Raoult's law should be removed from introductory chemistry curriculums. It is an unreliable approximation that only applies to very specific solutions and concentrations. For most real solutions, activity coefficients can differ from Raoult's predictions by orders of magnitude. Continuing to teach it deceives students about how intermolecular interactions actually impact vapor pressure in solutions. There are better qualitative ways to discuss these concepts without relying on Raoult's inaccurate law.
Raoult's law should be removed from introductory chemistry curriculums. It is an unreliable approximation that only applies to very specific solutions and concentrations. For most real solutions, activity coefficients can differ from Raoult's predictions by orders of magnitude. Continuing to teach it deceives students about how intermolecular interactions actually impact vapor pressure in solutions. There are better qualitative ways to discuss these concepts without relying on Raoult's inaccurate law.
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Raoult's law should be removed from introductory chemistry curriculums. It is an unreliable approximation that only applies to very specific solutions and concentrations. For most real solutions, activity coefficients can differ from Raoult's predictions by orders of magnitude. Continuing to teach it deceives students about how intermolecular interactions actually impact vapor pressure in solutions. There are better qualitative ways to discuss these concepts without relying on Raoult's inaccurate law.
Copyright:
Attribution Non-Commercial (BY-NC)
Available Formats
Download as DOCX, PDF, TXT or read online from Scribd
Raoult’s Law Is a Deception Raoult’s law is usually a reasonable approximation. Intermolecular interactions are illustrated more usefully Sthepen J. Hawkes by their affect on solubility and the practical problem of choosing a solvent, abandoning archaic “like dissolves Oregon State University, Corvallis, OR 97331 like” in favor of a discussion of dipole-dipole, dipole- induced dipole. London, H-bond and electron donor- acceptor interactions. Raoult’s law should not be in the introductory chemistry curriculum. It is unlikely that a student ever Some theory will need to know the vapor pressure of a solution and, if they do, Raoult’s unreliable guidance will deceive The deviation from Raoult’s law may be expressed by more often than it helps. an activity coefficient γ thus It works only for dilute solutions (and then only for the solvent, not the solute, and not polymers) or for p=γ xp0 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 For Raoult’s law to apply, γ must be unity. It may be the case, for example, with n-hexane/n-hexadecane several orders of magnitude in real solutions. (1) or dextrose/water (2). It fails completely when either For solutions where “regular solution” theory (9) component is a polymer, even at infinite dilution (3, 4). applies γ Is given (9) by In many cases it is not even the best guess. For polymers, the volume fraction gives better guidance logγsolvent = Vsolvent Φsolute (δsolvent – δsolute)2/4.575T than the mole fraction (3, 4). Solutions of perfluorobutane in n-butane conform better to mass where Φis the volume fraction, v is the molal volume, fraction relation than to the mole fraction at most and δ is the solubility parameter in cal/cm 3 (δ2 is the concentrations (calculated from the data in (5)). energy of vaporization to the gas at zero pressure, per It is not even pedagogically useful. The law illustrates unit volume). no wider principle. It is not the foundation for any later This function is plotted in the figure, which shows that teaching. It cannot be proved or even made to appear there is only a very limited number even of “regular” reasonable by any argument that can be fallowed by solutions in which the activity coefficient γ is less than undergraduates (the statistical proof is the subject of a 1.1 and the error from Raoult’s law consequently less graduate course). Intuitive argument based on the area than 10%. The law is, therefore, a poor approximation available for evaporation suggests the volume fraction even in these cases. The practice in introductory texts rather than the mole fraction, and is correct in the case of giving results of Raoult’s law calculations to two or of polymers. For the substantial number of students even three significant figures is deceptive to our who are “mathophobic”, the calculation of the mole students, even for “regular” solutions. Moreover, if it is fraction is another algorithm to be uncomprehendingly insisted that Raoult’s must be taught then our students memorized. It is never used again in the introductory also should be instructed and tested on how to decide course so their education is not furthered by learning it. whether a solution is one to which it can be applied as I do not know that is was ever popular for the a reasonable approximation. determination of approximate molecular weights, but it Moreover, many solutions are to even “regular”. For is seldom used for that purpose now. If a need should these, the activity coefficient may differ from those in arise to calculate the vapor pressure of a solution, a “regular” solutions by orders of magnitude. A listing of chemical engineer should be consulted because their such solutions in (10) shows activity coefficients at texts, e.g. (6, 7), show how to perform the calculation infinite dilution with a median value around 15 and a with more reliable algorithms. Even so, it is better to maximum of 27000 (for hexadiene/water). To suggest seek a published table as in (7, 8). These tables to students that Raoult’s law in generally a reasonable usually are not be found in regular chemical engineers. approximation is to deceive them. This must mean that chemists and most other people who use chemistry do not use the data so the law and Polymers its corrections are not worth learning. Its unreliability does not resemble the unreliability of In the extreme case where a polymer is dissolved in a the ideal gas law. Most gases behave nearly ideally in monomeric solvent, the equations shown in reference situations that students are likely to meet; whereas, (9) reduce to most solutions behave non-ideally. Deviations from Raoult’s law are occasionally used to Psolvent = Φsolvent Posolvent illustrate the effect of intermolecular interaction When the polymer has much higher molecular weight between solute and solvent. The discussion always is than the solvent, the solution is dilute, and the polymer held to small deviations that cause only curvature of and solvent are sufficiently chemically similar that the the tie line on graphs of vapor pressure against 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.