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.