Unit-6
Solution
A solution may be regarded as a single phase containing more than one component.
Every solution consists of a solvent and one or more solutes.
Solvent in a solution is its constituent substances which has the same state of aggregation as that
of the solution. Generally the component present in greater amount than any or all the other
components is called the solvent.
Solutions containing relatively high concentration of solute are called concentrated solutions.
Solutions containing relatively low concentration of solute are called dilute solutions.
Properties of liquids
Vapour pressure:
The Pressure exerted by vapour molecules on the surface area of a liquid, when liquid
phase and vapour phase are in equilibrium, at a given temperature, is called vapour
pressure of the liquid.
When temperature of a liquid is increased, the rate of vapourisation increases. The
temperature at which the vapour pressure of a liquid becomes equal to the external
pressure, the liquid boils. The temperature at which the liquid boils is called boiling
point.
Thus, the temperature at which the vapour pressure of liquid is equal to the
atmospheric pressure is called boiling point.
The boiling temperature of a liquid at 1 atm pressure is called normal boiling point.
The boiling temperature of a liquid at 1 bar pressure is called standard boiling point.
a) Surface Tension:
The force acting along the surface of a liquid at right angles to any line of unit length
is called surface tension (γ).
Units: dynes cm-1 (C.G.S system)
Nm-1 (S.I system)
The phenomenon of surface tension is due to the existence of strong intermolecular
forces of attraction in liquids.
Effect of temperature: Increase in the temperature increases the kinetic energy of
molecules, then their inter molecular attractions decreases. So surface tension
decreases with the increase of temperature.
Examples:
1) The liquid drops are spherical, due to surface tension.
2) The rise of liquid in a capillary tube is due to surface tension.
b) Viscosity:
The property of resistance flow is called Viscosity. Viscosity of a liquid is a measure
of its frictional resistance to the flow of liquid. If viscosity increases then flow of
liquid is decreases. Liquid which flow rapidly have low internal resistance. So their
viscosity is less. Liquids which flow slowly have high internal resistance. So their
viscosity is high.
Examples:
1) Glass is not a solid. It is a super-cooled liquid with a very high viscosity.
2) H2SO4 is viscous, due to H-bonding.
Concentration terms:
Molarity (M):
The number of moles of the solute per litre of the solution, i.e.,
Molarity (M) = Number of moles of solute/number of litres of solution
Or Molarity X number of litres of solution = Number of moles of solute
Let wA g of the solute of molecular mass mA be dissolved in V litre of solution.
wA 1
Molarity of the solution (M) = mA
V
Or
If V is taken in mL, then
Unit of molarity is mol litre-1
Molality (m):
The number of moles of the solute present in 1 kg of the solvent,
Molality (m) = Number of moles of solute/number of kilo-grams of the solvent
Let wA grams of the solute of molecular mass mA be present in wB grams of the solvent, then
Normality (N):
The number of gram equivalents of solute present per litre of solution.
Normality = Number of gram equivalents of solute/Number of litres of the solution
Let wA g of the solute of equivalent mass EA be present in V litres of the solution, then,
Relation between normality and molarity:
Normality = n X Molarity
Mole fraction:
This method is used when the solution is constituted by mixing two or more components.
It is defined as the ratio of number of moles of one component to the total number of moles of
the solution (i.e., all the components).
For example taking three components A, B and C containing solution.
Components A B C
Mass (in grams) w1 w2 w3
Molecular mass m1 m2 m3
[Link] g moles w1/m1 w2/m2 w3/m3
Thus,
Mole fraction of A = (w1/m1) / (w1/m1 + w2/m2 + w3/m3) = fA
Mole fraction of B = (w2/m2) / (w1/m1 + w2/m2 + w3/m3) = fB
Mole fraction of C = (w3/m3) / (w1/m1 + w2/m2 + w3/m3) = fC
The sum of mole fractions of a solution is equal to 1,
i.e., fA + fB + fC = 1.
