COLLIGATIVE PROPERTIES

Colligative Property : A property of a solvent that depends

on the total number of solute particles present in a given
volume of solvent and not at all upon the nature of the
solute
• Elevation of Boiling Point
• Depression of Freezing Point
• Lowering of Vapor Pressure
• Osmotic Pressure
 RAOULT’S LAW
• In Ideal Solutions:
• p1 = x1 p10

• Note:
• p10 = Vapor Pressure of Pure
Solvent
• P1 = partial pressure of the
solvent
Raoult’s Law breaks down when
solvent-solvent and solute-solute
intermolecular forces of attraction
are much stronger or weaker than
solute-solvent intermolecular forces.
Elevation in boiling point

The change in boiling point is

proportional to the number of
solute particles present and can
be related to the molality of the
solution:

DTb = Kb.m
where DTb = boiling point elevation
Kb = molal boiling point elevation
constant (ebullioscopic constant)
m = molality of solution

The value of Kb depends only on the identity of the solvent

Depression in freezing point

• The addition of a
nonvolatile solute
causes solutions to have
lower freezing points
than the pure solvent.

DTf = Kf  m
where DTf = freezing point depression
Kf = molal freezing point depression
constant (cryoscopic constant)
m = molality of solution
 Relative lowering of vapour pressure
• The addition of a non-volatile solute to a solvent at a given temperature and
pressure, results in the lowering of vapour pressure of the solvent.
• According to Raoult’s law,
• 𝑝1 = 𝑥1 𝑝10 ……..(1)
• If x2 is the mole fraction of the solute in the solution, then
• 𝑥1 + 𝑥2 = 1, 𝑥1 = 1 − 𝑥2
• Equation (1) can be written as,
• 𝑝1 = 𝑥1 𝑝10 = (1 − 𝑥2 )𝑝10 = 𝑝10 − 𝑥2 𝑝10
𝑝10 −𝑝1
• 𝑥2 𝑝10 = 𝑝10 − 𝑝1 , 𝑥2 = ⟹ 𝑟𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑙𝑜𝑤𝑒𝑟𝑖𝑛𝑔 𝑜𝑓 𝑣𝑎𝑝𝑜𝑢𝑟 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒
𝑝10
• We see that the relative lowering of vapour pressure is proportional to the mole
fraction of the non-volatile solute in solution is independent on the nature of the
solute
𝑛2
• 𝑥2 = , for very dilute solution the number of moles of the solute n2 can be
𝑛1 +𝑛2
neglected as compared to the number of moles of the solvent (n1)

