Ethyl Oleate and Ethyl Elaidate Ozonides: Thermal Decomposition and Photolysis

Abstract

Highly pure ethyl oleate and ethyl elaidate were ozonized to their secondary ozonides (respectively EO-SOZ and EE-SOZ). The decomposition enthalpies of EO-SOZ and EE-SOZ were determined by DSC (Differential Scanning Calorimetry) and found, respectively, at --266 kJ/mol and --264 kJ/mol, a value much closer to the theoretically calculated upper limit of --278 kJ/mol than the decomposition enthalpy of --243 kJ/mol measured on EO-SOZ prepared from an ethyl oleate sample conforming to the European Pharmacopoeia. Although a considerable amount of heat was liberated, EO-SOZ and EE-SOZ cannot be defined as explosive based on their DSC traces at a heating rate of 10 °C/min. Pure EO-SOZ and EE-SOZ show a decomposition peak at the DSCs of 137 °C and 139 °C, respectively. The thermal decomposition of EO-SOZ and EE-SOZ was studied also by FT-IR spectroscopy showing that the decomposition involves the loss of the ozonide infrared band at 1110 cm⁻¹ and the formation of the expected decomposition products (pelargonic acid, pelargonaldehyde, ethyl azelate, etc.). The kinetics of the photochemical decomposition of EO-SOZ and EE-SOZ were studied by FT-IR spectroscopy, and the relative rate constants were determined. EO-SOZ when overozonized forms a spin adduct with nitrosobenzene and the relative nitroxyl radical was clearly detected by the Electron Spin Resonance (ESR). Secondary ozonation products known as trioxides may be responsible for these adducts.

Keywords:

• Decomposition Enthalpy
• DSC
• ESR
• FT-IR
• Ethyl Oleate Ozonide
• Ethyl Elaidate Ozonide
• Photolysis
• Thermochemistry