Russian Journal of Biological Physics and Chemisrty Russian Journal of Biological Physics and Chemisrty АКТУАЛЬНЫЕ ВОПРОСЫ БИОЛОГИЧЕСКОЙ ФИЗИКИ И ХИМИИ 2499-9962 55171 10.29039/rusjbpc.2022.0565 МЕДИЦИНСКАЯ БИОФИЗИКА И БИОФИЗИЧЕСКАЯ ХИМИЯ MEDICAL BIOPHYSICS AND BIOPHYSICAL CHEMISTRY МЕДИЦИНСКАЯ БИОФИЗИКА И БИОФИЗИЧЕСКАЯ ХИМИЯ THERMODYNAMIC MODELING OF SYSTEMS WITH BENZOIC ACID AS MODEL SYSTEMS FOR PHARMACEUTICALS ТЕРМОДИНАМИЧЕСКОЕ МОДЕЛИРОВАНИЕ СИСТЕМ С БЕНЗОЙНОЙ КИСЛОТОЙ КАК “МОДЕЛЬНЫХ СИСТЕМ” ДЛЯ ФАРМАЦЕВТИКИ Пастухов А. А. Pastukhov A. A. pastukhov.2013@mail.ru Институт органической химии им. Н.Д. Зелинского РАН; Москва Россия N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences Moscow Russian Federation 24 11 2022 24 11 2022 7 4 587 592 25 07 2022 https://rusjbpc.ru/en/nauka/article/55171/view

Проведено экспериментальное исследование и термодинамическое моделирование растворимости бензойной кислоты (БК) в органических растворителях. Методами термического анализа исследованы бинарные системы бензойная кислота – бензофенон и бензойная кислота - бензил. Построены фазовые диаграммы и определены координаты эвтектических точек в этих системах. В системе бензойная кислота – бензофенон температура эвтектической точки равна 310,3 К при 18 мол. %. БК, в системе с бензилом температура равна 348,5 К при 35 мол. % БК. Политермы растворимости бензойной кислоты представлены в виде линейной зависимости: ln X = a – b/T, X – мол. доля БК, Т – температура в К: в метилацетате (a = 2,7748, b = 1389,7), этилацетате (a = 1,8099, b = 1102,6), н-пропилацетате (a = 0,9580, b = 854,2), н-бутилацетате (a = 1,2178, b = 902,0), н-пентилацетате (a = 1,0719, b = 836,0), 1,4-диоксане (a = 0,0164, b = 406,0), хлорбензоле (a = 8,2765, b = 3268,4), н-декане (a = 12,332, b = 4916,9), н-додекане (a = 14,623, b = 5808,1). Рассчитаны значения растворимости бензойной кислоты в растворителях при 298 К с использованием параметров растворимости Гильдебранда и Хансена. Проведено сравнение экспериментальных и литературных данных. Установлена зависимость растворимости от разности параметров растворимости компонентов и приведенного радиуса. Рассмотрены модели для термодинамического описания растворимости веществ в органических растворителях на примере бензойной кислоты. Рекомендованы модели регулярных растворов с параметром растворимости Хансена для экспресс-метода расчета растворимости бензойной кислоты в органических растворителях.

In this article, experimental investigation and thermodynamic modelling of benzoic acid (BA) solubility in organic solvents was made. Phase diagrams of binary systems of benzoic acid – benzophenone and benzoic acid – benzil were investigated by the thermal analysis methods. Phase diagrams are studied and eutectic coordinates in these systems were determinated. Eutectic point temperature (310.3 K) and composition of benzoic acid (18 mol. %) for benzoic acid – benzophenone system and eutectic point temperature (348.5 K) and mole fraction of benzoic acid (35 mol. %) for benzoic acid – benzil system were found. In the form of a linear relationship solubility curves of benzoic acid ln X = a – b/T, X – mole fraction BA, T – temperature in K in methyl acetate (a = 2.7748, b = 1389.7), ethyl acetate (a = 1.8099, b = 1102.6), n-propyl acetate (a = 0.9580, b = 854.2), n-butyl acetate (a = 1.2178, b = 902.0), n-pentyl acetate (a = 1.0719, b = 836.0), 1,4-dioxane (a = 0.0164, b = 406.0), chlorobenzene (a = 8.2765, b = 3268.4), n-decane (a = 12.332, b = 4916.9), n-dodecane (a = 14.623, b = 5808.1) were introduced. The solubility of benzoic acid in solvents at 298 K were calculated using the Hildebrand and Hansen solubility parameters. Comparison of the experimental and literature data was hold. Dependence of benzoic acid solubility on difference of the solubility parameters and the reduced radius was established. Models for the thermodynamic description of the solubility of substances in organic solvents are considered using benzoic acid as an example. Regular solution models with Hansen solubility parameters for express calculate solubility method of benzoic acid in organic solvents were recommended.