𝑛2
𝑊2
𝑀2 𝑊2 𝑀1
• M2 molar mass of solute, W2 wt/ amount of solute
• 𝑥2 = = 𝑊1 = • M1 molar mass of solvent, W1 wt/ amount of solvent
𝑛1 𝑊1 𝑀2
𝑀1
 Relative lowering of vapour pressure
𝑝10 −𝑝1 𝑊2 𝑀1
• = LVP in terms of molarity
𝑝10 𝑊1 𝑀2
• LVP in terms of molality
• If m moles of the solute are dissolved in 1000 g of solvent, molality
𝑊2
• = 𝑚, 𝑊1 = 1000𝑔
𝑀2
𝑝10 −𝑝1 𝑚𝑀 1
• 𝑥2 = = 1000𝑔
𝑝10
• Derivation of EBP &DFP
• At normal BP of pure solvent A (𝑇𝑏∗ ), the solvent vapor and liquid are in equilibrium at 1
atm, so their chemical potentials are equal;
• 𝜇𝐴∗ 𝑔, 1𝑎𝑡𝑚, 𝑇𝑏 ∗ = 𝜇𝐴∗ 𝑙, 1𝑎𝑡𝑚, 𝑇𝑏 ∗ ……….(1)
• In the presence of a solute B, the mole fraction of A is reduced from 1 to 𝑥𝐴 = 1 − 𝑥𝐵
and the BP is Tb at equilibrium the solvent vapour and liquid are equilibrium
• 𝜇𝐴∗ 𝑔, 1𝑎𝑡𝑚, 𝑇𝑏 = 𝜇𝐴 (𝑙, 𝑥𝐴 , 1𝑎𝑡𝑚, 𝑇𝑏)……….(2)
• The chemical potential of the solvent in the solution is related to its mole fraction by,
• 𝜇𝐴 𝑙, 𝑥𝐴 , 1𝑎𝑡𝑚, 𝑇𝑏 = 𝜇𝐴∗ 𝑙, 1𝑎𝑡𝑚, 𝑇𝑏 + 𝑅𝑇𝑏 𝑙𝑛𝑥𝐴
• The equation 2 becomes,
• 𝜇𝐴∗ 𝑔, 1𝑎𝑡𝑚, 𝑇𝑏 = 𝜇𝐴∗ 𝑙, 1𝑎𝑡𝑚, 𝑇𝑏 + 𝑅𝑇𝑏 𝑙𝑛𝑥𝐴
∗ ∗
𝜇𝐴 𝑔,1𝑎𝑡𝑚,𝑇𝑏 −𝜇𝐴 𝑙,1𝑎𝑡𝑚,𝑇𝑏
• 𝑙𝑛𝑥𝐴 = 𝑅𝑇𝑏
 Derivation of EBP &DFP
• The chemical potential of a pure substance is the same as the molar Gibb’s energy of the
substance, so this expression is the same as,
𝐺𝑚 𝑔,1𝑎𝑡𝑚,𝑇𝑏 −𝐺𝑚 𝑙,1𝑎𝑡𝑚,𝑇𝑏 ∆𝑣𝑎𝑝 𝐺(1 𝑎𝑡𝑚,𝑇𝑏)
• 𝑙𝑛𝑥𝐴 = =
𝑅𝑇𝑏 𝑅𝑇𝑏
• When xA = 1 (so 𝑙𝑛𝑥𝐴 =0), the pure solvent the BP is 𝑇𝑏 ∗ and we can write
∆𝑣𝑎𝑝 𝐺(1 𝑎𝑡𝑚,𝑇𝑏∗ )
• 𝑙𝑛𝑥𝐴 = 0 = 𝑅𝑇𝑏∗
• The difference between these 2,
∆𝑣𝑎𝑝 𝐺( 𝑇𝑏) ∆𝑣𝑎𝑝 𝐺(𝑇𝑏∗ )
• 𝑙𝑛𝑥𝐴 = −
𝑅𝑇𝑏 𝑅𝑇𝑏∗
• Now we use, ∆𝐺 = ∆𝐻 − 𝑇∆𝑆 and the approximate temperature independent of ∆𝐻
and ∆𝑆 to turn this equation into,
∆𝑣𝑎𝑝 𝐻 𝑇𝑏 −𝑇𝑏∆𝑣𝑎𝑝 𝑆 𝑇𝑏 ∆𝑣𝑎𝑝 𝐻 𝑇𝑏∗ −𝑇𝑏∗ ∆𝑣𝑎𝑝 𝑆 𝑇𝑏∗
• 𝑙𝑛𝑥𝐴 = −
𝑅𝑇𝑏 𝑅𝑇𝑏∗
∆𝑣𝑎𝑝 𝐻 𝑇𝑏 𝑇𝑏∆𝑣𝑎𝑝 𝑆 𝑇𝑏 ∆𝑣𝑎𝑝 𝐻 𝑇𝑏∗ 𝑇𝑏∗ ∆𝑣𝑎𝑝 𝑆 𝑇𝑏∗
• = − − 𝑅𝑇𝑏∗ +
𝑅𝑇𝑏 𝑅𝑇𝑏 𝑅𝑇𝑏∗

