Section 1: Concentration Terms and Henry's Law
Concentration of a solution is expressed as molality (mol/kg solvent — temperature independent), molarity (mol/L solution — temperature dependent), or mole fraction. Henry's law (p = K_H × x) describes gas dissolution: at constant temperature, the amount of gas dissolved in a liquid is proportional to the partial pressure of that gas above the liquid. K_H increases with temperature, so gas solubility decreases with rising temperature. This underpins the physics of carbonated drinks and the physiology of decompression sickness.
Section 2: Raoult's Law and Types of Solutions
Raoult's law gives the vapour pressure of each component in a binary liquid mixture. Ideal solutions (benzene + toluene) obey it perfectly with _mix = 0 and _mix = 0. Non-ideal solutions deviate: positive deviation (ethanol + water — weaker A-B forces, _mix > 0, _mix > 0, minimum boiling azeotrope) and negative deviation ( + acetone — stronger A-B forces, _mix < 0, _mix < 0, maximum boiling azeotrope). Azeotropes cannot be separated by simple distillation because the vapour and liquid phases have the same composition at the azeotrope.
Section 3: Colligative Properties
All four colligative properties depend exclusively on the number of solute particles per unit of solvent:
- Relative lowering of VP: /P° = x_solute (measured by manometer)
- Boiling point elevation: = Kb·m (measured by Beckmann thermometer; Kb water = 0.52 K·kg/mol)
- Freezing point depression: = Kf·m (Kf water = 1.86 K·kg/mol; Kf > Kb because us < ap)
- Osmotic pressure: π = CRT (measured by osmometer; most sensitive — preferred for macromolecules)
Molar mass is calculated from each: most commonly = Kb × w_{2} × 1000 / ( × w_{1}). Camphor (Kf = 40 K·kg/mol) gives the largest per mole — ideal for Rast's camphor method.
Section 4: Electrolytes and Van't Hoff Factor
The van't Hoff factor (i) corrects colligative property formulas for electrolytes: = iKbm, = iKfm, π = iCRT. For dissociating electrolytes: i = 1 + (n−1)α. For associating solutes: i = 1 − (n−1)α/n (for dimerization: i = 1 − α/2). Complete dissociation of NaCl gives i = 2, gives i = 3, gives i = 4. Acetic acid in benzene completely dimerizes (α = 1) giving i = 0.5. Association causes the apparent molar mass to exceed the true value; dissociation makes it appear lower.
Section 5: Osmosis and Applications
Osmosis is the spontaneous passage of solvent through a semipermeable membrane from lower to higher solute concentration (lower to higher osmotic pressure). Osmotic pressure π = iCRT. Applying pressure exceeding π reverses the flow (reverse osmosis) — the basis of RO water purification and desalination. Isotonic solutions (equal π) do not cause osmotic stress on cells. Blood cells require isotonic environment (0.9% NaCl) — hypotonic solutions cause haemolysis; hypertonic cause crenation.