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There are idealand non-ideal mixtures. In the second case the intermolecular forces between the different molecules of the mixture are less (Positive deviations from Raoult's Law) or more (Negative deviations from Raoult's Law) strong than they are in the pure liquids.

This difference in the intermolecular forces causes a expansion (less strong) or retraction (more strong) of the volume after the mixing, this is the cause of the excess molar volume.

The excess molar volumes VE can be calculated by using measured experimental densities and correlated by the Redlich−Kister type equation.

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