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Dissociation Must Be Taken into Account in Raoult’s Law

Amparo Gómez-Siurana* and Sergio Menargues

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ABSTRACT: This communication shows that although some textbooks do not discuss how to apply Raoult’s law to electrolyte
solutions, we should not ignore dissociation, and the van’t Hoff factor must be considered.
KEYWORDS: Introductory Chemistry, Misconceptions, Solution, Raoult’s Law, Electrolytes

■ INTRODUCTION
Raoult’s law states that at a temperature T, the solvent vapor
considered,14−18 some of them19−22 include the van’t Hoff
factor in equations for other colligative properties but do not
pressure, P, of an ideal solution is the product of the mole mention how to perform the vapor pressure calculation for
fraction of solvent, xsolvent, and the vapor pressure of pure solutions of electrolytes. In other cases,23−25 although the
solvent at the same temperature, P°: explicit equation for the vapor pressure lowering in electrolyte
solutions is not given or suggested, the reader can infer that
(1) dissociation is required for this calculation. On the other hand,
There are many scientific papers focusing on how Raoult’s law in some books, the discussion of vapor pressure depression
should be explained or applied to aqueous salt solutions.1−7 when considering colligative properties is excluded26−28 or
Some authors have stated that it should not be included in the only briefly mentioned.29,30 It is possible that these different
introductory chemistry curriculum.8,9 This has been the approaches contribute to the misinterpretation mentioned
subject of controversy,1,4,6,8−10 and papers have been published above. Some literature on student or teacher misconceptions
focusing on the application of thermodynamic principles10−12 about colligative properties also does not consider the case of
or on how to calculate the mole fraction of the solvent.1,5−7,13 vapor pressure of electrolyte solutions.31,32 Therefore, the aim
In this context, there is no doubt that the effect of solute here is to highlight that the lack of explicit expressions for
dissociation, which can be accounted for by the van’t Hoff calculating the vapor pressure of electrolyte solutions may lead
factor, i, defined as the ratio of moles of particles formed by the to misunderstanding by some readers and to suggest a very
solute in solution to moles of dissolved solute, must be simple exercise to demonstrate the need to consider
considered. Even the need to take into account the concept of dissociation.
“free water”, i.e., the total amount of water (in moles) minus
any amount bound to solutes, and the actual number of
particles formed per mole of solute to evaluate the solvent
■ DISCUSSION
When Raoult’s law is applied to aqueous salt solutions, it is
concentration has been pointed out.1−3,5−7,13 However, the clear that the actual mole fraction of water available for
fact that most general chemistry textbooks explicitly include evaporation must be taken into account. However, calculating
the effect of dissociation in the calculation of the other
colligative properties but not for vapor pressure depression
may lead to a misunderstanding at the introductory levels of Received: April 26, 2023
chemistry, with the consequence that the same expression for Revised: August 23, 2023
vapor pressure is used for aqueous salt solutions as for ideal Published: September 11, 2023
solutions, without considering dissociation.
In this regard, although there are general chemistry
textbooks that explicitly state that dissociation must be
© 2023 The Authors. Published by
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of Chemical Education, Inc. 4106 J. Chem. Educ. 2023, 100, 4106−4108
Journal of Chemical Education pubs.acs.org/jchemeduc Communication

the relative amount of free water per mole of solute added and
the actual number of entities formed in solution per mole of
solute, which may differ from the stoichiometric values if the
salt is not completely dissociated or if there is association
between particles from the solute, is beyond the scope of the (5)
introductory chemistry courses. Nevertheless, at such levels,
the van’t Hoff factor must be considered when Raoult’s law is Since the boiling temperature of water at atmospheric pressure
applied to electrolyte solutions. A simple exercise can be is 100 °C, the boiling temperature of this solution would be
performed to demonstrate this easily: consider an aqueous 100 + 2.6 = 102.6 °C, which is taken as the correct value. The
actual boiling temperature of this solution may differ from this
solution of a salt such as aluminum sulfate, Al2(SO4)3, at a
value if there is significant bound water and/or ion pair
concentration of 1 molal (342.1 g of solute/kg of solvent). To formation and should be determined experimentally. Never-
solve the exercise, the contribution of water molecules bound theless, the calculated value is taken as correct for comparison
to the solute is assumed to be negligible, complete dissociation purposes only.
of the solute is assumed, and the possibility of ion association (2) The normal boiling temperature of an aqueous salt
is ignored. Although these approximations may result in some solution can be obtained by finding the temperature at which
deviation from the actual boiling point temperature, and the solvent vapor pressure, P, calculated using Raoult’s law (eq
Al2(SO4)3 aqueous solutions can be highly nonideal, they allow 1), is equal to the atmospheric pressure of 760 mmHg:
comparisons to be made and are certainly preferable to
ignoring dissociation. (6)
The vapor pressure of pure water, P°, as a function of the
temperature, T, can be calculated using the Antoine equation, In eq 6, the vapor pressure of pure water is calculated with the
Antoine equation (eq 2). The results obtained are T = 100.5
taken from the ChemCAD 8.0.2 database:33
°C when xw is calculated with i = 1 (eq 3) and 102.4 °C when
xw is calculated with i = 5 (eq 4). Therefore, upon comparison
(2)
of these results with those obtained from the boiling point
According to eq 2, the calculated vapor pressure of pure water elevation, it is clear that the solvent vapor pressure calculation
requires the application of Raoult’s law taking into account
at 25 °C is 23.59 mmHg. The complete dissociation of
dissociation.
Al2(SO4)3 gives 5 moles of ions per mole of dissolved salt.
Then the van’t Hoff’s factor, with the assumed simplifications,
is i = 5. The solvent mole fraction, ignoring dissociation, for a 1 ■ CONCLUSIONS
Although not all introductory chemistry textbooks include an
molal solution, which contains 1 mol of solute per 1 kg of explicit description of how to calculate the vapor pressure of
water, i.e., per 55.5 mol of water, is electrolyte solutions, dissociation must be considered if
Raoult’s law is to be applied in early-level chemistry courses.

