Liquid-Liquid-Solid Equillibrium of Water + 2-propanol + Kosmotropic Salts: Construction of Phase Diagrams and Understanding of Salting-out Effects Using Volumetric and Compressibility Studies

Author(s): Vidhya Jadhav, Shubhangi Mane-Gavade, Rajendra Kumbhar, Sanjay Kolekar, Bhaskar Tamhankar, Sandip Sabale*

Journal Name: Current Physical Chemistry

Volume 9 , Issue 1 , 2019

Become EABM
Become Reviewer
Call for Editor

Graphical Abstract:


Background: Triangular phase diagrams are important to understand the phase behaviors in ternary systems. The salting out of alcohol from water by kosmotropic salt has long been known, but the molecular interactions and the mechanism of bond breaking and making processes has not yet been fully understood.

Objective: To understand the salting-out of 2-propanol from water using kosmotropic salts (Na2S2O3, Na2SO4 and Na2SO3). To study the phase equilibria of liquid-liquid, liquid-solid and liquid-liquid-solid system by constructing ternary phase diagrams. To determine the solute-solute, solute-solvent, and solvent-solvent molecular interactions to resolve the salting- out effect.

Methods: The solubility data of Na2S2O3/Na2SO4/Na2SO3 salts have been reported in pure water, 2-propanol and water + 2-propanol mixtures in different concentrations at 298.15 ± 1 K. The ternary phase diagrams have been constructed from the obtained solubility data. The volumetric and acoustic data of binary and ternary systems of water + 2-propanol, water + salt and water + 2-propanol + salt has been determined using density meter and interferometer.

Results: The ternary phase diagrams have been constructed for water+2-propanol+ Na2S2O3/Na2SO4/Na2SO3 system. The rise in sound velocity signifies more structural interactions in binary water-alcohol and water-salt systems, while the relation is rather change with the ternary system, as the water-alcohol sheath will be broken by the kosmotropic salt which results in to salt-water sheath.

Conclusion: The density, sound velocity and adiabatic compressibility results suggest that phase separation phenomenon is due to the bond breaking and bond making process along with hydrophobic hydration and hydrophobic interactions. The anion S2O3 2-, SO4 2- and SO3 2- promote salting-out effect and the strength of these effects decreases in the order S2O3 2- >SO4 2- >SO3 2-.

Keywords: Acoustic parameter, density, kosmotropic salts, phase diagram, salting-out effect, solubility.