 бензойная кислота фазовые диаграммы политермы растворимости параметры растворимости benzoic acid phase diagrams solubility solubility parameters

Craig D.Q.M., Reading M. Thermal analysis of pharmaceuticals. Boca Raton: CRC Press, 2007, 400 p. Craig D.Q.M., Reading M. Thermal analysis of pharmaceuticals. Boca Raton: CRC Press, 2007, 400 p. Bernstein J. Polymorphism of molecular crystals. M.: Nauka, 2007, 500 p. (In Russ.) Bernstein J. Polymorphism of molecular crystals. M.: Nauka, 2007, 500 p. (In Russ.) Brittain H.G. Polymorphism in pharmaceutical solids. New York: Informa Healthcare, 2009, 640 p. Brittain H.G. Polymorphism in pharmaceutical solids. New York: Informa Healthcare, 2009, 640 p. Hilfiker R., von Raumer M. Polymorphism in the Pharmaceutical Industry. Weinheim: Wiley-VCH, 2019, 496 p. Hilfiker R., von Raumer M. Polymorphism in the Pharmaceutical Industry. Weinheim: Wiley-VCH, 2019, 496 p. Byrn S.R., Zografi G., Chen X. Solid-state properties of pharmaceutical materials. Hoboken: Wiley, 2017, 406 p. Byrn S.R., Zografi G., Chen X. Solid-state properties of pharmaceutical materials. Hoboken: Wiley, 2017, 406 p. Augustijns P. Solvent systems and their selection in pharmaceutics and biopharmaceutics. New York: Springer, 2007. Augustijns P. Solvent systems and their selection in pharmaceutics and biopharmaceutics. New York: Springer, 2007. Balakrishnan I., Venkatachalam S., Datta D., Jawahar N. A brief review on eutectic mixture and its role in pharmaceutical field. Int. J. of Research in Pharmaceutical Sciences, 2020, vol. 11, no. 3, pp. 3017-3023, doi: 10.26452/ijrps.v11i3.2398. Balakrishnan I., Venkatachalam S., Datta D., Jawahar N. A brief review on eutectic mixture and its role in pharmaceutical field. Int. J. of Research in Pharmaceutical Sciences, 2020, vol. 11, no. 3, pp. 3017-3023, doi: 10.26452/ijrps.v11i3.2398. Sunita Budhwar V., Choudhary M. Pharmaceutical eutectics: A promising drug delivery system. Research Journal of Pharmacy and Technology, 2020, vol. 13, no.11, pp. 5515-5523, doi: 10.5958/0974-360X.2020.00963.4. Sunita Budhwar V., Choudhary M. Pharmaceutical eutectics: A promising drug delivery system. Research Journal of Pharmacy and Technology, 2020, vol. 13, no.11, pp. 5515-5523, doi: 10.5958/0974-360X.2020.00963.4. Lei Z., Chen B., Li C., Liu H. Predictive Molecular Thermodynamic Models for Liquid Solvents, Solid Salts, Polymers, and Ionic Liquids. Chemical Reviews, 2008, vol. 108, no. 4, pp. 1419-1455, doi: 10.1021/cr068441+. Lei Z., Chen B., Li C., Liu H. Predictive Molecular Thermodynamic Models for Liquid Solvents, Solid Salts, Polymers, and Ionic Liquids. Chemical Reviews, 2008, vol. 108, no. 4, pp. 1419-1455, doi: 10.1021/cr068441+. Jouyban A. Handbook of solubility data for pharmaceuticals. Boca Raton: CRC Press, 2010, 306 p. Jouyban A. Handbook of solubility data for pharmaceuticals. Boca Raton: CRC Press, 2010, 306 p. Acree W.E. Solubility of Benzoic Acid and Substituted Benzoic Acids in Both Neat Organic Solvents and Organic Solvent Mixtures. Journal of Physical and Chemical Reference Data, 2013, vol. 42, no. 3, 526 p., doi: 10.1063/1.4816161. Acree W.E. Solubility of Benzoic Acid and Substituted Benzoic Acids in Both Neat Organic Solvents and Organic Solvent Mixtures. Journal of Physical and Chemical Reference Data, 2013, vol. 42, no. 3, 526 p., doi: 10.1063/1.4816161. Hansen C.M. Hansen solubility parameters: a user's handbook. Boca Raton: CRC Press, 2007., 519 p. Hansen C.M. Hansen solubility parameters: a user's handbook. Boca Raton: CRC Press, 2007., 519 p. Acree J.W., Chickos J.S. Phase Transition Enthalpy Measurements of Organic and Organometallic Compounds. Sublimation, Vaporization and Fusion Enthalpies From 