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Chemistry and Technology of Fuels and Oils, Vol. 44, No.

5, 2008

METHODS OF ANALYSIS

DETERMINATION OF THE MACROSCOPIC DIPOLE MOMENT OF ASSOCIATED SOLVENTS

S. V. Tyumkin

The solubility (crystallization) of n-alkanes and mixtures (paraffins) in unassociated (chloroalkanes, toluene, hexane) and associated (ketones, alcohols, carboxylic acids) solvents and in binary mixtures of these solvents was investigated. The values of the macroscopic dipole moment (arbitrary polarity) were determined for the first time for acetone and its homologs, up to methyl hexyl ketone, for C 4-C7 aliphatic alcohols, and for carboxylic acids from butyric to caprylic. Using the dependences of the arbitrary polarity on the molecular weight and molar refraction of the solvents, the polarity values were calculated for water, methanol, formic acid, and other associated substances. The mechanism of the increase in the solubility of water, glucose, and glycine with a decrease in the difference between the polarity of the solvent and the dissolved substance was demonstrated. The effect of the nature of the solvent on the solubility (crystallization) in the liquid liquid and liquid solid system is evaluated with empirical polarity parameters [1-10] determined with the spectral, thermodynamic, kinetic, or polar (dielectric constant, dipole moments of the molecules, etc.) characteristics of the substances. The dipole moments m of molecules of associated solvents with polar functional OH groups alcohols and water, CO groups ketones and COOH in monocarboxylic acids create the following values of m for homologs of these classes of compounds: 1.70.1, 2.70.1, 0.20.2 D.* In the electrostatic theory of the intermolecular interaction, the significant difference in associated solvents with respect to the dissolving power cannot be explained by the values of m. Modeling of the structure of water [11, 12] and a number of solvents [13, 14] with calculation of m in the assumption of formation of associates (clusters) with 2 to 100 molecules showed that the value of the dipole moment for the associates can be 2-5 times

*1 D = 3.33566410-30 Cm. ____________________________________________________________________________________________________ Central Volga Research Institute on Oil Refining Co. Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 5, pp. 45 47, September October, 2008. 352 0009-3092/08/44050352 2008 Springer Science+Business Media, Inc.

higher than the value for the molecule. The problem of experimental determination of the dipole moment of an associated solvent as macroproperties of a substance in the liquid phase has not yet been solved. We propose a method for determining the polarity of associated solvents in the sense of the dipole moment and understood in [3] as the global ability of a solvent to react with a dissolved substance with formation of a solid phase. The method is based on use of data on the solubility (crystallization) of high-melting n-alkanes and mixtures of them (paraffins) in three groups of solvents: in almost unassociated substances low-molecular-weight alkanes, chloroalkanes, nitroalkanes, toluene; the dipole moment of these substances characterizes their dissolving power [15 16]; in associated substances ketones, aliphatic alcohols, monocarboxylic acids, water; in binary mixtures of solvents from the first and second groups. When the solubility of a substance (for t = const) in the listed groups of solvents is the same, the dipole moment of the solvents in the second and third groups was set equal to the dipole moment of the solvents in the first group. The dipole moment of a polar associated solvent was calculated with the molar composition of twothree binary solvents [15, 16]. Its values differed from the average by a maximum of 0.1 D. Binary solvents were used in the case of formation of a second liquid and/or solid phase in the dissolved substance single-component associated solvent system and for verifying the rules of additivity. The results of determining the arbitrary polarity P a of associated solvents are reported in Table 1. The values of P a obtained are correlated to a high degree (r 2 > 0.99) with the molecular weight M and molar refraction R for ketones and alcohols and to a lesser degree (r 2 = 0.94-0.96) for carboxylic acids in equations of the type

Pa = a + b/M Pa = a + b/R
where a and b are coefficients. Table 1
Coefficient of Eq. Solvent Acetone Methyl ethyl ketone Methyl isobutyl ketone Methyl hexyl ketone Butanol Hexanol Octanol Acid butyric valeric caproic caprylic Pa, D a 3.2 2.55 1.85 1.4 2.5 1.8 1.4 2.3 1.8 1.6 1.4 0.064 200.55 0.276 43.25 (1) b a (2) b

(1) (2)

0.064

189.4

0.188

48.89

0.05

189.2

0.113

52.68

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Using the coefficients reported in Table 1, the values of the convention polarity P a for water, low-molecular-weight alcohols, and carboxylic acids, in which nonpolar high-melting n-alkanes and their mixtures (paraffins) are almost insoluble or form a second liquid phase, were calculated with Eqs. 1 and 2 (Table 2). The values of P a calculated with the molecular weight and equations for ketones and alcohols are almost the same, but are 0.15-0.62 D lower than the values calculated with the equation for acids. The differences of P a from the average value are maximum for water (0.4 D) and methanol (0.2 C) and do not exceed 0.1 D for the other solvents. The data from calculating P a with the molar refraction vary within wider limits and with greater differences from the average values, except for the data for alcohols.

