Colligative Properties
Colligative properties depend only on the number of solute particles in solution, not on their chemical identity. The four colligative properties are: (i) relative lowering of vapour pressure, (ii) elevation of boiling point (), (iii) depression of freezing point (), and (iv) osmotic pressure (). All four can be used to determine unknown molar masses of non-volatile solutes. Everyday applications include ethylene glycol as car radiator antifreeze, salting icy roads in winter, and reverse osmosis desalination of sea water.
- Relative lowering of vapour pressure:
- Elevation of boiling point: ; molar mass
- Depression of freezing point: ; molar mass
- Ebullioscopic constant: ; Cryoscopic constant:
- Osmotic pressure: (Van't Hoff equation) or
- Molar mass from osmotic pressure:
- Isotonic condition: (same molar concentration at same T)
- For water: K kg mol, K kg mol
1. What Are Colligative Properties
Colligative properties are properties of a solution that depend only on the number of solute particles dissolved, not on their nature (mass, size, or chemistry).
The Latin root colligatus means "bound together" - colligative properties tie together several apparently different observations under one common cause: dissolved solute particles reduce the escape tendency of solvent molecules from the liquid phase.
There are four colligative properties:
- Relative lowering of vapour pressure - the drop in vapour pressure caused by dissolving a non-volatile solute
- Elevation of boiling point - the increase in boiling point of the solvent when solute is added
- Depression of freezing point - the decrease in freezing point of the solvent
- Osmotic pressure - the pressure needed to stop osmosis of pure solvent into the solution
All four are useful for finding the molar mass of an unknown non-volatile solute, because the "number of particles" is directly related to .
Assumption: the standard colligative-property formulas assume the solute is non-volatile and does not dissociate or associate. When a solute dissociates (like NaCl into Na and Cl) or associates (like benzoic acid dimerising in benzene), the actual number of particles differs from the assumed count. This is handled by the Van't Hoff factor , covered in the next concept (Abnormal Molar Masses).
2. Relative Lowering of Vapour Pressure
When a non-volatile solute is added to a solvent, the vapour pressure of the solvent decreases. If is the vapour pressure of the pure solvent and is that of the solution, applying Raoult's law:
Rearranging gives the relative lowering of vapour pressure:
The relative lowering equals the mole fraction of the solute - it is independent of the nature of the solute, so it is a colligative property.
For dilute solutions, , so
In terms of molality: (where is molality and is molar mass of solvent in g/mol).
From first case: mmHg.
From second case: .
Mole fraction of solvent .
Consider 1 L of solution: mass of dissolved g.
Mass of 1 L solution g.
Mass of water in 1 L g. Moles of water mol.
dissociates as (3 particles per formula unit).
Total moles of solute particles mol.
Mole fraction of water .
mmHg.
3. Elevation of Boiling Point
The boiling point of a liquid is the temperature at which its vapour pressure equals the external (usually atmospheric) pressure. When a non-volatile solute is added, the vapour pressure decreases, so the solution must be heated to a higher temperature than the pure solvent to bring its vapour pressure up to atmospheric. This upward shift is called elevation of boiling point.
where is elevation, is molality (mol/kg of solvent), and is the molal elevation constant (also called the ebullioscopic constant) of the solvent. Unit of : K kg mol.
can be derived from solvent properties:
Physical meaning of : the boiling point elevation produced (theoretically) by a 1 molal solution of a non-volatile, non-electrolyte solute.
Determining molar mass: if g of solute of molar mass is dissolved in g of solvent, then
For water, K kg mol - meaning 1 mole of any non-electrolyte solute in 1 kg of water raises the boiling point by 0.512 °C.
Empirical formula: mole ratios C : H : O .
Empirical formula = ; empirical mass = 30 g/mol.
Molar mass from BP elevation: K.
Mass of solute = 5 g in 100 g total, so mass of water = 95 g.
g/mol.
Molecular formula: (glucose).
All three are isomeric alcohols with the same molar mass, but their boiling points differ because of shape (branching).
Going from -butanol to tert-butanol, branching increases, which decreases the surface area available for intermolecular van der Waals interactions. Weaker intermolecular attraction means the liquid boils at a lower temperature - so decreases in the same order.
From the formula and Trouton's rule that is nearly constant for similar liquids, we get . So follows the same order as : -butanol isobutanol tert-butanol.
