Colligative Properties of Simple Solutions

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Science  05 Nov 1976:
Vol. 194, Issue 4265, pp. 567-571
DOI: 10.1126/science.194.4265.567


Vapor pressure lowering, osmotic pressure, boiling point elevation, and freezing point depression are all related quantitatively to the decrease in µ1soln upon the addition of solute in forming a solution. In any equilibrium system, regardless of whether it is in a gravitational field or whether it contains walls, semipermeable membranes, phase transitions, or solutes, all equilibria are maintained locally, in the small region of the equilibrium, by the equality of µ1soln. If there are several subsystems in a gravitational field, at any fixed height, µi will have the same value in each subsystem into which substance i can get, and µi + Migh is constant throughout the entire system.

In a solution, there is no mechanism by which solvent and solute molecules could sustain different pressures. Both the solvent and solute are always under identical pressures in a region of solution, namely, the pressure of the solution in that region. Since nature does not know which component we call the solvent and which the solute, equations should be symmetric in the two (acknowledging that the nonvolatile component, if any, is commonly chosen to be solute).

Simple molecular pictures illustrate what is happening to cause pressure (positive or negative) in liquids, vapor pressure of liquids, and the various colligative properties of solutions. The only effect of solute involved in these properties is that it dilutes the solvent, with the resulting increase in S and decrease in µ1soln.

Water can be driven passively up a tree to enormous heights by the difference between its chemical potential in the roots and the ambient air. There is nothing mysterious about the molecular bases for any of these phenomena. Biologists can use the well-understood pictures of these phenomena with confidence to study what is happening in the complicated living systems they consider.