Various techniques of molecular thermodynamics and solution theory have been applied, through the transition state theory, to problems in chemical kinetics. These include experimental techniques for ascertaining the structure and properties of the transition states for various classes of reactions, plus analytical methods for using this information to predict the effect of solvents or reactant structure on chemical reaction rates. Such methods provide the chemical engineer with an additional parameter to use in the optimal design of reaction systems–that is, the chemistry of the reaction itself.

A static-type apparatus equipped with a visual cell was utilized in the present study to measure isothermal vapor-liquid equilibrium (VLE) and vapor-liquid-liquid equilibrium (VLLE) data over a temperature range of 323.24 to 393.15 K. The VLE data were determined experimentally for binary mixtures of propylene glycol monomethyl ether (PGME) + propylene glycol methyl ether acetate (PGMEA) and acetic acid + PGME. A minimum pressure azeotrope exhibits on each isotherm of acetic acid + PGME. The VLLE data were also measured for water + PGMEA and water + PGMEA + PGME. The VLLE data could be correlated well by the NRTL and the UNIQUAC models accompanied with the Hayden-O'Connell (HOC) correlation for water + PGMEA over a wide temperature range as linearly temperature-dependent parameters were adopted. The NRTL-HOC model, together with the parameters determined from the phase-equilibrium data of the constituent binaries, predicted reasonably well the binodal curves of water + PGMEA + PGME. By adjustment of six parameters simultaneously, the NRTL-HOC and the UNIQUAC-HOC models correlated satisfactorily the ternary VLLE properties of water + PGMEA + PGME.

No abstract

No abstract

Various versions of the Soave−Redlich−Kwong (SRK) equation of state incorporating different mixing rules were applied to calculate vapor−liquid equilibrium (VLE), liquid−liquid equilibrium (LLE), and vapor−liquid−liquid equilibrium (VLLE) properties for the systems containing water, alcohols, and esters. The calculated results showed that the SRK equation with the T-type α function and the Chung−Twu (CT) mixing rules embedded in the UNIFAC−Lyngby model (SRK-T/CT− UNIFAC− Lyngby) not only predicts accurately the VLE properties of the constituent binaries but also represents the ternary LLE and VLLE phase behavior reasonably well. Using this model, the vapor pressure data of the pure constituent components are the only required property for the phase equilibrium calculations.