The reasons for such a +ve deviations could be linked to the fact that after mixing the interactions between the liquid A and B is less than the interaction between A–A system and B–B system.

i.e. A–B interactions < A–A interactions and B–B interactions.

Non-Ideal Solution with Negative Deviation

The B set of solutions show a relationship where the vapour pressure of solution observed is lesser than the vapour pressure of the solution under ideal conditions i.e.

Ps (obs) < Psolution (ideal)

Ps < Pi.

Þ Ps <

A–B interaction > A–A interaction and B–B interactions.

Then the heat energy released when A–B interaction take place will be more than compared to the heat energy required for breaking the A–A interaction or B–B interactions. Hence the net result is

DHmix < 0 Þ DHmix = –ve and also

DVmix < 0 Þ DVmix = –ve

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