4. Depression of Freezing Point
The freezing point of a solvent is the temperature at which its solid and liquid phases have the same vapour pressure. When a non-volatile solute is added, the vapour pressure of the liquid solution falls below the vapour pressure of the pure solid at the original freezing point. To re-establish solid-liquid equilibrium, the temperature must be lowered - giving a depression of the freezing point.
where is depression, is molality, and is the molal depression constant (also called cryoscopic constant) of the solvent.
Analogous to :
Determining molar mass:
For water, K kg mol. Because is generally larger than (freezing produces bigger temperature shifts per mole than boiling), FP depression is more sensitive for measuring small solute amounts and is preferred for molar mass determination.
At °C, the remaining liquid solution has K.
g.
Ice separated g.
Consider 100 g of solution: 5 g urea, 1 g KCl, 10 g glucose, 84 g water.
Total = sum of contributions from each solute:
(For KCl, since it dissociates into K and Cl.)
K
Freezing point K °C.
Boiling point elevation . For the same and same solvent, .
- Glucose: non-electrolyte,
- NaCl Na + Cl:
- + 2Cl:
- :
Order of increasing : glucose NaCl .
(The FP depression follows the reverse order for temperatures below 0 °C.)
5. Osmosis and Osmotic Pressure
Certain membranes allow small solvent molecules to pass through but block larger solute molecules. Such membranes are called semipermeable membranes (SPM) - examples are animal bladders, vegetable tissues, cellophane, and cellulose acetate.
Osmosis is the spontaneous flow of solvent molecules through a semipermeable membrane from a region of lower solute concentration (or pure solvent) to a region of higher solute concentration.
Osmotic pressure () is the external pressure that must be applied to the solution side to just stop osmosis. It is a property of the solution and depends on the molar concentration of solute particles.
or equivalently
This is the Van't Hoff equation for dilute solutions. Notice its similarity to the ideal gas law - a coincidence that reflects the "gas-like" behaviour of dispersed solute particles.
Determining molar mass by osmotic pressure:
Osmotic pressure is especially useful for measuring molar masses of polymers and biomolecules because can be significant even at very low concentrations - unlike BP elevation or FP depression, which give tiny shifts for large molecules.
atm.
Isotonic, Hypertonic, and Hypotonic Solutions
- Isotonic solutions have the same osmotic pressure (). At the same temperature this implies equal molar concentrations of solute particles (). No net osmosis occurs between two isotonic solutions.
- Hypertonic solution: higher osmotic pressure than a reference. Water flows out of a cell placed in a hypertonic solution (cell shrinks - crenation).
- Hypotonic solution: lower osmotic pressure than a reference. Water flows into a cell placed in a hypotonic solution (cell swells and may burst - haemolysis for red blood cells).
Medical application: intravenous drips must be isotonic with blood (osmotic pressure ~7.65 atm at body temperature 310 K), otherwise red blood cells rupture or shrivel. A 0.9% w/v saline solution (or a 5.4% w/v glucose solution) is isotonic with blood plasma and is used for IV drips and eye drops.
For isotonic solutions: .
g/L g/100 mL w/v.
6. Reverse Osmosis and Water Purification
The direction of osmosis can be reversed by applying an external pressure larger than the osmotic pressure on the solution side. Pure solvent then flows out of the solution through the semipermeable membrane. This is called reverse osmosis.
Practical use: reverse osmosis is the primary technology for desalination of sea water. A pressure greater than the osmotic pressure of sea water (~30 atm) is applied on the sea-water side; a suitable membrane (typically cellulose acetate on a porous support) lets pure water through but blocks dissolved salts. Countries such as Israel, Saudi Arabia, and coastal parts of India depend on RO plants for drinking water.
Domestic RO water purifiers work on the same principle at much lower pressures, using thin-film composite membranes to remove dissolved ions, bacteria, and small organic molecules.
7. Everyday Applications of Colligative Properties
- Antifreeze in car radiators: ethylene glycol added to radiator water lowers its freezing point (via ), preventing radiator damage in freezing weather. It simultaneously raises the boiling point, protecting against overheating.
- Salting icy roads: NaCl and CaCl spread on winter roads dissolve in the surface layer of water and depress its freezing point to well below 0 °C, melting the ice. CaCl is more effective because it dissociates into three ions () vs NaCl's two.
- Food preservation: salting meats (bacon, fish) and adding sugar to jams create a hypertonic environment. Water is drawn out of bacterial cells by osmosis, killing them and preventing spoilage.
- Osmoregulation in living cells: plants take up water through roots by osmosis. Kidneys use osmotic pressure gradients to filter blood.
- Reverse osmosis desalination and purification as above.
- Cryoscopy and ebullioscopy - laboratory determination of molar masses of unknown solids.
