The solutions which show a large positive deviation from Raoult’s law form minimum boiling
azeotrope at a specific composition.
Maximum boiling azeotrope
The solutions that show large negative deviation from Raoult’s law form maximum boiling
azeotrope at a specific composition
Colligative Properties:
Properties depend on the number of solute particles independent on their nature eg.: Relative lowering of
vapour pressure (2) depression of freezing point (3) elevation of boiling point and (4) osmotic pressure
Relative Lowering of VapourPressure

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 If a non-volatile solute is added to a solvent, the vapour pressure of the solution is lower than
the vapour pressure of the pure solvent at the same temperature. In the solution, the surface has both
solute and solvent molecules; there by the fraction of the surface covered by the solvent molecules
gets reduced. Hence number of solvent molecules escaping from the surface is reduced, thus, the
vapour pressure is also reduced.
Raoult’s law: Partial vapour pressure of each volatile component in the solution is directly
proportional to its mole fraction.
PA = P0A XA
Lowering of Vapour Pressure = vapour pressure of pure solvent – vapour pressure of solution
∆P= P0A - PA
Relative Lowering of Vapour Pressure = Lowering of Vapour Pressure
vapour pressure of pure solvent
∆P = P0A - PA
P0A P0A
= P0A - P0A XA = P0A (1- XA)
P0A P0A
= XB
ie Relative Lowering of Vapour Pressure = molefraction of solute
= nB = nB (since nB< < nA)
nA + nB nA

= WB MA
MB WA
Elevation of boiling point
When a nonvolatile solute is added to a pure solvent at its boiling point, the vapour pressure of
the solution is lowered below 1 atm.
As a result, the solution boils at a higher temperature (Tb ) than the boiling point of the pure solvent (Tb ° )
This increase in the boiling point is known as elevation of boiling point.
Elevation of boiling point (ΔTb ) = boiling point of the solution - boiling point of the pure solvent
ΔTb = Tb - Tb°
Elevation of boiling point is directly proportional to the molal concentration of the solution
∆Tb α m ∆Tb = Kb m
Where Kb = molal boiling point elevation constant or Ebullioscopic constant.
Ebullioscopic constant: Elevation in boiling point for 1 molal solution
∆Tb = Kb m M2- Molar mass of solute
= Kb X W2 X1000 M2 = Kb X W2 X1000 Kb- Ebullioscopic constant
M2 XW1 ∆Tb x W1 W1 –mass of solvent in gm
0 2
Kb = RT b M solvent ∆Tb - Elevation of boiling point
0
1000X ∆Hvapourisation T b- boiling point of solvent
Depression in freezing point R- gas constant
Freezing point: The temperature at which the solid and the liquid states of the substance have the
same vapour pressure
When a nonvolatile solute is added to water at its freezing point, the freezing point of the solution is
lowered from 0 ˚C
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The lowering of the freezing point of the solvent when a solute is added is called depression in
freezing point (ΔTf ).
Depression of freezing point (ΔTf ) = freezing point of the pure solvent - freezing point of the solution
ΔTf = T0f - Tf
Depression in freezing point point is directly proportional to the molal concentration of the solution
∆Tf α m ∆Tf = Kf m
Where Kf = molal freezing point elevation constant or Cryoscopic Constant
Cryoscopic Constant: Depression in freezing point point for 1 molal solution
∆Tf = Kf m M2- Molar mass of solute
= Kf X W2 X1000 M2 = Kf X W2 X1000 Kf- Cryoscopic Constant
M2 XW1 ∆Tf x W1 W1 –mass of solvent in gm
02
Kf = RT f M solvent ∆Tf - Cryoscopic Constant
1000X∆Hfusion T0f- freezing point of solvent
Osmosis and Osmotic Pressure R- gas constant
semipermeable membrane(SPM):The membrane allows only solvent molecules to pass through
it in either direction but not solute .eg. animal membrane like pig’s bladder, plant membrane etc.
Osmosis: Solvent molecules pass through a semi permeable membrane from a solution of lower
concentration to a solution of higher concentration
Osmotic Pressure: The pressure that must be applied to the solution to stop the solvent osmosis
through the semipermeable membrane
osmotic pressure is proportional to the molarity, C of the solution at a given temperature T
π = CRT
C = Concentration of the solution in molarity T = Temperature R = Gas constant
π = n2 RT since C = n2 n2 = W2
V V M2
π = W2 RT W2 – mass of solute in gm, M2 – molar mass of solute
V M2 V- volume of solution in litre
Significances of osmotic pressure over other colligative properties
[Link] elevation of boiling and the depression in freezing point, magnitude of osmotic pressure is large.
2. Osmotic pressure for determination of molar mass of solutes is useful for biomolecules as they
are generally not stable at higher temperatures and polymers have poor solubility.
[Link] pressure is measured under room temperature and the molarity of the solution is used
instead of molality
Isotonic solutions: Two solutions having same osmotic pressure at a given temperature
The net solvent flow between the two isotonic solutions is zero.
Hemolysis: If the Intravenous solutions are too dilute (hypotonic), the solvent from outside of the
cells will flow into the cell to normalise the osmotic pressure and this process is called hemolysis,
causes the cells to burst.
Crenation: If the Intravenous solutions are too concentrated (hypertonic) the solvent
molecules will flow out of the cells, which causes the cells to shrink and die.
Edema: 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
Reverse osmosis: In this process solvent passes through a semipermeable membrane in the opposite
direction of osmosis, when subjected to a hydrostatic pressure greater than the osmotic pressure.
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Application of reverse osmosis: When a pressure higher than the osmotic pressure is applied on
the solution side (sea water) the water molecules moves from solution side to the solvent side
through semipermeable membrane (Opposite to the Osmotic flow). Pure water can be collected.
commonly used SPM: cellulose acetate
Abnormal Molar Masses
In certain solvents, solute molecules associate to form a dimer or trimer etc… This reduces the
total number of particles (molecules) formed in solution and increase in value of colligative
property like ∆Tb , ∆Tf osmatic pressure etc. As a result the calculated molar mass will be
higher than the actual molar mass
2CH3COOH → (CH3COOH)2
The molar mass of acetic acid ( in benzene )calculated using colligative properties is found to be
(around 120 g mol-1 ) two times the actual molar mass (60 g mol-1).
The electrolytes such as KCl or NaCl dissociates completely into its constitutent ions in their
aqueous solution. This causes an increase in the total number of particles (ions) present in the
solution. The calculated molar mass using colligative property measurement for this type of
solutions will be lower than the actual molar mass.
NaCl (s) → Na+ (aq) + Cl– (aq)
Molar mass that is either lower or higher than the expected or normal value is called
as abnormal molar mass.
van’t Hoff factor
To quantify the extent of association or dissociation of solutes in solution, van’t Hoff introduced a
term 'i' which is now called van’t Hoff factor.
i= Normal ( actual) molar mass (OR) = Observed colligative property
Observed (abnormal) molar mass Calculated colligative property
Inclusion of van’t Hoff factor modifies the equations for colligative properties as follows:
Relative Lowering of Vapour Pressure =
∆P = P0A - PA = i n solute
P0A P0A n solvent
Elevation of boiling point (ΔTb ) = i Kb m
Depression of freezing point (ΔTf ) = i Kf m
Osmotic Pressure π = i W solute RT
V M solute
i value Solute nature Molar mass
i=1 does not dissociate or associate molar mass equal to actual molar mass
i<1 solutes associate to form higher observed molar mass will be greater than the
oligomers in solution actual molar mass
i>1 solutes dissociates into their constituent observed molar mass will be less than the normal
ions molar mass.

