THERMODYNAMICS OF LIQUID–GAS PHASE EQUILIBRIA OF DIISOPROPYLSULFOXIDE–WATER SYSTEM
Abstract
The saturated vapor pressure of diisopropylsulfoxide aqueous solutions was measered at temperatures of 303.15 K and 308.15 K. It was shown that the total saturated vapor pressure increases with decreasing diisopropylsulfoxide concentration in the solution and with increasing temperature. As in the cases of diethylsulfoxide and dipropylsulfoxide aqueous solutions, a negative deviation from Raoult’s law is also observed. This confirms the ability of diisopropylsulfoxide molecules to associate with water molecules. Based on the results obtained, the partial pressures, the activity coefficients of diisopropylsulfoxide and water and the excess Gibbs energy of their mixing, were calculated. It is shown that the excess Gibbs energy of mixing is negative and reaches its minimum value at a mole fraction of diisopropylsulfoxide equal to 0.38. The obtained data on the excess Gibbs energy of mixing DiPSO and water were treated using the Redlich–Kister equation. It has been established that the interaction between the molecules of diisopropylsulfoxide and water is stronger than in the diethylsulfoxide+water system, and weaker than in the dipropylsulf-oxide+water system. This fact can be explained by an increase in the electron-donating ability of the alkyl group with increasing hydrocarbon chain length, which increases the reactivity of the oxygen atom of the sulfoxide group. As a result, when moving from diethylsulfoxide to diisopropylsulfoxide or dipropylsulfoxide, the ability of their molecules to interact with water molecules to form hydrogen bonds increases. At the same time, a decrease in hydrophobic effects and dispersion forces between diisopropylsulfoxide molecules with a branched hydrocarbon chain leads to a weakening of the interaction between molecules in the diisopropylsulfoxide+water system compared to the dipropylsulfoxide+water system, which is also observed experimentally.
For citation:
Grigoryan G.S., Sargsyan H.R. Thermodynamics of liquid–gas phase equilibria of diisopropylsulfoxide–water system. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2024. V. 67. N 1. P. 67-73. DOI: 10.6060/ivkkt.20246701.6933.
References
Grigoryan K., Zatikyan A., Shilajyan H. Effect of Monovalent Ions on the Thermal Stability of Bovine Serum Albumin in Dimethylsulfoxide Aqueous Solutions. Spectroscopic approach. J. Biomol. Struct. Dyn. 2021. V. 39. N 6. P. 2284-2288. DOI: 10.1080/07391102.2020.1743759.
Aznauryan M.G., Markarian S.A. Properties of DNA + Dipropylsulfoxide or Dibutylsulfoxide + Water Ternary So-lutions. J. Solution Chem. 2010. V. 39. P. 43-50. DOI: 10.1007/s10953-009-9481-5.
Gabrielyan L.S. FTIR and ab Initio Studies of Diisopropyl-sulfoxide and its Solutions. J. Solution Chem. 2017. V. 46. P. 759-776. DOI: 10.1007/s10953-017-0600-4.
Wallace V.M., Dhumal N.R., Zehentbauer F.M., Kim H.J., Kiefer J. Revisiting the Aqueous Solutions of Dime-thyl Sulfoxide by Spectroscopy in the Mid- and Near-Infrared: Experiments and Car-Parrinello Simulations. J. Phys. Chem. B. 2015. V. 119. N 46. P. 14780-14789. DOI: 10.1021/acs.jpcb.5b09196.
Ghazoyan H.H., Markarian S.A. Densities and Thermo-chemical Properties of Dimethylsulfone in Dimethylsulfoxide and Dimethylsulfoxide/Water Equimolar Mixture. J. Mol. Liq. 2013. V. 183. P. 85-88. DOI: 10.1016/j.molliq.2013. 04.010.
Chaban V.V. Force Field Development and Simulations of Senior Dialkylsulfoxides. Phys. Chem. Chem. Phys. 2016. V. 18. P. 10507–10515. DOI: 10.1039/C5CP08006A.
Gabrielyan L.S., Markaryan Sh.A. Dielectric Relaxation Spectroscopy Study of the Structure and Dynamics of Dialkyl Sulfoxide Solutions. Russ. J. Phys. Chem. A. 2018. V. 92. N 2. P. 205-213. DOI: 10.1134/S0036024418020073.
Senent M.L., Dalbouha S., Cuisset A., Sadovski D. Theoretical Spectroscopic Characterization at Low Temperatures of Dimethyl Sulfoxide: The Role of Anharmonicity. J. Phys. Chem. A. 2015. V. 119. N 37. P. 9644-9652. DOI: 10.1021/acs.jpca.5b06941.