In contrast, the solvent mole fraction considering i = 5 is

(3)
■ AUTHOR INFORMATION
Corresponding Author
Amparo Gómez-Siurana − Department of Chemical
Engineering, University of Alicante, 03690 San Vicente del
Raspeig, Alicante, Spain; orcid.org/0000-0001-8334-
0606; Email: [email protected]
(4)
Author
The corresponding solvent vapor pressures calculated by Sergio Menargues − Department of Chemical Engineering,
applying eq 1 are 23.17 mmHg without considering the van’t University of Alicante, 03690 San Vicente del Raspeig,
Hoff factor and 21.64 mmHg considering i = 5. If there is any Alicante, Spain
doubt as to which result is closest to the actual (i.e., Complete contact information is available at:
experimentally measured) value, the boiling point of this https://pubs.acs.org/10.1021/acs.jchemed.3c00369
solution can be calculated by using two different approaches:
(1) by using the colligative property of the boiling point Notes
elevation for an electrolyte solution and (2) by finding the The authors declare no competing financial interest.
temperature at which the vapor pressure of the solution,
calculated using Raoult’s law, is equal to atmospheric pressure.
The comparison of the results obtained by the two procedures
■ REFERENCES
(1) Zavitsas, A. A. Quest to demystify water: ideal solution behaviors
will help us to choose between the two values 23.17 and 21.64 are obtained by adhering to the Equilibrium Mass Action law. J. Phys.
mmHg. Chem. B 2019, 123, 2461.
(1) By applying the colligative property of boiling point (2) Karelin, A. I.; Tarasenko, V. A. Hydration numbers of perchloric
acid: estimation method based on the Raoult law. Chem. Phys. 2019,
elevation, ΔT = iKem, where Ke is the ebullioscopic constant 523, 211−221.
for the solvent (0.52 °C kg/mol in the case of water) and m is (3) Karelin, A. I.; Tarasenko, V. A. Corrigendum “Hydration
the molality (m = 1 mol/kg), we find that numbers of perchloric acid: estimation method based on the Raoult

4107 https://doi.org/10.1021/acs.jchemed.3c00369
J. Chem. Educ. 2023, 100, 4106−4108
Journal of Chemical Education pubs.acs.org/jchemeduc Communication