In a binary solution,
Mole fraction of solute + Mole fraction of solvent =1
Let n moles of solute (A) and N moles of solvent (B) be present in a solution.
Thus, XA + XB = 1
Mole fraction is independent of temperature of the solution.
Colligative properties of dilute solutions:
Dilute solutions containing non-volatile solute exhibit some special properties which depend
only upon the number of solute particles present in the solution irrespective of their nature.
These properties are termed as colligative properties.
The colligative properties are,
1) Lowering in the vapour pressure,
2) Elevation in the boiling point,
3) Depression in the freezing point, and
4) Osmotic pressure.
Colligative properties are the properties of dilute solutions, that is why these are termed as
colligative properties of dilute solutions.
The importance of these properties lies in the fact that they provide methods for the
determination of molecular masses of dissolved solutes. The results are excellent if the
following 3 conditions are satisfied.
1) The solution should be very dilute.
2) The solute should be non-volatile.
3) The solute does not dissociate or associate in solution.
1) Lowering in the vapour pressure:
When a non-volatile solute is added to a solvent, the vapour pressure is lowered due to the
following reasons.
(i) Solvent occupied surface area percentage is decreases. Thus, the rate of evaporation
and vapour pressure decreases. The solute molecules occupy the surface, and so the
percentage of surface area occupied by the solvent decreases.
(ii) According to Graham’s law of evaporation,
When a non-volatile solute is dissolved in a liquid, its density increases. Thus both rate of
evaporation and vapour pressure are lowered.
If p0 is the vapour pressure of pure solvent and ps is the vapour pressure of solution, the
difference (p0- ps) is known as lowering in vapour pressure and the ratio [p0- ps/ p0] is known as
relative lowering in vapour pressure
Raoult established a relationship between relative lowering in vapour pressure and
composition of the solution after a series of experiments in various solvents. The relationship
is known as Raoult’s law. It states that “the relative lowering in vapour pressure of a
dilute solution is equal to mole fraction of the solute present in the solution.”
If n moles of solute be dissolved in N moles of the solvent, the mole fraction of the solute
will be n/n+N.
According to Raoult’s law,
This is mathematical expression for Raoult’s law.
Modified form of Raoult’s law: the above relationship can be written as,
2) Elevation of boiling point (ΔTb)(Ebullioscopy):
The boiling point of the solvent is elevated by the addition of non-volatile solute. The difference
in the boiling point of the solution and the boiling point of the pure solvent is known as
elevation of boiling point.
Elevation of boiling point (ΔTb) = boiling point of the solution – boiling point of pure solvent
From Raoult’s law for dilute solution
Po - Ps w mB
= mA wB
Po A
where, ps = vapour pressure of solution
po = vapour pressure of solute
w mB
Po - Ps = mAA wB Po
For the pure solvent, po (its vapour pressure at the boiling point) and mB (its molecular mass)
are constant.
Therefore,
Where Kb is called as elevation constant.
3) Depression of Freezing point (ΔTf) (Cryoscopy):
Freezing point of a substance is defined as the temperature at which the vapour pressure of its
liquid is equal to the vapour pressure of the corresponding solid.
When non volatile solute is added to the solvent, lowers the vapour pressure of the solvent,
therefore it will be in equilibrium with solid phase at a lower pressure and hence at lower
temperature.
The difference between the freezing points of the pure solvent and its solution is called
depression of freezing point.
Depression of freezing point (ΔTf) = freezing point of the solvent – freezing point of the
solution
From Raoult’s law for dilute solution
Where, ps = vapour pressure of solution
po = vapour pressure of solute
w mB
Po - Ps = mA wB Po
A
For the pure solvent, po and mB are constant.
Therefore,
Where Kf is called as depression constant.
4) Osmosis and osmotic pressure:
Osmosis: The spontaneous flow of solvent molecules through semi permeable membrane from a
pure solvent to a solution or from a dilute to a concentrated solution.
