Vapor-Pressure Lowering of Solutions: Raoults Law Recall from Section 10.

5 that a liquid in a closed container is in equilibrium with its vapor and that the amount of pressure exerted by the vapor is called the vapor pressure. When you compare the vapor pressure of a pure solvent with that of a solution at the same temperature, however, you find that the two values are different. If the solute is nonvolatile and has no appreciable vapor pressure of its own, as occurs when a solid is dissolved, then the vapor pressure of the solution is always lower than that of the pure solvent. Solutions with a Nonvolatile Solute Just as the ideal gas law discussed in Section 9.3 applies only to ideal gases, Raoults law applies only to ideal solutions. Raoults law approximates the behavior of most real solutions, but significant deviations from ideality occur as the solute concentration increases. The law works best when solute concentrations are low and when solute and solvent particles have similar intermolecular forces. If the intermolecular forces between solute particles and solvent molecules are weaker than the forces between solvent molecules alone, then the solvent molecules are less tightly held in the solution and the vapor pressure is higher than Raoults law predicts. Conversely, if the intermolecular forces between solute and solvent molecules are stronger than the forces between solvent molecules alone, then the solvent molecules are more tightly held in the solution and the vapor pressure is lower than predicted. Solutions of ionic substances, in particular, often have a vapor pressure significantly lower than predicted, because the iondipole forces between dissolved ions and polar water molecules are so strong. A further complication is that ionic substances rarely dissociate completely, so a solution of an ionic compound usually contains fewer particles than the formula of the compound would suggest.