Date of Award

Spring 1-1-2013

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry & Biochemistry

First Advisor

G. Barney Ellison

Second Advisor

Mark R. Nimlos

Third Advisor

W. Carl Lineberger

Fourth Advisor

J. Mathias Weber

Fifth Advisor

John W. Daily

Abstract

Furans are important biomass monomers. They are also under consideration as possible biofuels for internal combustion engines. This thesis considers the pyrolysis of methylated furans. In particular, the thermal decomposition of 2-methylfuran, 3-methylfuran, and 2,5-dimethylfuran has been studied in a high temperature (1000 K --1600 K) microtubular flow reactor. The approximate residence time in the heated SiC reactor is 100 -- 200 μsec. The nascent pyrolysis products are identified by 118.2 nm (10.487 eV) photoionization mass spectroscopy and are complemented by matrix infrared absorption spectroscopy. The three furans that are the subject of this thesis are shown to undergo pyrolysis in a manner that is completely analogous to the parent compound, furan. The result of this thesis is the validation of a general mechanism for unimolecular, thermal decomposition of any alkylated furans. The initial steps in the pyrolysis are the formation of a set of carbenes. These carbenes undergo further fragmentation to a set of simple alkynes, ketenes, and CO.

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