Osmotic pressure:
It is defined as the hydrostatic pressure built up on the solution which just stops the osmosis.
Osmotic pressure = hydrostatic pressure
van’t Hoff theory of dilute solutions:
van’t Hoff realized that an analogy exists between gases and solutions provided osmotic pressure
of solutions is used in place of ordinary gas pressure. He showed that for dilute solutions of non-
electrolytes the following laws hold good.
1) Boyle-van’t Hoff law: the osmotic pressure (P or π) of a solution is directly proportional
to its concentration (C) when the temperature is kept constant. The concentration of the
solution containing one gram mole in V litres is equal to 1/V (C = 1/V)
Thus PαC
or PV = constant or πV = constant
2) Gay-Lussac-van’t Hoff law:
Concentration remaining same, the osmotic pressure of a dilute solution is directly
proportional to its absolute temperature (T), i.e.,
PαT
Combining above two laws,
P α CT
P = SCT
PV = ST or πV = ST
Where S is called molar solution constant. S = 0.082 lit atm K-1 mol-1
If solution contains n gram moles in V litres, the general equation would become
PV = nST or πV = nST
3) Third law:
Equimolecular solutions of different solutes exert equal osmotic pressure under identical
conditions of temperature. Such solutions which have the same osmotic pressure are termed as
isotonic solutions.
Avogadro hypothesis, “equal volumes of dilute solutions of different solutes, having the same
temperature and osmotic pressure, contain equal number of molecules.”
For solution I, PV = n1ST
For solution II, PV = n2ST
Thus, n1 must be equal to n2 when P, V and T are same.
Determination of molecular masses:
For dilute solutions PV = nST,
Instead of one gram mole of the solute present in V litres of solution, let wA gram of solute
(mol. Mass mA) be present in V1 litres of solution, then
thus, the equation PV = nST becomes
Knowing the value of P experimentally, the value of mA, i.e., molecular mass of the solute can be
determined.
Consider two solutions I and II having n1 and n2 moles of the solute in V1 and V2 litres of
solution respectively. Let P1 and P2 be their osmotic pressures at the same temperature (T).
From the equation, PV = nST,
For solution I, P1V1 = n1ST
For solution II, P2V2 = n2ST
If both solutions are isotonic, i.e., P1 = P2
This is the condition for isotonic solutions.
Raoult’s Law:
According to this law, the partial pressure of any volatile constituent of a solution at a constant
temperature is equal to the vapour pressure of pure constituent multiplied by the mole fraction of
that constituent in the solution.
Let a mixture (solution) be prepared by mixing nA moles of liquid A and nB moles of liquid B.
Let pA and pB be the partial pressures of two constituents A and B in solution and pA0 and pB0 the
vapour pressures in pure state respectively.
Thus, according to Raoult’s law,
pA = (nA/nA+nB) pA0 = (mole fraction of A) (pA0) = XA pA0
and pB = (nB/nA+nB) pB0 = (mole fraction of B) (pB0) = XB pB0
If the total pressure be P, then
P = pA + pB
= (nA/nA+nB) pA0 + (nB/nA+nB) pB0
= XA pA0 + XB pB0
Ideal solutions obey Raoult’s law at every range of concentration. Non-ideal solution
does not obey Raoult’s law. They show either positive or negative deviation from Raoult’s law.
Relation between dalton’s law and Raoult’s law:
The composition of the vapour in equilibrium with the solution can be calculated applying
Dalton’s law of partial pressures. Let the mole fractions of vapours A and B be Y A and YB. Let
pA and pB be the partial pressures of vapours A and B respectively and total pressure P.
pA = YA P -------------------(i)
pB = YB P -------------------(ii)
pA = XA pA0 -------------------(iii)
pB = XB pB0 -------------------(iv)
Equating (i) and (iii)
YA P = XA pA0
Similarly equating (ii) and (iv)