Theoretical investigation of the formic acid decomposition kinetics

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Abstract Decomposition of formic acid (HCO 2 H) proceeds via three unimolecular channels: dehydration, decarboxylation, and dissociation, the latter expected to be of minor contribution to the overall kinetics. In addition, despite the similar values reported for the individual activation energies for the dehydration and decarboxylation reactions, experimental works have shown that the former is dominant in the reaction mechanism. These reactions show pressure‐dependent rate coefficients, and the high‐pressure condition is not yet verified at atmospheric pressure. This work aims to investigate the influence of temperature and pressure on the rate coefficients. Hence, theoretical calculations at the CCSD(T)/CBS level have been performed to accurately describe the unimolecular reaction and Rice‐Ramsperger‐Kassel‐Marcus (RRKM) rate coefficients have been calculated and integrated for the prediction of k ( T , P ) rate coefficients, adopting both strong and weak collision models, over the intervals 0.5‐10 atm and 298‐2200 K. Our results suggest that the isomerization path is important and explains the preference for the (CO + H 2 O) channel. Rate coefficients for the (CO 2 + H 2 ) and (CO + H 2 O) formations are given, in s −1 , as exp(−34404/ T ) and exp(−33785/ T ), respectively. The dissociation limit of 107.29 kcal mol –1 , with respect the Z ‐HCO 2 H conformer, leading to OH + HCO, via a barrierless potential curve, with rate coefficients, in s −1 , expressed as k HCO+OH ( T ) = 1.68 × 10 17 exp(−56018/ T ). Temperature and pressure dependence for the HCO + OH → CO 2 + H 2 and HCO + OH → CO + H 2 O reactions have also been estimated.

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