Set-A solution shows a relationship where the vapour pressure of the solution observed is greater than the vapour pressure of solution under ideal conditions
i.e. Ps (obs) > Ps(actual)
or Ps > Pi where Pi = .....(8)
i.e. Ps > .....(9)
Such solutions are said to have a +ve deviation from ideality. The graph obtained resembles as given below
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.
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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