Kirillov S.A., Gorobets M.I., Gafurov M.M., Ataev M.B., Rabadanov K.Sh. Self-Association and Picosecond Dynamics in Liquid Dimethyl Sulfoxide. J. Phys. Chem. B. 2013. V. 117. P. 9439-9448. DOI: 10.1021/jp403858c.
Ghazoyan H.H., Markarian S.A. Volumetric Properties of Solutions of Dimethylsulfone in Ethanol–Water Mixture at Temperatures Range of 298.15-323.15 K. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2017. V. 60. N 7. P. 27-33 (in Russian). DOI: 10.6060/tcct.2017607.5564.
Gabrielyan L.S., Markarian S.A., Weingärtner H. Dielectric Relaxation of Dipropylsulfoxide. J. Mol. Liq. 2011. V. 159. P. 201–203. DOI: 10.1016/j.molliq.2011.01.007.
Gabrielyan L.S., Markarian S.A. Dielectric Relaxation Study of Dipropylsulfoxide/Water Mixtures. J. Mol. Liq. 2011. V. 162. P. 135-140. DOI: 10.1016/j.molliq.2011.06.016.
Mkhitaryan A.S., Papanyan Z.K., Gabrielyan L.S., Markarian Sh.A. Heat of Hydration of Diethylsulfone by Quantum Chemical Calculation. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2018. V. 61. N 8. P. 17-21 (in Russian). DOI: 10.6060/ivkkt20186 1008.5737.
Markarian S.A., Gabrielyan L.S., Bonora S. The Volumetric and Thermochemical Properties of Dipropylsulfoxide in Water. J. Solution Chem. 2010. V. 39. P. 591-602. DOI: 10.1007/s10953-010-9536-7.
Celso F.L., Aoun B., Triolo A., Russina O. Liquid Struc-ture of Dibutylsulfoxide. Phys. Chem. Chem. Phys. 2016. V. 18. P. 15980–15987. DOI: 10.1039/C6CP02335E.
Ghazoyan H.H., Grigoryan Z.L., Gabrielyan L.S., Markarian Sh.A. Study of Thermodynamic Properties of Binary Mixtures of Propionitrile with Dimethylsulfoxide (or Diethylsulfoxide) at Temperatures from (298.15 to 323.15) K. J. Mol. Liq. 2019. V. 284. P. 147-156. DOI: 10.1016/j.molliq.2019.03.147.
Kazakova A.I., Yakovlev I.G., Garkushin I.K. Phase Equilibrium States in a Two-Component Diphenyl-n-Nonadecane System. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2023. V. 66. N 6. P. 46-53 (in Russian). DOI: 10.6060/ivkkt.20236606.6733.
Ghazoyan H.H. Volumetric properties of acryloni-trile+ethanol mixture over temperature range from (293.15 to 323.15) K at ambient pressure. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2020. V. 63. N 2. P. 32-37. DOI: 10.6060/ivkkt.20206302.6068.
Grigoryan Z.L., Kazoyan E.A., Markaryan Sh.A. Thermodynamics of Liquid–Gas Phase Equilibrium in Dimethyl Sulfoxide–Alkanol Systems in the Range of 293.15–323.5 Russ. J. Phys. Chem. A. 2015. V. 89. N 10. P. 1790-1794. DOI: 10.1134/S0036024415100131.
Qian X., Han B., Liu Y., Yan H., Liu R. Vapor Pressure of Dimethyl Sulfoxide and Water Binary System. J. Solution Chem. 1995. V. 24. N 11. P. 1183-1188. DOI: 10.1007/ bf00972964.
Markarian S.A., Zatikyan A.L., Grigoryan V.V., Gri-goryan G.S. Vapor Pressures of Pure Diethyl Sulfoxide from (298.15 to 318.15) K and Vapor-Liquid Equilibria of Binary Mixtures of Diethyl Sulfoxide with Water. J. Chem. Eng. Data. 2005. V. 50. P. 23-25. DOI: 10.1021/je034278t.
Grigoryan G.S., Markaryan S.A. Thermodynamics of Liquid–Gas Phase Equilibria in the Dipropylsulfoxide–Water System in the Range of 303.15 to 323.15 K. Russ. J. Phys. Chem. A. 2013. V. 87. N 2. P. 191-193. DOI: 10.1134/S0036024413020027.
Grigoryan G.S., Markaryan S.A. Thermodynamics of Liquid–Gas Phase Equilibria of Diisopropyl and Dibutyl Sulfoxides. Russ. J. Phys. Chem. A. 2014. V. 88. N 6. P. 1071-1072. DOI: 10.1134/S0036024414060132.
Pratt L.R. Theory of Hydrophobic Effects. Ann. Rev. Phys. Chem. 1985. V. 36. N 1. P. 433-449. DOI: 10.1146/annurev.pc.36.100185.002245.