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Reaction kinetics of nitrogen dioxide with methanol in the gas phase.

The reaction between diluted nitrogen dioxide and methanol in Nz has been investigated in the gas phase at room temperature. The observations that 1 mol of methyl nitrite is produced from 2 mol of NOz and that almost no methyl nitrate is produced support that the reaction proceeds as CH30H + 2NOZ CH30N0 + HN03. The rate depends on the second power of the NOz concentration. It depends on the first power of the methanol concentration at low concentration in accord with previous researchers but gradually becomes independent with the increase of the concentration. From the above kinetics as well as the rate constant, the reaction is considered to proceed via the formation of a certain kind of asymmetric NOz dimer which subsequently reacts with methanol bimolecularly.