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Ideal and Non-ideal Solutions

Liquid-liquid solutions can be classified into ideal and non-ideal solutions on the basis of Raoult’s law.

Ideal Solutions

The solution which obeys Raoult's law over the entire range of concentration when enthalpy of mixing and vol. of mixing of pure component to form solution is zero.

The condition for ideal Solution

1. space straight P subscript straight A space equals space straight P subscript straight A superscript straight o straight X subscript straight A space space space space straight P subscript straight B space equals space straight P subscript straight B superscript 0 straight X subscript straight B
2. space increment straight H subscript mix space equals space 0
3. space increment straight V subscript mix space equals space 0

This is only possible if A-B interaction is nearly equal to those between A-A and B-B interactions. Example, a solution of n-hexane and n-heptane.

Non-ideal Solutions

The solution which does not obey Raoult's law over the entire range of concentrations known as a Non-Ideal solution.

Conditions

straight I. space straight P subscript straight A space not equal to space straight P subscript straight A superscript 0 space straight X subscript straight A space space space space space space space space space space space space space space space space space space space straight P subscript straight B space not equal to space straight P subscript straight B superscript 0 space straight X subscript straight B
II. space increment straight H subscript mix space not equal to 0
III. increment straight V subscript mix space not equal to 0

The vapour pressure of such solutions is either higher or lower than that predicted for Raoult's law.

I. If vapour pressure is higher, the solutions show positive deviation (A-B interaction are weaker than those between A-A and B-B).
Example: Mixture of ethanol and acetone.

straight P subscript straight A space greater than space straight P subscript straight A superscript 0 space straight X subscript straight A space semicolon space straight P subscript straight B space greater than thin space straight P subscript straight B superscript 0 space straight X subscript straight B
increment straight H subscript mix space equals space Positive
increment straight V subscript mix space equals space Positive

II. If vapour pressure is lower, the solution shows negative deviation (A-B interaction are stronger than those between A-A and B-B).

straight P subscript straight A space less than space straight P subscript straight A superscript 0 space straight X subscript straight A space space space semicolon space straight P subscript straight B space less than thin space straight P subscript straight B superscript 0 straight X subscript straight B
increment straight H subscript mix space equals space negative space increment straight V subscript mix space equals space negative

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