Q.(a) A solution contains 5.85 g NaCl (Molar mass = 58.5 g ) per litre of solution. It has an osmotic pressure of 4.75 atm at 27 °C. Calculate the degree of dissociation of NaCl in this solution. (Given: R = 0.082 L atm )
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Start your 14-day free trial to unlock the full solution →Concept understanding — Van't Hoff Factor
The Intuition: Why a Single Solute Can Act Like Many
Imagine you drop a sugar cube into a cup of tea. The sugar molecules stay whole — each molecule remains one particle. Now imagine you drop a pinch of table salt (NaCl) into water. The salt doesn't stay as NaCl molecules; it splits apart into Na⁺ and Cl⁻ ions. One formula unit of NaCl becomes two separate particles in solution.
If you measure the boiling point elevation or freezing point depression of these solutions, the salt solution behaves as if it has twice as many solute particles as the sugar solution — even though you dissolved the same number of formula units. That's the core idea: colligative properties depend on the number of particles, not the identity of the particles.
But what about substances that do the opposite? Acetic acid in benzene, for example, can pair up into dimers — two molecules associating to form one effective particle. That reduces the particle count.
The Van't Hoff factor is simply the number that tells you: for every one formula unit you dissolve, how many particles actually end up floating around in solution?
The Precise Definition
For an ideal, non-dissociating, non-associating solute, . For a solute that dissociates completely, equals the number of ions produced per formula unit. For a solute that associates, is less than 1.
How It Connects to Colligative Properties
Every colligative property formula gets multiplied by :
- Relative lowering of vapour pressure:
- Elevation of boiling point:
- Depression of freezing point:
- Osmotic pressure:
Where is molality, is molar concentration, and , are moles of solvent and solute respectively.
The Two Cases in Detail
Dissociation (i > 1)
When a solute breaks into ions, the number of particles increases. For a compound that dissociates completely:
The maximum possible is . But if dissociation is partial, lies between 1 and .
The degree of dissociation relates to by:
where is the number of ions produced from one formula unit. For example, for NaCl (), if , then .
For complete dissociation of NaCl, . For CaCl₂, . For Al₂(SO₄)₃, . Memorise these common ones — they appear frequently in numerical problems.
Association (i < 1)
When solute molecules combine to form larger aggregates, the particle count drops. For a dimerisation:
If molecules associate to form one aggregate, and the degree of association is :
For dimerisation (), this becomes .
A common mistake: assuming is always greater than 1. It is not. Association in non-polar solvents (like carboxylic acids in benzene) gives . Always check whether the solute is likely to dissociate or associate in the given solvent.
A Worked Example …
(a) For NaCl, ; Henry's law ; He used (low solubility) to avoid bends.
(b) For , ; KCl > glucose in b.p. (dissociates); salting dehydrates microbes osmotically.
NaCl and Henry's law
Degree of dissociation of NaCl
Concentration: ; K.
Van't Hoff factor from :
For , :
Henry's law and scuba diving
Henry's law: at constant temperature the partial pressure of a gas above a solution is directly proportional to the mole fraction of the gas in solution,
At the high pressures underwater, more dissolves in a diver's blood; on rapid ascent it bubbles out ("bends"). Air is therefore diluted with helium, which is much less soluble in blood (larger ) and non-narcotic, so far less gas dissolves and decompression sickness is avoided.
(a) For NaCl, ; Henry's law ; He used (low solubility) to avoid bends.
(b) For , ; KCl > glucose in b.p. (dissociates); salting dehydrates microbes osmotically.
Fluoroacetic acid and reasoning
Degree of dissociation of --
Molality: moles ; solvent kg → .
From :
For , :
(i) 0.1 M KCl vs 0.1 M glucose …
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