Khayati, G.; Anvari, M. Aqueous two-phase systems composed of different molecular weight of polyethylene glycol and diammonium phosphate for extraction of bovine serum albumin. Ital. J. Food Sci., 2012, 24, 279-283.
Khayati, G.; Alizadeh, S. Extraction of lipase from Rhodotorula glutinis fermentation culture by aqueous two-phase partitioning. Fluid Phase Equilib., 2013, 353, 132-134.
Khayati, G. Optimization of propionic acid extraction by aqueous two-phase system using response surface methodology. Chem. Eng. Commun., 2013, 200, 667-677.
Wang, Y.; Wang, J.; Han, J.; Hu, S.; Yan, Y. Liquid-liquid equilibrium of novel aqueous two-phase systems and evaluation of salting-out abilities of salts. Cent. Eur. J. Chem., 2010, 8, 886-891.
Khayati, G.; Shahriari, M. Measurement and correlation of phase diagram data of hydrophilic alcohols (1-propanol/2-propanol) + salts (Na2SO4/(NH4)2SO4/ NH4NO3) + water systems. Chem. Biochem. Eng. Q., 2016, 30(1), 73-80.
Mills, A.; Smith, F. Isopropyl alcohol-sodium sulfate-water system. Liquid-liquid equilibria. Ind. Eng. Chem. Chem. Eng. Data Series, 1957, 2(1), 30-31.
Dagade, H.; Kumbhar, R.; Sabale, S.; Patil, K. Phase diagram of Na2S2O3+ethanol+water at ambient pressure and temperature. Fluid Phase Equilib., 2007, 255, 110-114.
Sabale, S. Phase diagram of Na2S2O3)+t-butanol+water at ambient pressure and temperature. Chin. J. Chem., 2011, 29, 2562-2564.
Deng, T.; Yu, X.; Li, D. Metastable phase equilibrium in the aqueous ternary system K2SO4+MgSO4+H2O at (288.15 and 308.15) K. J. Solution Chem., 2009, 38(1), 27-34.
Silverio, S.; Rodrguez, O.; Teixeira, J.; Macedo, E. The effect of salts on the liquid-liquid phase equilibria of PEG600+salt aqueous two-phase systems. J. Chem. Eng. Data, 2013, 58, 3528-3535.
Ananthapadmanabhan, K.; Godard, E. Aqueous biphase formation in polyethylene oxide-inorganic salt systems. Langmuir, 1987, 3(1), 25-31.
Onori, G. Adiabatic compressibility and structure of aqueous solutions of ethyl alcohol. J. Chern. Phys., 1988, 89(7), 4325-4332.
Freire, M.G.; Neves, C.M.S.S.; Silva, A.M.S.; Santos, L.M.N.B.F.; Marrucho, I.M.; Rebelo, L.P.N.; Shah, J.K.; Maginn, E.J.; Coutinho, J.A.P. 1H NMR and molecular dynamics evidence for an unexpected interaction on the origin of salting-in/salting-out phenomena. J. Phys. Chem. B, 2010, 114, 2004-2014.
Sadeghi, R.; Mostafa, B.; Parsi, E.; Shahebrahimi, Y. Towards an understanding of the salting-out effects in aqueous ionic liquid solutions using vapor-liquid equilibria, liquid-liquid equilibria, volumetric, compressibility and conductivity behavior. J. Phys. Chem. B, 2010, 114, 16528-16541.
Franks, F.; Ives, D. The structural properties of alcohol-water mixtures. Q. Rev. Chem. Soc., 1968, 20, 1-44.
Castellan, G.W. Physical Chemistry.Editor, Addison- Wesley Publishing Company, London; , 1964.
Frankforter, G.; Frary, F. Equilibria in systems containing alcohols, salts and water, including a new method of alcohol analysis. J. Phys. Chem., 1913, 17, 402-473.
Pang, F.; Seng, C.; Teng, T.; Ibrahim, M. Densities and viscosities of aqueous solutions of 1-propanol and 2-propanol at temperatures from 293.15 K to 333.15 K. J. Mol. Liq., 2007, 136, 71-78.
Paez, S.; Contreras, M. Densities and viscosities of binary mixtures of 1-propanol and 2-propanol with acetonitrile. J. Chem. Eng. Data, 1989, 34, 455-459.
Savaroglu, G.; Aral, E. Densities, speed of sound and isentropic compressibilities of the ternary mixture 2-propanol+acetone+cyclohexane and the constituent binary mixtures at 298.15 and 313.15 K. Fluid Phase Equilib., 2004, 215(2), 253-262.
Aminabhavi, T.; Aralaguppi, M.; Harogoppad, S.; Balundgi, R. Densities, viscosities, refractive indices, and speeds of sound for methyl acetoacetate+aliphatic alcohols (C1-C8). J. Chem. Eng. Data, 1993, 38, 31-39.
Grosso, D.V.; Mader, C. Speed of sound in pure water. J. Acoust. Soc. Am., 1972, 52, 1442-1446.
Tanaka, M.; Girard, G.; Davis, R.; Peuto, A.; Bignell, N. Recommended table for the density of water between 0 °C and 40 °C based on recent experimental reports. Metrologia, 2001, 38, 301-309.
Patil, P.; Patil, S.; Borse, A.; Hundiwale, D. Density, excess molar volume and apparent molar volume of binary liquid mixtures. Rasayan J. Chem., 2011, 4, 599-604.
Shivkumar, H.R.; Antony, S.N. Thermoacoustical investigations on potassium thiocyanate in 2-propanol+water mixture. Int. J. Pure Appl. Chem., 2011, 6(1), 65-73.
Eisenberg, D.; Kauzmann, W. The structure and properties of matter.Oxford University Press, Ely House: London, ; , 1969.
Santosh, M.; Bhat, D.K.; Bhat, A.S. Molecular interactions in glycylglycine-MnCl2 aqueous solutions at (288.15, 293.15, 298.15, 303.15, 308.15, 313.15, and 318.15) K. J. Chem. Eng. Data, 2009, 54, 2813-2818.

open access plus

Rights & PermissionsPrintExport Cite as

Article Details

Year: 2019
Published on: 02 June, 2019
Page: [36 - 49]
Pages: 14
DOI: 10.2174/1877946809666190201145050

Article Metrics

PDF: 34