Kinetics of nopyl acetate synthesis by homogeneously catalyzed esterification of acetic acid with nopol

Abstract

The esterification of nopol with acetic acid to produce nopyl acetate using sulfuric acid as homogeneous catalyst was studied. The reactions were carried out in a batch reactor, at different temperatures (50, 60, 70 and 80 °C), catalyst concentrations (0.0184, 0.0275, 0.0367 and 0.0480 molL−1 and molar ratio of acetic acid to nopol (1: 1, 1:2, 1:3 and 1: 4); the chemical equilibrium composition was measured at those reaction conditions. It was found that the equilibrium composition is a weak function of temperature, equilibrium conversion was 63, 68, 71 and 75% at 50, 60, 70 and 80°C, respectively. The reaction was described with a simple power-law model with a second-order kinetic model for both the forward and the backward reaction, using concentration and activities which were predicted by the Universal Functional group Contribution (UNIFAC) method for considering non-ideal behavior of the liquid phase. The forward reaction rate and the equilibrium constants increased with temperature; the relation of the pre-exponential factor with the catalyst amount was evaluated. The activation energy and pre-exponential factor estimated for the forward reaction using the kinetic model based on concentration, were respectively, 28.08 kJmol−1 and 11126 Lmol−1h −1 with a concentration of catalyst of 0.0275 M. Using the kinetic model based on activities, the forward reaction rate constant was 28.56 kJmol−1 and the kfo,act was 33860 Lmol−1h −1 . The enthalpy (34.90 kJmol−1 ) and the entropy (0.12 kJmol−1K−1 ) of reaction were determined using van’t Hoff equation.

Keywords

• activity coefficients
• nopol
• reaction rate
• equilibrium constant
• sulfuric acid