provocative opinion

Raoult’s Law Is a Deception

Stephen 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
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solvent, not the solute, and not for polymers) or for solu-
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tions 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 ex-
ample, 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 a mass fraction relation than to the mole
fraction at most concentrations (calculated from the data
in (5)).
It is not even pedagogieally useful. The law illustrates no
wider principle. It is not the foundation for any later teach-
ing. It cannot be proved or even made to appear reasonable
by any argument that can be followed by undergraduates
(the statistical proof is the subject of a graduate course). Activity coefficients y for “regular" solutions at 25 °C assuming molar
Intuitive argument based on the area available for evapo- volume = 100 cm against volume fraction $ of solute. The number
,

ration suggests the volume fraction rather than the mole against each line is the difference between the solubility parameters
fraction, and is correct in the case of polymers. For the sub- 6 for solute and solvent.
stantial number of students who are “mathophobic”, the
calculation of the mole fraction is another algorithm to be chaic “like dissolves like” in favor of a discussion of dipole-
uncomprehendingly memorized. It is never used again in dipole, dipole-induced dipole, London, H-bond and electron
the introductory course so their education is not furthered donor-acceptor interactions.
by learning it.
I do not know that it was ever popular for the determina- Some Theory
tion of approximate molecular weights, but it is seldom The deviation from Raoult’s law may be expressed by an
used for that purpose now. If a need should arise to calcu- activity coefficient ythus
late the vapor pressure of a solution, a chemical engineer
should be consulted because their texts, e.g. (6, 7), show P =
Y*P°
how to perform the calculation with more reliable algo- For Raoult’s law to apply, y must be unity. It may be several
rithms. Even so, it is better to seek a published table as in orders of magnitude in real solutions.
(7, S). These tables usually are not to be found in regular For solutions where “regular solution” theory (9) applies,
chemical literature but are in the reference works of
y is given (9) by
chemical engineers. This must mean that chemists and
most other people who use chemistry do not use the data log Ysolvent “

^solvent^solut^i® solvent
—

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 situ-
ations that students are likely to meet; whereas, most so-
lutions behave non-ideally.
Deviations from Raoult’s law are occasionally used to il-
lustrate 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 composition thus convey-
ing the impression that Raoult’s law is usually a reason-
able approximation. Intermolecular interactions are illus-
trated more usefully by their effect on solubility and the
practical problem of choosing a solvent, abandoning the ar-
^solute) /4.575T
where g is the volume fraction, v is the molal volume, and
5 is the solubility parameter in eal/cm3 (6” is the energy of
vaporization to the gas at zero pressure, per unit of vol-
ume).
This function is plotted in the figure, which shows that
there is only a very limited number even of “regular” solu-
tions in which the activity coefficient y 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” so-
lutions. Moreover, if it is insisted that Raoult’s law must be

204 Journal of Chemical Education

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 not 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 is 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
Solvent —
4* solventPsolvent
when the polymer has much higher molecular weight than
the solvent, the solution is dilute, and the polymer and sol-
vent are sufficiently chemically similar that the Flory in-
teraction parameter is unity. In other conditions, the
formula is more complex, and I have been unable to reduce
it to 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
^solute —
^solutePsolute
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.1
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 fig-
ures into the calculation of weather patterns, though the
2% is smaller than the present uncertainty of the calcula-
tions.
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 lower vapor pressure more
than similar masses of larger molecules. For the same rea-
son, substances that ionize 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 be-
comes 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 question 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.
Literature Cited
1. Hildebrand, J. H.; Sweny, J. W. J. Phys. Chem. 1939,43, 297.
2. Torgesen, J. L,; Bower, V. E.; Smith, E. R. J. Res. Nat. Bur. Standards 1950, 45,458.
3. Patterson, D.; Tewari, Y. B.; Schreiber. H. P. Macromolecules 1972. 4. 356.
4. Roberts, G. L.; Hawkes, S. J. J. Ckromatog. Sci. 1973. 22,16.
5. Simons. J. H.: Mausteller. J. W. J. Chem. Phys. 1952, 20. 1516.
6. Reid. R. C.: Prausnitz, J. M .; Sherwood, T. K. The Properties of Gases and Liquids,
3rd.ed.; McGraw-Hill: New York, 1977.
7. Hirato, M.; Ohe, S.; Nagahama, K. Computer-Aided Data Book of Vapor-Liquid
Equilibria: Kodansha, Tokyo and Elsevier Scientific: Amsterdam, 1976.
8. Perry. R. H.; Green, D. Perry's Chemical Engineers Handbook; McGraw-Hill: New
York, 1984.
9. Hildebrand, J. H.; Prausnitz, J. M.; Scott, R. L. Regular and Related Solutions, 3rd
ed.; Van Nostrand Reinhold: New York, 1970, p 110.
10. Fredenslund, A.; Jones, R. L.; Prausnitz, J. M. Amer. Inst. Chem. Eng. 1975. 276.
1086.
11. Millero, F. J.; Leung, W. H. Amer. J. Sci. 1976,276. 1063.
1I was appalled by a reviewer’s suggestion that instructors should
focus on volume fraction rather than mole fraction. This would give
correct answers for uncomplicated polymer solutions, but wrong an-
swers for the solutions mentioned earlier where Raoult’s law works
well. Introductory chemistry should not include any attempt to quan-
tify vapor pressure lowering.
Volume 72 Number 3 March 1995 205