Thermodynamic Characteristics of the Dissolution of Fullerene C60 in Benzene, Toluene, o-Xylene, o-Dichlorobenzene, and Carbon Disulfide at Different Temperatures

Authors: Solovyev S.N., Krusheva M.A., Gurov A.A., Aiguzhin V. Published: 09.06.2020
Published in issue: #3(90)/2020  
DOI: 10.18698/1812-3368-2020-3-107-118

Category: Chemistry | Chapter: Physical Chemistry  
Keywords: enthalpy, dissolution Gibbs energy and enthropy, crystallosolvates, clusters, anomalous temperature dependence of solubility

The enthalpy of the fullerene C60 dissolution in carbon disulfide CS2 at 298.15 K was measured in a calorimeter with an isothermal shell. The value of the standard enthalpy of the fullerene C60 dissolution in this substance was found. Standard thermodynamic functions of fullerene C60 dissolution in benzene, chlorobenzene, bromobenzene, carbon disulfide, toluene, o-xylene, and o-dichlorobenzene at 298.15 K were determined based on the results of thermometric measurements and theoretical data. The standard thermodynamic functions have also been determined for toluene, o-xylene, and o-dichlorobenzene at temperatures of 288.15 and 308.15 K. The possible causes of the abnormal temperature dependence of the fullerene C60 solubility in some solvents, as well as sign changes in their dissolution enthalpies, in the temperature range of 288.15--308.15 K have been discussed


[1] Ruoff R.S., Malhorta R., Huestis D.L., et al. Anomalous solubility behavior of C60.Nature, 1993, vol. 362, pp. 140--141. DOI: https://doi.org/10.1038/362140a0

[2] Zhou X., Liu J., Jin Z., et al. Solubility of C60 and C70 fullerenes in toluene, o-xylene and carbon disulfide at various temperatures. FST, 1997, vol. 5, iss. 1, pp. 285--290. DOI: https://doi.org/10.1080/15363839708011990

[3] Domanska U., Letcher T.M. Reply to comments concerning the solubility of backminsterfulleren in tetrahydrofuran, thiophene, tetrahydrothiophene, 1,2-dichlorobenzene, 1, 2, 4-trichlorobenzene and n-butylamine. S. Afr. J. Chem-S-Afr. T., 2000, vol. 53, no. 2, pp. 98--99.

[4] Akhapkina T.E., Krusheva M.A., Solov’ev S.N., et al. Thermochemistry of С60 fullerene solutions in benzene, toluene, о-xylene, and о-dichlorobenzene at 298.15 K. Russ. J. Phys. Chem., 2017, vol. 91, iss. 2, pp. 301--304. DOI: https://doi.org/10.1134/S0036024417020029

[5] Gurov A.A., Krusheva M.A., Solovev S.N. Thermochemistry of fullerene C60 solutions in toluene, o-xylene and o-dichlorobenzene. Herald of the Bauman Moscow State Technical University, Series Natural Sciences, 2019, no. 3, pp. 89--95. DOI: http://doi.org/10.18698/1812-3368-2019-3-89-95

[6] Korobov M.V., Mirakyan A.L., Avramenko N.V., et al. Calorimetric studies of solvates of C60 and C70 with aromatic solvents. J. Phys. Chem. B, 1999, vol. 103, iss. 8, pp. 1339--1346. DOI: https://doi.org/10.1021/jp983165r

[7] Sidorov L.N., Yurovskaya M.A., Borshchevskiy A.N., et al. Fullereny [Fullerenes]. Moscow, Ekzamen Publ., 2005.

[8] Bezmel’nitsyn V.N., Eletskii A.V., Okun’ M.V. Fullerenes in solutions. Phys.-Usp., 1991, vol. 41, no. 11, pp. 1091--1114. DOI: https://doi.org/10.1070/PU1998v041n11ABEH000502

[9] Bezmel’nitsyn V.N., Eletskii A.V., Stepanov E.V. On origin of abnormal temperature dependence of fullerene solvability in organic solvents. Zhurnal fizicheskoy khimii, 1995, vol. 69, no. 4, pp. 735--738 (in Russ.).

[10] Doome R.J., Dermaut S., Fonseca A., et al. New evidences for the anomalous temperature-dependent solubility of C60 and C70 fullerenes in various solvents. FST, 1997, vol. 5, iss. 7, pp. 1593--1606. DOI: https://doi.org/10.1080/15363839708013340

[11] Sun Y.-P., Bunker C.E. C70 in solvent mixtures. Nature, 1993, vol. 365, no. 6445, pp. 398--408. DOI: https://doi.org/10.1038/365398a0

[12] Turanov A.N., Kremenskaya I.N. Interaction of fullerene C60 with iodine in organic solvents. Russ. Chem. Bull., 1995, vol. 44, iss. 3, pp. 465--466. DOI: https://doi.org/10.1007/BF00702388