The degree of dissociation or association can be related to Van't Hoff factor (i) using the following
relationships
α dissociation = i-1 (n is number ions formed by the dissociation )
n-1
α association = (1-i) n (n is the number of solute involved in association)
n-1

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1.A litre of sea water (weight 1030g) contains 6 X 10-3g of dissolved oxygen Calculate its
mass % and ppm
Mass % of A = WA/(WA+WB) X100
Mass % of O2 = (6X〖10〗^(-3))/1030 X100
= 5.8X 10-4 %
Ppm of O2 = (6X〖10〗^(-3))/1030 X106 = 5.8 ppm
[Link] aqueous solution has higher concentration: 1molar or 1molalsolution of the same
solute.
Give reason
One molar solution means 1 mole solute present in 1 litre of solution
( ie. Volume of solute + volume of solvent = 1 litre)
One molal solution means 1 mole solute dissolved in 1000 ml of water ( because density of water
is one)
ie. Volume of solvent alone one litre
Volume of solvent in 1 molar solution is less. Hence one malar solution has higher concentration
than 1molal solution
[Link] out of molarity or molality will change with change in temperature and why?
Molarity = No. of Moles of solute
Volume of solution in litre
Molality (m) = No. of Moles of solute
Mass of solvent in kg
Volume of solution increases with increase in temperature due to expansion. Hence when temperature
increases volume of solution increases which causes decrease in molarity
When temperature increases mass of solvent does not change. and molality does not change

Practice Questions;
[Link] Henry’s [Link] is the effect of temperature on the solubility of a Gas in a liquid
[Link] species are more comfortable in cold waters rather than in warm waters