8. Determination of Molar Mass - Summary
| Property | Formula | Molar Mass Expression | Best For |
|---|---|---|---|
| Relative VP lowering | Non-volatile solutes | ||
| BP elevation | Small molecules | ||
| FP depression | Small-medium molecules (bigger effect) | ||
| Osmotic pressure | Polymers, proteins (large molecules) |
Common Mistakes to Avoid
- Colligative property formulas use molality (mass of solvent), not molarity. The exception is osmotic pressure , which uses molarity. Do not mix them up.
- For electrolyte solutes, the standard formulas underestimate the effect. Multiply by the Van't Hoff factor : , , .
- and are solvent properties, not solute properties. They do not change when you change the solute. Water has , ; benzene has , .
- When calculating amount of ice separated on cooling, use - the molality is based on the water that stays liquid, not the original water.
- Boiling point elevates and freezing point depresses - both are shifts caused by adding solute, but in opposite directions on the temperature axis.
- Osmotic pressure formulas use in kelvin, not Celsius.
- Reverse osmosis requires applied pressure greater than , not equal to . At exactly, osmosis just stops - it does not reverse.
Frequently Asked Questions
Q1. Why are colligative properties called "colligative"?
The word comes from Latin colligatus meaning "bound together". These four properties share a common cause: dissolved solute particles reduce the escape tendency of solvent molecules. Because the effect depends only on the number of solute particles and not their identity, all four properties are "tied together" by this single mechanism.
Q2. Why is freezing point depression preferred over boiling point elevation for molar mass determination?
The cryoscopic constant is generally larger than the ebullioscopic constant (for water 1.86 vs 0.512). This means FP depression gives a bigger temperature shift per mole of solute, making the measurement more precise. Also, freezing point can be measured accurately without worry about decomposition of thermolabile solutes, which is a concern at boiling temperatures.
Q3. Why is osmotic pressure the best method for determining molar masses of polymers?
Polymers have very large molar masses (10,000 g/mol and up), so even at 1% concentration the molality is tiny. BP elevation and FP depression give unmeasurably small temperature changes. Osmotic pressure, being expressed in atmospheres and depending on molar concentration, can still produce measurable pressure differences (millimetres of solvent column) for dilute polymer solutions.
Q4. What happens if a plant is watered with sea water?
Sea water is hypertonic to plant cell sap. Water flows out of the root cells by osmosis instead of into them, dehydrating the plant. The plant wilts and eventually dies. This is why irrigation with brackish water damages crops - a real problem in coastal agriculture.
Q5. Why does adding salt to icy roads melt the ice?
Salt dissolves in the thin film of liquid water always present on the ice surface. This saltwater solution has a freezing point well below 0 °C (because ; for NaCl, ). If the ambient temperature is above this new freezing point, the salt solution stays liquid and continues to dissolve more ice, gradually melting it away. CaCl works even better because it dissociates into 3 ions instead of 2.
Q6. Why does ethylene glycol work as antifreeze in car radiators?
Ethylene glycol is highly soluble in water and non-volatile. When added to radiator water it produces two protective effects at once: freezing point depression (prevents the coolant from freezing and cracking the radiator in winter) and boiling point elevation (raises the boiling point above 100 °C, preventing coolant loss on hot engines). Typical 50% ethylene glycol lowers the freezing point to about °C.
Q7. What is the difference between osmosis and diffusion?
Diffusion is the general movement of any particles (solute or solvent) from high to low concentration, requiring no membrane. Osmosis is specifically the movement of solvent through a semipermeable membrane from lower to higher solute concentration. The membrane selectively blocks the solute; only solvent can move. Osmosis is a special case of diffusion restricted by the membrane.
Q8. Why is Van't Hoff's equation similar to the ideal gas equation?
In a dilute solution, solute particles are spread far apart with little interaction, behaving somewhat like gas molecules in a container. Van't Hoff showed that the pressure they exert on a semipermeable barrier obeys the same formula as gas pressure. The similarity is real but limited to dilute solutions where solute-solute interactions are negligible - just as ideal gas behaviour requires low density.
Q9. Why does BP elevation depend on molality but osmotic pressure on molarity?
BP and FP shifts are measured over a range of temperatures, and molality is preferred because it is temperature-independent (mass does not change with T). Osmotic pressure, however, is measured at a fixed temperature and uses molar concentration (mol/L). At the fixed measurement temperature, no temperature-independence issue arises, so molarity is the natural choice - and it also connects directly to the ideal gas-like form .
Previous year questions on Colligative Properties
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