Concerted pericyclic reactions appear to dominate the pyrolysis of celluose and hemicellulose in the absence of ions. In the present work, we use laboratory pyrolysis experiments and computational quantum chemistry to relate elementary thermal-decomposition steps for glucose and small alcohols to analogous steps for cellulose and hemicellulose. Seshadri and Westmoreland (J. Phys. Chem. A 2012  , 16, 11997) showed that elementary steps for glucose pyrolysis were rationalized as pericyclic isomerizations and decompositions involving -OH groups, including catalysis of the steps by -OH groups from H2O or from the glucose. Similar steps, computed at a CBS-QB3 level and converted to rate constants by transition-state theory, appear to explain the formation of esters from alcohols and aldehydes. The glucose, alcohol, and aldehyde steps could occur in cellulose and hemicellulose pyrolysis, explaining rates and products of pyrolysis steps.

Role of pericyclic reactions in the pyrolysis of cellulose and hemicellulose

248th National Meeting (2014)

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