[13] Smith A.L., Walter E., Korobov M.V., et al. Some enthalpies of solution of C60 and C70. Thermodynamics of the temperature dependence of fullerene solubility. J. Phys. Chem., 1996, vol. 100, iss. 16, pp. 6775--6780. DOI: https://doi.org/10.1021/jp952873z

[14] Avramenko N.V., Mirakyan A.L., Korobov M.V. Thermal behaviour of the crystals formed in the buckminsterfullerene-toluene, o-xylene and bromobenzene systems. Thermochim. Acta, 1997, vol. 299, iss. 1-2, pp. 141--144. DOI: https://doi.org/10.1016/S0040-6031(97)00170-6

[15] Korobov M.V., Mirakyan F.L., Avramenko N.V., et al. Abnormal temperature dependence of S60 solvability. Dokl. RAN, 1996, vol. 349, no. 3, pp. 346--349 (in Russ.).

[16] Volge P.L.O., Dias G.Y.M., Herbst M.H., et al. Enthalpy of solution of fullerene C60 in aromatic solvents. Abs. 28th Int. Conf. on Solution Chemistry. Debrecen, Hungary, 2003, pp. 175.

[17] Nikolskiy B.P., ed. Spravochnik khimika. T. 3. [Handbook of the chemist. Vol. 3]. Moscow, Leningrad, Khimiya Publ., 1964.

[18] Kirgintsev A.N., Trushnikova L.N., Lavrentyeva V.P. Rastvorimost’ neorganicheskikh veshchestv v vode [Solvability of non-organic substances in water]. Leningrad, Khimiya Publ., 1972.

[19] Avramenko N.V., Mirakyan A.L., Korobov M.V., et al. Stability and rule in solubility phenomena. HTHP, 1998, vol. 30, pp. 71--75.

[20] Avramenko N.V., Korobov M.V., Parfenova A.M., et al. Thermochemistry of C60 and C70 fullerene solvates. J. Therm. Anal. Calorim., 2006, vol. 84, iss. 1, pp. 259--262. DOI: https://doi.org/10.1007/s10973-005-7172-z

[21] Yin J., Wang B.-H., Li Z.-F., et al. Enthalpies of dissolution of C60 and C70 in o-xylene, toluene and CS2 at temperatures from 293.15 to 313.15 K. J. Chem. Thermodyn., 1996, vol. 28, iss. 10, pp. 1145--1151. DOI: https://doi.org/10.1006/jcht.1996.0100

[22] Sodikov F., Tabarov S.Kh., Tuychiev Sh., et al. The study influence of C60 on the thermophysical properties of ortho-xylene and chlorobenzene. Doklady AN Respubliki Tadzhikistan [Reports of the Academy of Sciences of the Republic of Tajikistan], 2016, vol. 59, no. 5-6, pp. 218--222 (in Russ.).

[23] Tuychiev Sh., Tabarov S.Kh., Aknazarova Sh., et al. Influence of concentration of fullerene C60 on temperature of freezing of its solutions in p-ksylene. Izv. AN Respubliki Tadzhikistan. Otd. fiz-mat., khim., geolog. i tekh. nauk [News of the Academy of Sciences of the Republic of Tajikistan. Department of Physical, Mathematical, Chemical, Geological and Technical Sciences], 2010, no. 1 (138), pp. 65--69 (in Russ.).

[24] Ginzburg B.M., Tuichiev Sh., Tabarov S.H. Formation of zero density regions during the dissolving of C60 and C70. J. Macromol. Sci. Part B, 2013, vol. 52, iss. 6, pp. 773--787. DOI: https://doi.org/10.1080/00222348.2012.721654

[25] Tropin T.V., Avdeev M.V., Aksenov V.L. Small-angle neutron scattering data on C60 clusters in weakly polar solutions of fullerenes. Crystallogr. Rep., 2007, vol. 52, iss. 3, pp. 483--486. DOI: https://doi.org/10.1134/S1063774507030261

[26] Avdeev M.V., Aksenov V.L., Tropin T.V. Models of cluster formation in solutions of fullerenes. Russ. J. Phys. Chem., 2010, vol. 84, iss. 8, pp. 1273--1283. DOI: https://doi.org/10.1134/S0036024410080017

[27] Kadish K.M., Rouff R.S., eds. Recent advances in the chemistry and physics of fullerenes and related materials. The Electrochemical Society, 1995.

[28] Wang Y., Suna A. Fullerenes in photoconductive polymers. Charge generation and charge transport. J. Phys. Chem. B, 1997, vol. 101, iss. 29, pp. 5627--5638. DOI: https://doi.org/10.1021/jp964019t

[29] Konarev D.V., Shul’ga Yu.M., Roshchupkina O.S., et al. Synthesis and some properties of charge transfer complexes of C60 with asymmetric donors of tetrathiafulvalene family. J. Phys. Chem. Solids, 1997, vol. 58, iss. 11, pp. 1869--1872. DOI: https://doi.org/10.1016/S0022-3697(97)00089-9