Solubility and critical phenomena in reactive liquid–liquid systems

Abstract

The goal of this work is to consider solubility phenomena in reactive fluid mixtures with liquid-phase splitting. One of the main tasks is to analyze peculiarities of liquid-liquid (LL) systems with equilibrium and nonequilibrium chemical reaction. The special aim is to consider the critical states in these systems. The reactive liquid-liquid equilibrium (LLE) is treated on the base of phase rule. The topology of diagrams of reactive LLE is discussed for some types of binary and ternary systems. Examples are presented of a possible transformation of phase diagrams caused by the shifting of chemical equilibrium and by changes in the shape of the binodal. The transformations resulting in the reactive critical phase formation are considered. Quaternary mixtures are also discussed with the use of experimental data on the solubility in the system with n-propyl acetate synthesis reaction. The mutual crossing of the chemical equilibrium surface and binodal in the composition tetrahedron leads to the origin of the area of simultaneous chemical and LLE with two critical points (reactive critical phases). The shape of the curve of simultaneous chemical and phase equilibrium is also presented in the square of transformed composition variables.

Chemical equilibrium for the reactive system acetic acid+n-butanol+n-butyl acetate+water at 308.15K

“…Such tie-lines belonging to the curves of CE in ternary systems were called by Ung and Doherty as unique reactive tie-lines [9]. In the case of quaternary system linear surface formed by set of unique reactive tie-lines should be considered [10].…”

Solubility, liquid–liquid equilibrium and critical states for the quaternary system acetic acid–ethanol–ethyl acetate–water at 293.15K

“…Liquid-liquid envelop should significantly influence on the chemical reaction run and the study of solubility is a necessary both for process design and basic consideration. The description of phase diagrams should also include the data on liquid-liquid equilibrium (LLE) and critical states: some new experimental results for the system with n-propyl acetate synthesis reaction and thermodynamic consideration of critical states of LLE in reacting systems had been recently presented in our papers [9,10]. Calculation of the disposition of critical points is discussed in [11][12][13][14]; new experimental data on critical states in multicomponent systems are reported in [15].…”

Solubility, liquid–liquid equilibrium and critical states for the quaternary system acetic acid–ethanol–ethyl acetate–water at 303.15K and 313.15K

“…It gives, for example, new data on the structure and features of phase diagrams, such as critical states [18][19][20][21][22][23][24][25].…”