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Concept
Regular solution
Summary
In chemistry, a regular solution is a solution whose entropy of mixing is equal to that of an ideal solution with the same composition, but is non-ideal due to a nonzero enthalpy of mixing. Such a solution is formed by random mixing of components of similar molar volume and without strong specific interactions, and its behavior diverges from that of an ideal solution by showing phase separation at intermediate compositions and temperatures (a miscibility gap). Its entropy of mixing is equal to that of an ideal solution with the same composition, due to random mixing without strong specific interactions. For two components
where is the gas constant, the total number of moles, and the mole fraction of each component. Only the enthalpy of mixing is non-zero, unlike for an ideal solution, while the volume of the solution equals the sum of volumes of components.
A regular solution can also be described by Raoult's law modified with a Margules function with only one parameter :
where the Margules function is
Notice that the Margules function for each component contains the mole fraction of the other component. It can also be shown using the Gibbs-Duhem relation that if the first Margules expression holds, then the other one must have the same shape. A regular solutions internal energy will vary during mixing or during process.
The value of can be interpreted as W/RT, where W = 2U12 - U11 - U22 represents the difference in interaction energy between like and unlike neighbors.
In contrast to ideal solutions, regular solutions do possess a non-zero enthalpy of mixing, due to the W term. If the unlike interactions are more unfavorable than the like ones, we get competition between an entropy of mixing term that produces a minimum in the Gibbs free energy at x1 = 0.5 and the enthalpy term that has a maximum there. At high temperatures, the entropic term in the free energy of mixing dominates and the system is fully miscible, but at lower temperatures the G(x1) curve will have two minima and a maximum in between.
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Enthalpy of mixing
In thermodynamics, the enthalpy of mixing (also heat of mixing and excess enthalpy) is the enthalpy liberated or absorbed from a substance upon mixing. When a substance or compound is combined with any other substance or compound, the enthalpy of mixing is the consequence of the new interactions between the two substances or compounds. This enthalpy, if released exothermically, can in an extreme case cause an explosion. Enthalpy of mixing can often be ignored in calculations for mixtures where other heat terms exist, or in cases where the mixture is ideal.
Ideal solution
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.