∆𝑣𝑎𝑝 𝐻 𝑇𝑏 ∆𝑣𝑎𝑝 𝑆 𝑇𝑏 ∆𝑣𝑎𝑝 𝐻 𝑇𝑏∗ ∆𝑣𝑎𝑝 𝑆 𝑇𝑏∗

• 𝑙𝑛𝑥𝐴 = − − +
𝑅𝑇𝑏 𝑅 𝑅𝑇𝑏∗ 𝑅
• Let us assume that ∆𝑣𝑎𝑝 𝐻 and ∆𝑣𝑎𝑝 𝑆 are independent of Temp.
 Derivation of EBP &DFP
∆𝑣𝑎𝑝 𝐻 𝑇𝑏 ∆𝑣𝑎𝑝 𝑆 𝑇𝑏 ∆𝑣𝑎𝑝 𝐻 𝑇𝑏∗ ∆𝑣𝑎𝑝 𝑆 𝑇𝑏∗
• 𝑙𝑛𝑥𝐴 = − − +
𝑅𝑇𝑏 𝑅 𝑅𝑇𝑏∗ 𝑅
• Let us assume that ∆𝑣𝑎𝑝 𝐻 and ∆𝑣𝑎𝑝 𝑆 are independent of Temp.
∆𝑣𝑎𝑝 𝐻 ∆𝑣𝑎𝑝 𝑆 ∆𝑣𝑎𝑝 𝐻 ∆𝑣𝑎𝑝 𝑆
• 𝑙𝑛𝑥𝐴 = − − +
𝑅𝑇𝑏 𝑅 𝑅𝑇𝑏∗ 𝑅
∆𝑣𝑎𝑝 𝐻 1 1
• 𝑙𝑛𝑥𝐴 = − 𝑇𝑏∗
𝑅 𝑇𝑏
• Now we use 𝑙𝑛𝑥𝐴 = ln 1 − 𝑥𝐵 = −𝑥𝐵 (when xB is very small by Taylor series)

∆𝑣𝑎𝑝 𝐻 1 1 ∆𝑣𝑎𝑝 𝐻 𝑇𝑏∗ −𝑇𝑏

• −𝑥𝐵 = − = 𝑅
𝑅 𝑇𝑏 𝑇𝑏∗ 𝑇𝑏𝑇𝑏∗
• Here the EBP is, ∆𝑇𝑏 = 𝑇𝑏 − 𝑇𝑏 ∗ Then we
note that the values of Tb ans Tb* is very
close , little error is involved in replacing TbTb* by Tb*2
∆𝑣𝑎𝑝 𝐻 ∆𝑇𝑏
• 𝑥𝐵 = . Tb∗2 we can see that the mole fraction of solute is proportional to ∆𝑇𝑏
𝑅
𝑅𝑇𝑏∗2
• ∆𝑇𝑏 = × 𝑥𝐵 = 𝑘𝑏 𝑚
∆𝑣𝑎𝑝 𝐻
• Derivation for DFP, 𝜇𝐴∗ 𝑆, 1𝑎𝑡𝑚, 𝑇𝑓 = 𝜇𝐴 (𝑙, 𝑥𝐴 , 1𝑎𝑡𝑚, 𝑇𝑓)……….(2)
𝑅𝑇𝑓∗2
• ∆𝑇𝑓 = ∆ × 𝑥𝐵 = 𝑘𝑓 𝑚
𝑓𝑢𝑠 𝐻
• Use of EBP & DFP : purity of organic compounds, impurity lowers the MP
• Salt is spread on the highways to delay freezing
 Osmosis
• The passage of a pure solvent
into a solution separated from it
by a semipermeable membrane
(SPM)
• SPM: permeable to solvent not to
solute
Van’t Hoff equation

Constant, B is called osmotic virial coefficient

 Osmosis

Measuring OP @ series of mass concentrations

RO systems
high salt and sugar
concentration is
hypertonic to
bacteria cells, and
bacteria cells lose
water and it kills
them by
Pruned or Wrinkled Fingers dehydration
Thermodynamic treatment
Thermodynamic treatment
 Thermodynamic treatment

According to this equation, the osmotic pressure of a solution is proportional to

the amount n of solute B present in it
Abnormal colligative properties
• CPs doesn’t follow the number of solute particles
• Reason: association or dissociation of solute particles

Association : effective number decreases

Egs:
• acetic acid in benzene : molar mass determined by FP is
118 instead of 60, (CH3COOH)2

Dissociation : effective number increases

Egs:
• NaCl exists as Na+ and Cl- OP, LVP, EBP, DFP α 1/ molar mass

Degree of association: The fraction of the total number of molecules which combine to
form bigger molecules
 Van’t HOFF FACTOR
Δ Tf = imK f OR Δ Tb = imK b

i = No. of particles in solution per formula

unit (range 1 – n)
i.e. for sucrose i = 1 [no dissociation]
for NaCl i = 2 [NaCl → Na++Cl-]
for K2SO4 i = 3 [K2SO4 → 2K+ + SO42- ]