law” [Chem. Phys 523 (2019) 211−221. Chem. Phys. 2019, 525, (31) Azizoglu, N.; Alkan, M.; Geban, Ö . Undergraduate Pre−Service
110421. Teachers’ Understandings and Misconceptions of Phase Equilibrium.
(4) Yang, Z. H. Comment on “The quest to demystify water: ideal J. Chem. Educ. 2006, 83 (6), 947−953.
solution behaviors are obtained by adhering to the Equilibrium Mass (32) Canpolat, N.; Pinarbasi, T.; Sözbilir, M. Prospective Teachers’
Action Law”. J. Phys. Chem. B 2019, 123, 2459−2460. Misconceptions of Vaporization and Vapor Pressure. J. Chem. Educ.
(5) Zavitsas, A. A. Properties of aqueous solutions. A treatise against 2006, 83 (8), 1237−1242.
osmotic and activity coefficients. J. Mol. Liq. 2022, 348, 118410. (33) CHEMCAD|Chemical Engineering Simulation Software. Chem-
(6) Zavitsas, A. A. Reply to “Comment on “Quest to demystify stations, 2020. https://www.chemstations.com/CHEMCAD/ (ac-
water: ideal solution behaviors are obtained by adhering to the cessed August 2023).
Equilibrium Mass Action law. J. Phys. Chem. B 2019, 123, 869−883.
(7) Zavitsas, A. A. Ideal Thermodynamic behaviors of aqueous
electrolyte solutions at very high concentrations. Chem. Phys. Lett.
2020, 759, 137941.
(8) Hawkes, S. J. Raoult’s law is a deception. J. Chem. Educ. 1995, 72
(3), 204−205.
(9) Peckham, G. D. Vapor pressure lowering by nonvolatile. J. Chem.
Educ. 1998, 75 (6), 787−7888.
(10) Wexler, A. S. Raoult was right after all. ACS Omega 2019, 4,
12848−12852.
(11) Rioux, F. Colligative properties. J. Chem. Educ. 1973, 50 (7),
490−492.
(12) Chinard, F. P. Colligative properties. J. Chem. Educ. 1955, 32
(7), 377−380.
(13) Wexler, A. S.; Patel, K.; Gen, M.; Chan, C. K. (2020)
Reconciling measurement and prediction of free and solvated water in
solution. ACS Omega 2020, 5, 8754−8765.
(14) Zumdahl, S. S.; Zumdahl, S. A.; DeCoste, D. J. Chemistry, 10th
ed.; Cengage Learning: Boston, 2018; pp 447−448.
(15) Robinson, J. K.; McMurry, J. E.; Fay, R. C. Chemistry, 8th ed.;
Pearson Education: Hoboken, NJ, 2020; pp 511−512.
(16) Tro, N. J. Chemistry: A Molecular Approach, 5th ed.; Pearson
Education: Hoboken, NJ, 2020; pp 614−615.
(17) Burdge, J. Chemistry, 5th ed.; McGraw-Hill Education: New
York, 2020; p 582.
(18) Brown, T. L.; LeMay, H. E., Jr.; Bursten, B. E.; Murphy, C. J.;
Woodward, P. M.; Stoltzfus, M. W.; Lufaso, M. W. Chemistry: The
Central Science, 15th global ed.; Pearson, 2021; pp 633−640.
Recommended by ACS
(19) Gilbert, T. R.; Kirss, R. V.; Foster, N.; Bretz, S. L.; Davies, G.
Chemistry: The Science in Context, 5th ed.; W. W. Norton & Company: Le Chatelier’s Principle Observed in Real-Time: A
New York, 2018; pp 550−575. Classroom Demonstration Using Digital Probeware
(20) Masterton, W. L.; Hurley, C. N. Chemistry: Principles and Alisha U. Asif, Stephen G. Prilliman, et al.
Reactions, 3rd ed.; Cengage Learning: Boston, 2014; pp 269−271. DECEMBER 05, 2023
(21) Petrucci, R. H.; Herring, F. G.; Madura, J. D.; Bissonnette, C. JOURNAL OF CHEMICAL EDUCATION READ
General Chemistry: Principles and Modern Applications, 11th ed.;
Pearson Canada: Toronto, 2017; pp 672−674. Visualization of Validity Ranges for Acid Approximations:
(22) Overby, J.; Chang, R. Chemistry, 14th ed.; McGraw Hill: New Error Contour Plots as a Function of Concentration and Ka
York, 2022; pp 552−553.
(23) Witthen, K. W.; Davis, R. E.; Peck, M. L.; Stanley, G. G. Taweetham Limpanuparb and Junming Ho
NOVEMBER 15, 2023
Chemistry, 10th ed.; Brooks/Cole, Cengage Learning: Belmont, CA,
JOURNAL OF CHEMICAL EDUCATION READ
2010; pp 527−528.
(24) Jespersen, N. D.; Brady, J. E.; Hyslop, A. Chemistry: The
Molecular Nature of Matter, 6th ed.; John Wiley & Sons, 2012; Spreadsheet Methodology for the Calculation of Equilibrium
Hoboken, NJ; p 618. Diagrams Including Precipitation Reactions and Formation
(25) Moore, J. W.; Stanitski, C. L. Chemistry: The Molecular Science, of Mixed Ligand and Polynuclear Hydroxo Complexes
5th ed.; Cengage Learning: Stamford, CT, 2015; p 592. Ulrich Briones-Guerash S., Julio C. Aguilar-Cordero, et al.
́
(26) Quimica: Un Proyecto de la American Chemical Society, rev. ed.; NOVEMBER 15, 2023
American Chemical Society: Barcelona, 2007; pp 558−569. JOURNAL OF CHEMICAL EDUCATION READ
(27) Atkins, P.; Jones, L.; Laverman, L. Chemical Principles: The
Quest for Insight, 7th ed.; W. H. Freeman McMillan Learning: New
Is There Still a Place for Linearization in the Chemistry
York, 2016; pp 388−396.
Curriculum?
(28) Blackman, A.; Southam, D.; Lawrie, G.; Williamson, N.;
Thompson, C.; Bridgeman, A. Chemistry: Core Concepts, 2nd ed.; John Andrew R. McCluskey.
Wiley & Sons: Milton, QLD, 2019; pp 606−613. OCTOBER 09, 2023

(29) Seager, S. L.; Slabaugh, M. R.; Hansen, M. S. Chemistry for JOURNAL OF CHEMICAL EDUCATION READ
Today: General, Organic and Biochemistry, 9th ed.; Cengage Learning:
Boston, 2018; pp 229−233.
Get More Suggestions >
(30) Bauer, R.; Birk, J.; Marks, P. Introduction to Chemistry, 5th ed.;
McGraw-Hill Education: New York, 2019; pp 469−474.

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