Gas phase pyrolysis of alkyl acetates

Abstract

An investigation was made into the thermal decomposition of twenty-seven aliphatic acetates, using a micro-scale flow reactor connected to a gas chromatograph. The rate of elimination increases markedly as the degree of alkylation of the u-carbon atom becomes higher. The accelerating effect of B-alkyl substituents on the rate of elimination is small, as compared with that of a-alkyl substituents. The reactivity of the aliphatic acetates approaches a limiting value as the carbon chain is extended. The reactivity decreases on the introduction at the 8-carbon atom of an electron-attracting group and increases on the introduction of an electron-releasing group. A tentative mechanism is proposed which is based on the reversible formation of an ion-pair.

Experimental and Modeling Study of Trends in the High-Temperature Ignition of Methyl and Ethyl Esters

“…This channel is also expected to be important in the oxidation of ethyl formate and ethyl acetate, proceeding as shown in eqs and . The rate for the EA reaction has been assigned based on work by Scheer et al while that of the EF reaction is assigned based on the pyrolysis study of ethyl and isopropyl formates and acetates by Blades EA ⇋ CH 3 COOH + normalC 2 normalH 4 EF ⇋ HCOOH + normalC 2 normalH 4 The activation energies reported for reactions and , are 46.580 and 44.172 kcal/mol, respectively.…”

“…The rate for the EA reaction has been assigned based on work by Scheer et al while that of the EF reaction is assigned based on the pyrolysis study of ethyl and isopropyl formates and acetates by Blades EA ⇋ CH 3 COOH + normalC 2 normalH 4 EF ⇋ HCOOH + normalC 2 normalH 4 The activation energies reported for reactions and , are 46.580 and 44.172 kcal/mol, respectively. El Nahas et al reported a barrier of 50.2 kcal/mol (210 kJ/mol) for the concerted elimination of ethylene and propanoic acid from ethyl propanoate.…”

Structures and Energetics of Unimolecular Thermal Degradation of Isopropyl Butanoate as a Model Biofuel: Density Functional Theory and Ab Initio Studies

“…Therefore, studying isopropyl ester as a model biodiesel will shed some light onto the combustion behavior of a branched ester as a biodiesel. There are some experimental studies on isopropyl acetate and isopropyl propanoate esters concerned with determination of the rate coefficients of their unimolecular decompositions. − Only one theoretical study has been reported on the mechanistic details of pyrolysis of isopropyl acetate to propene and acetic acid . Better simulation of fatty acid esters can be achieved by increasing the alkyl chain length at the acid side.…”

Computational studies on thermo-kinetics aspects of pyrolysis of isopropyl acetate and its methyl, bromide and hydroxyl derivatives

“…Many biodiesel models [ 6 , 7 , 8 , 9 ] received a lot of attention both theoretically and experimentally. A few experimental and computational studies [ 10 , 11 , 12 , 13 , 14 ] have been conducted on isopropyl acetate (IPA) and its derivatives. IPA as the simplest branched biodiesel ester molecule is commercially produced by esterifying acetic acid and isopropanol and is widely used in the production of fats, oil, plastics, printing inks, perfumes, varnishes, adhesive agents, and synthetic resins [ 15 , 16 , 17 ].…”