Vapor Pressure of Binary Solutions
Prepared by S.M. Blinder/modified by R. Baumann & J.L. Falconer
An ideal solution of two liquids A and B obeys Raoult's law, which states that the partial vapor pressure of each component is proportional to its mole fraction: pA = poAxA and pB = poBxB, where poA and poB are the vapor pressures of the pure components at a given temperature (very often 25 °C). The total vapor pressure above the solution is then given by
p = pA + pB = poA(1 - xB) + poB, assuming Dalton's law. Ideal solutions are fairly uncommon but serve as a convenient reference system to describe nonideal solutions. Pairs of liquids that are well approximated by Raoult's law usually contain molecules of similar size, shape, and chemical structure. Some well-known examples are benzene and toluene, chlorobenzene and bromobenzene, and carbon tetrachloride and silicon tetrachloride.
Most real solutions exhibit deviations from Raoult's law. A positive deviation is characterized by pA > poAxA and pB > poBxB and indicates that the attractive interactions between like molecules is greater than that between A and B molecules. A negative deviation has pA < poAxA and pB < poBxB, implying stronger mutual interactions between unlike molecules. The curves shown in the graphic are qualitative approximations to the actual dependence of vapor pressures on composition. The blue and green curves represent the partial pressures of A and B, respectively, while the black curve shows the total vapor pressure. The dashed lines refer to the hypothetical ideal behavior of the corresponding vapor pressures.
Even for nonideal solutions, Raoult's law is asymptotically approached for xA or xB ≈ 1. Dilute solutions, on the other hand, are approximated by Henry's law: the linear relations pA ≈ KAxA for xA ≈ 0 and pB ≈ KBxB for xB ≈ 0. Check "show Henry's law" to show this behavior, dotted purple and orange lines represent Henry's law.
Set the vapor pressures of the liquids and the deviation from ideality with sliders. Move the mouse over a curve to see its label (real or ideal).
By: S. M. Blinder, modified by R. Baumann & J. L. Falconer