Canadian Journal of Chemistry · 1976 · 28 citations · 1 references
Natural SciencesChemistryPhysical ChemistryThermal AnalysisThermodynamicsCalorimetryChemical ThermodynamicsHigh-pressure ThermodynamicsTemperature MeasurementNon-isothermal KineticsNonisothermal Rate LawsTemperature-dependent Rate Constants
The thermal isomerisation of methyl isocyanide has been measured in the rigorous absence of self-heating over a temperature range from 120–320 °C and at pressures from 2–100 torr. Expressions are given for the rate constant as functions of both temperature and pressure in these ranges of the two variables. The infinite-pressure rate constant is accurately represented by an Arrhenius line with no curvature having E ∞ = 38.2 ± 0.2 kcal mol −1 and log 10 A ∞ (s −1 ) = 13.35 ± 0.11, although at all other pressures, E is a function of temperature.
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