Abstract

Four non-polymeric plasticizers, propylene glycol, diethyl phthalate, triacetin, and glycerin have been subjected to rising temperature thermogravimetry for kinetic analysis and vaporization-based thermal stability evaluation. Since volatile loss of a substance is a function of its vapor pressure, the thermal stability of these plasticizers has been analyzed by generating vapor pressure curves using the Antoine and Langmuir equations. Unknown Antoine constants for the sample compounds, triacetin and glycerin have been derived by subjecting the vapor pressure curves to nonlinear regression. For the first time, the entire process of obtaining the unknown Antoine constants through thermogravimetry has been validated by developing an approach called the 'double reference method.' Based on this method, it has been possible to show that this technique is accurate even for structurally diverse compounds. Kinetic analysis on the volatilization of compounds revealed a predominant zero order process. The activation energy values for vaporization of propylene glycol, diethyl phthalate, triacetin, and glycerin, as deduced from the Arrhenius plots, have been determined to be 55.80, 66.45, 65.12, and 67.54 kJ/mol, respectively. The enthalpies of vaporization of the compounds have been determined from the Clausius-Clapeyron plots. Rising temperature thermogravimetry coupled with nonlinear regression analysis has been shown to be an effective and rapid technique for accurately predicting the vapor pressure behavior and thermal stability evaluation of volatile compounds.

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