Raoult's law (ˈrɑːuːlz law) is a relation of physical chemistry, with implications in thermodynamics. Proposed by French chemist François-Marie Raoult in 1887, it states that the partial pressure of each component of an ideal mixture of liquids is equal to the vapor pressure of the pure component (liquid or solid) multiplied by its mole fraction in the mixture. In consequence, the relative lowering of vapor pressure of a dilute solution of nonvolatile solute is equal to the mole fraction of solute in the solution.
Mathematically, Raoult's law for a single component in an ideal solution is stated as
where is the partial pressure of the component in the gaseous mixture above the solution, is the equilibrium vapor pressure of the pure component , and is the mole fraction of the component in the liquid or solid solution.
Where two volatile liquids A and B are mixed with each other to form a solution, the vapor phase consists of both components of the solution. Once the components in the solution have reached equilibrium, the total vapor pressure of the solution can be determined by combining Raoult's law with Dalton's law of partial pressures to give
In other words, the vapor pressure of the solution is the mole-weighted mean of the individual vapour pressures:
If a non-volatile solute B (it has zero vapor pressure, so does not evaporate) is dissolved into a solvent A to form an ideal solution, the vapor pressure of the solution will be lower than that of the solvent. In an ideal solution of a nonvolatile solute, the decrease in vapor pressure is directly proportional to the mole fraction of solute:
If the solute associates or dissociates in the solution, the expression of the law includes the van 't Hoff factor as a correction factor.
Raoult's law is a phenomenological relation that assumes ideal behavior based on the simple microscopic assumption that intermolecular forces between unlike molecules are equal to those between similar molecules, and that their molar volumes are the same: the conditions of an ideal solution.
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In chemistry, an ideal solution or ideal mixture is a solution that exhibits thermodynamic properties analogous to those of a mixture of ideal gases. The enthalpy of mixing is zero as is the volume change on mixing by definition; the closer to zero the enthalpy of mixing is, the more "ideal" the behavior of the solution becomes. The vapor pressures of the solvent and solute obey Raoult's law and Henry's law, respectively, and the activity coefficient (which measures deviation from ideality) is equal to one for each component.
In chemical thermodynamics, activity (symbol a) is a measure of the "effective concentration" of a species in a mixture, in the sense that the species' chemical potential depends on the activity of a real solution in the same way that it would depend on concentration for an ideal solution. The term "activity" in this sense was coined by the American chemist Gilbert N. Lewis in 1907. By convention, activity is treated as a dimensionless quantity, although its value depends on customary choices of standard state for the species.
In thermodynamics, the chemical potential of a species is the energy that can be absorbed or released due to a change of the particle number of the given species, e.g. in a chemical reaction or phase transition. The chemical potential of a species in a mixture is defined as the rate of change of free energy of a thermodynamic system with respect to the change in the number of atoms or molecules of the species that are added to the system.
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