Propellants Explosives Pyrotechnics · 1997 · 84 citations · 55 references
Natural SciencesChemistryMaterials ScienceChemical KineticsThermal AnalysisThermodynamicsCatalytic Reaction KineticsChemical Reaction KineticsChemical ThermodynamicsDecomposition AnalysisEnzyme KineticsKinetic ModelingAutocatalytic KineticsAutocatalytic ReactionsDecomposition KineticsDecomposition MechanismsKinetic MeasurementPeroxide FormationThermal DecompositionThermal Decomposition Reactions
Abstract Kinetic constants for decomposition of nitrocellulose in the 50 °C to 500°C range are analyzed. At T < 100°C, three processes (depolymerization, peroxide formation, and hydrolysis) are consistent with the reported kinetics. For T = 100°C–200°C, 28 of 30 previously reported kinetic measurements can be organized clearly into two categories by the use of the kinetic compensation effect. These two groups fit the first‐order and autocatalytic processes. Conflicting interpretations are reconciled by this approach. At T > 200°C, the kinetics are consistent with the existence of the first‐order step and desorption of the products as two parallel processes which, together, control the rate. Time‐to‐exotherm and mass burning rate kinetics are compared as temperature‐dependent reaction‐desorption events.
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Chemical Kinetics and Chain Reactions
Nature · 1936 · 566 citations
An examination of the kinetic compensation effect
Paul D. Garn · Journal of thermal analysis · 1975 · 144 citations
Natural Sciences, Chemistry, Physics +16