proactive opinion
composition thus conveying the impression that
Raoult’s Law Is a Deception
Sthepen J. Hawkes
Oregon State University, Corvallis, OR 97331
Raoult’s law should not be in the introductory
chemistry curriculum. It is unlikely that a student ever
will need to know the vapor pressure of a solution and,
if they do, Raoult’s unreliable guidance will deceive
more often than it helps.
It works only for dilute solutions (and then only for the
solvent, not the solute, and not polymers) or for
solutions in which the intermolecular forces within the
pure solute and solvent are very similar to those
between the solvent and solute in the solution. This is
the case, for example, with n-hexane/n-hexadecane
(1) or dextrose/water (2). It fails completely when either
component is a polymer, even at infinite dilution (3, 4).
In many cases it is not even the best guess. For
polymers, the volume fraction gives better guidance
than the mole fraction (3, 4). Solutions of
perfluorobutane in n-butane conform better to mass
fraction relation than to the mole fraction at most
concentrations (calculated from the data in (5)).
It is not even pedagogically useful. The law illustrates
no wider principle. It is not the foundation for any later
teaching. It cannot be proved or even made to appear
reasonable by any argument that can be fallowed by
undergraduates (the statistical proof is the subject of a
graduate course). Intuitive argument based on the area
available for evaporation suggests the volume fraction
rather than the mole fraction, and is correct in the case
of polymers. For the substantial number of students
who are “mathophobic”, the calculation of the mole
fraction is another algorithm to be uncomprehendingly
memorized. It is never used again in the introductory
course so their education is not furthered by learning it.
I do not know that is was ever popular for the
determination of approximate molecular weights, but it
is seldom used for that purpose now. If a need should
arise to calculate the vapor pressure of a solution, a
chemical engineer should be consulted because their
texts, e.g. (6, 7), show how to perform the calculation
with more reliable algorithms. Even so, it is better to
seek a published table as in (7, 8). These tables
usually are not be found in regular chemical engineers.
This must mean that chemists and most other people
who use chemistry do not use the data so the law and
its corrections are not worth learning.
Its unreliability does not resemble the unreliability of
the ideal gas law. Most gases behave nearly ideally in
situations that students are likely to meet; whereas,
most solutions behave non-ideally.
Deviations from Raoult’s law are occasionally used to
illustrate the effect of intermolecular interaction
between solute and solvent. The discussion always is
held to small deviations that cause only curvature of
the tie line on graphs of vapor pressure against
Raoult’s law is usually a reasonable approximation.
Intermolecular interactions are illustrated more usefully
by their affect on solubility and the practical problem of
choosing a solvent, abandoning archaic “like dissolves
like” in favor of a discussion of dipole-dipole, dipole-
induced dipole. London, H-bond and electron donor-
acceptor interactions.
Some theory
The deviation from Raoult’s law may be expressed by
an activity coefficient γ thus
p=γ xp0
For Raoult’s law to apply, γ must be unity. It may be
several orders of magnitude in real solutions.
For solutions where “regular solution” theory (9)
applies γ Is given (9) by
logγsolvent = Vsolvent Φsolute (δsolvent – δsolute)2/4.575T
where Φis the volume fraction, v is the molal volume,
and δ is the solubility parameter in cal/cm 3 (δ2 is the
energy of vaporization to the gas at zero pressure, per
unit volume).
This function is plotted in the figure, which shows that
there is only a very limited number even of “regular”
solutions in which the activity coefficient γ is less than
1.1 and the error from Raoult’s law consequently less
than 10%. The law is, therefore, a poor approximation
even in these cases. The practice in introductory texts
of giving results of Raoult’s law calculations to two or
even three significant figures is deceptive to our
students, even for “regular” solutions. Moreover, if it is
insisted that Raoult’s must be taught then our students
also should be instructed and tested on how to decide
whether a solution is one to which it can be applied as
a reasonable approximation.
Moreover, many solutions are to even “regular”. For
these, the activity coefficient may differ from those in
“regular” solutions by orders of magnitude. A listing of
such solutions in (10) shows activity coefficients at
infinite dilution with a median value around 15 and a
maximum of 27000 (for hexadiene/water). To suggest
to students that Raoult’s law in generally a reasonable
approximation is to deceive them.
Polymers
In the extreme case where a polymer is dissolved in a
monomeric solvent, the equations shown in reference
(9) reduce to
Psolvent = Φsolvent Posolvent
When the polymer has much higher molecular weight
than the solvent, the solution is dilute, and the polymer
and solvent are sufficiently chemically similar that the
Flory interaction parameter is unity. It other conditions,
proactive opinion
the formula is more complex, and I have been unable
to reduce polymers, Raoult’s law in any case that I
could conceive. For polymers, Raoult’s law is
unambiguously false and is not even a poor
approximation.
The same relation applies (3, 4) to solutions of volatile
substances in polymeric solvents. Then

Psolute= Φsolute P0solute

and Raoult’s law is again false.
These two equations for polymer solutions are derived
rigorously but also result from the simplistic argument
that evaporation rates are proportional to the area of
the solution surface occupied by the evaporating
substance.

Qualitative Discussion

Vapor pressure lowering by a solute is interesting and

perhaps mildly important, and the fact that it is not
easily calculated does not reduce its interest.
Seawater has 2% lower vapor pressure than lakewater
(11) and this slightly increases the humidity around the
Great Lakes compared to places near oceans. It also
figures into the calculation of weather patterns, though
the 2% is smaller than the present uncertainty of the
calculations.
The vapor pressure of strong sucrose solutions is so
low that spilled pop never dries completely.
Because the lowering of the vapor pressure depends
on the number of molecules or ions, other things being
equal, small molecule substances that ionized reduce
vapor pressure more than covalent compounds.
When antifreeze is added to water, the vapor pressure
is lowered so that it evaporates less and is less likely
to boil. The lowering of vapor pressure by the solute
causes an increase in boiling point because a higher
temperature is needed for the vapor pressure to equal
the atmospheric pressure. Some texts use the vapor
pressure lowering to prove that the solute also will
reduce the freezing point. The proof is sound and the
approach is rational but it becomes irrational when
they imply that the freezing point depression is a
consequence of the vapor pressure lowering. The
freezing point is depressed even in a completely filled
container where there is no vapor. The cause is that
solute molecules hinder the formation of crystals of the
solvent.

Conclusion

The reform of introductory chemistry poses repeatedly

the hard questions of what must be left out, and
subjects for omission must be sought. Raoult’s law is
one fragment of the curriculum that deceives more
than it enlightens and should be omitted.