1880 to 2015. Part 1. C1-C10. J. Phys. Chem. Ref. Data, 2016, vol. 45, p. 033101-1-565, doi: 10.1063/1.4948363. Acree J.W., Chickos J.S. Phase Transition Enthalpy Measurements of Organic and Organometallic Compounds. Sublimation, Vaporization and Fusion Enthalpies From 1880 to 2015. Part 1. C1-C10. J. Phys. Chem. Ref. Data, 2016, vol. 45, p. 033101-1-565, doi: 10.1063/1.4948363. Acree J.W., Chickos J.S. Phase Transition Enthalpy Measurements of Organic and Organometallic Compounds and Ionic Liquids. Sublimation, Vaporization, and Fusion Enthalpies from 1880 to 2015. Part 2. C11-C192. J. Phys. Chem. Ref. Data., 2017, vol. 46, p. 013104-1-532, doi: 10.1063/1.4970519. Acree J.W., Chickos J.S. Phase Transition Enthalpy Measurements of Organic and Organometallic Compounds and Ionic Liquids. Sublimation, Vaporization, and Fusion Enthalpies from 1880 to 2015. Part 2. C11-C192. J. Phys. Chem. Ref. Data., 2017, vol. 46, p. 013104-1-532, doi: 10.1063/1.4970519. Molochko V.A., Pestov S.M. Phase equilibria and thermodynamics of systems with liquid crystals. M.: IPC MIFCT, 2003, 242 p. (In Russ.) Molochko V.A., Pestov S.M. Phase equilibria and thermodynamics of systems with liquid crystals. M.: IPC MIFCT, 2003, 242 p. (In Russ.) Walas S.M. Phase equilibria in chemical engineering: in two chapters. M.: MIR, 1989, 304 p. (In Russ.) Walas S.M. Phase equilibria in chemical engineering: in two chapters. M.: MIR, 1989, 304 p. (In Russ.) Stefanis E., Panayiotou C. Prediction of Hansen solubility parameters with a new group-contribution method. Int. J. Thermophys., 2008, vol. 29, pp. 568-585, doi: 10.1007/S10765-008-0415-Z. Stefanis E., Panayiotou C. Prediction of Hansen solubility parameters with a new group-contribution method. Int. J. Thermophys., 2008, vol. 29, pp. 568-585, doi: 10.1007/S10765-008-0415-Z. Mohammad M.A., Alhalaweh A., Velaga S.P. Hansen solubility parameter as a tool to predict cocrystal formation. International Journal of Pharmaceutics, 2011, vol. 407, pp. 63-71, doi: 10.1016/j.ijpharm.2011.01.030. Mohammad M.A., Alhalaweh A., Velaga S.P. Hansen solubility parameter as a tool to predict cocrystal formation. International Journal of Pharmaceutics, 2011, vol. 407, pp. 63-71, doi: 10.1016/j.ijpharm.2011.01.030. Salem A., Nagy S., Pal S., Szechenyi A. Reliability of the Hansen solubility parameters as co-crystal formation prediction tool. International Journal of Pharmaceutics, 2019, vol. 558, pp. 319-327, doi: 10.1016/j.ijpharm.2019.01.007. Salem A., Nagy S., Pal S., Szechenyi A. Reliability of the Hansen solubility parameters as co-crystal formation prediction tool. International Journal of Pharmaceutics, 2019, vol. 558, pp. 319-327, doi: 10.1016/j.ijpharm.2019.01.007. Gaikwad E.R., Khabade S.S., Sutar T.B., Bhat M.R., Payghan S.A. Three-dimensional Hansen solubility parameters as predictors of miscibility in cocrystal formation. Asian Journal of Pharmaceutics, 2017, vol. 11, no. 4, pp. 302-318, doi: 10.22377/AJP.V11I04.1627. Gaikwad E.R., Khabade S.S., Sutar T.B., Bhat M.R., Payghan S.A. Three-dimensional Hansen solubility parameters as predictors of miscibility in cocrystal formation. Asian Journal of Pharmaceutics, 2017, vol. 11, no. 4, pp. 302-318, doi: 10.22377/AJP.V11I04.1627. Van Krevelen D.W. Properties of polymers correlation with chemical structures. M.: Chemistry, 1976, 414 p. (In Russ.) Van Krevelen D.W. Properties of polymers correlation with chemical structures. M.: Chemistry, 1976, 414 p. (In Russ.) Askadsky A.A., Matveev J.I. Chemical structures and physical properties of polymers. M.: Chemistry, 1983, 248 p. (In Russ.) Askadsky A.A., Matveev J.I. Chemical structures and physical properties of polymers. M.: Chemistry, 1983, 248 p. (In Russ.)