Pa
Fig. 1. Dielectric constant e for C 1-C 8 alcohols, C 2-C 8 ketones, and water as a function of arbitrary polarity P a calculated with the molecular weight (solid curve) and molar refraction (dashed curve). Table 2
Value of Pa (D) calculated with the equation for Solvent ketones 10.45 5.85 4.05 3.09 4.05 3.09 2.49 12.89 6.04 3.98 2.99 5.99 3.95 2.96 alcohols With molecular weight 10.45 5.85 4.05 3.10 4.06 3.10 2.50 With molar refraction 13.80 6.41 4.19 3.13 6.37 4.17 3.10 acids 11.07 6.20 4.29 3.27 4.29 3.28 2.64 11.51 5.45 3.63 2.75 5.41 3.61 2.73 average 10.66 5.96 4.13 3.15 4.13 3.15 2.55 12.73 5.97 3.93 2.95 5.93 3.91 2.93 Difference of Pa (D) from average value 0.4 0.2 0.1 0.1 0.1 0.1 0.1 1.1 0.5 0.3 0.2 0.5 0.3 0.1

Water Methanol Ethanol Propanol Acid formic acetic propionic Water Methanol Ethanol Propanol Acid formic acetic propionic

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The values of P a for water (10.5-13.8 D) correspond to the modeling data [11] for stable clusters of 30-40 molecules and the value of P a for methanol (~6 D) correspond to the value for its pentameric cluster [13, 14]. The dielectric constant e as a function of the arbitrary polarity P a for alcohols, ketones (see Tables 1 and 2), and water is shown in Fig. 1. This curve is linear in determination of P a both with M and with R (in a first approximation), while there is no correlation between and m of the molecules. Figure 2 shows the effect of the dipole moment m of molecules of unassociated and the arbitrary polarity P a of associated solvents on the solubility (crystallization) of substances of different polarity, in particular, water (average P a = 11.7 D), glucose (m = 14.1 D), and glycine (m = 20.8 D) with the data in [17-19]. Solubility of these substances higher than 0.1 mole fraction is observed in solvents with polarity greater than 3, 10, and 12 D, which is in agreement with the change in the polarity of the dissolved substances. As the polarity of the solvent approaches the polarity of the dissolved substance, the solubility of the latter monotonically increases to the maximum, equal at the limit (in the case of solubility in itself) to 1 mole fraction. The greater the difference between the values of the polarity of the solvent and the dissolved substance, the lower the solubility of the dissolved substance (at t = const). Based on the data on the solubility (crystallization) of high-melting n-alkanes and their mixtures (paraffins) in associated and unassociated solvents, the macroscopic dipole moment (arbitrary polarity P a ) of molecules of water, aliphatic alcohols from methanol to octanol, homologs of acetone, and low-molecular-weight carboxylic acids was determined. The effect of the arbitrary polarity of the solvents on the solubility of substances of

Solubility, mole fraction

Pa, D Fig. 2. Effect of the dipole moment m of unassociated and arbitrary polarity P a of associated solvents on the solubility of water (P a = 11.7 D) at 38C (curve 1), glucose (m = 1.41 D) at 25C (curve 2), and glycine (m = 20.8 D) at 25C (curve 3): propanol; acetone; trichloroethylene; o trichloromethane; dimethylformamide; ethanol; ethanol and methanol; methanol; water; water; N-methylpyrrolidone; mixture of isopropanol; mixture of acetone and

mixture of ethanol and water.

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different polarity was demonstrated. The maximum solubility of a substance in a solvent (at t = const) is observed in equality of their polarity values. The values of the arbitrary polarity obtained for widely used solvents allow estimating their dissolving power relative to a dissolved substance from the point of view of the electrostatic theory of the intermolecular interaction in solvents. REFERENCES 1. M. I. Shakhparonov, Introduction to the Modern Theory of Solutions [in Russian], Vysshaya Shkola, 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. Moscow (1976). Yu. Ya. Fialkov et al., Physical Chemistry of Nonaqueous Solutions [in Russian], Khimiya, Leningrad (1973). C. Reichardt, Solvents and Solvent Effects in Organic Chemistry, VCH, Weinheim (1988). R. Taft, J. L. Abboud, and J. Kamlet, J. Org. Chem., 49, 2001-2005 (1984). M. Chastrette and J. Carrette, Can. J. Chem., 63, No. 12, 3492-3498 (1985). I. Vavruch, Chim. Labor Befrieb., 35, No. 11, 536-543 (1984). J. H. Hildebrand, J. M. Prausnitz, and R. L. Scott, Regular and Related Solutions, Van Nostrand-Reinhold, New York (1970). C. M. Hansen, Ind. Eng. Chem. Prod. Res. Dev., 8, No. 2, 2-11 (1969). Solvents Theory and Practice, Symp. Am. Chem. Soc., Washington, D. C. (1971), pp. 48-55. Yu. V. Gurikov, Zh. Fiz. Khim., 54, No. 5, 1223-1227 (1980). A. E. Galashev and O. R. Rakhmanova, Zh. Strukt. Khim., 46, No. 4, 648-654 (2005). D. H. V. Dos Santos et al., J. Chem. Soc., Faraday Trans., 93, No. 16, 2781-2785 (1, No. 16, 2781-2785 (1997). L. J. Bellamy, Infrared Spectra of Complex Molecules Wiley, New York (1964). Yu. Ya. Borovikov, Fiz. Zhidk. Sostoyaniya, 3, 125-132 (1975). S. V. Tyumkin, V. M. Shkolnikov, et al., Trudy VHII NP, 34, 26-34 (1979). S. V. Tyumkin, Khim. Tekhnol. Topl. Masel, No. 7, 37-38 (1993). Handbook of Dipole Moments [in Russian], 3 rd ed., Vysshaya Shkola, Moscow (1971). Handbook of Solubility [in Russian], Vol. 1, Books 1, 2; Vol. 2, Books 1, 2, Izd. Akad. Nauk SSSR, Moscow (1963). L. D. Afanasenko et al., Zh. Prikl. Khim., 54, No. 7, 1492-1497 (1981).

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