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Estimation of Time to Maximum Rate Under Adiabatic Conditions(TMR_(ad)) Using Kinetic Parameters Derived From DSC-Investigation of Thermal Behavior of 3-Methyl-4-Nitrophenol

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化学推进剂与高分子材料 2011年第1期9卷 84-96页

作者： Bertrand Roduit Patrick Folly Alexandre Sarbach Beat Berger Franz Brogli Francesco Mascarello Mischa Schwaninger thomas glarner Eberhard Irle Fritz Tobler Jacques Wiss Markus Luginbühl Craig Williams Pierre Reuse Francis Stoessel AKTS AG TechnoArk 13960 SidersSwitzerland Armasuisse Science and Technology Centre3602 ThunSwitzerland Ciba Schweizerhalle AG P.O.Box4002 BaselSwitzerland DSM Nutritional Products Ltd. Safety laboratory4334 SisselnSwitzerland F.Hoffmann-La Roche Ltd Safety laboratories4070 BaselSwitzerland Lonza AG Safety Laboratory VispRottenstr.63930 Visp Switzerland Novartis Pharma AG Novartis CampusWSJ-145.8.544002 BaselSwitzerland Syngenta Crop Protection Münchwilen AG WMU 3120.1.544333 MünchwilenSwitzerland Swiss Safety Institute Schwarzwaldallee 215WRO-1055.5.024002 BaselSwitzerland

Kinetic parameters of the decomposition of hazardous chemicals can be applied for the estimation of their thermal behavior under any temperature profile.Presented paper describes the application of the advanced kinetic approach for the determination of the thermal behavior also under adiabatic conditions occurring e.***.in batch reactors in case of cooling failure.The kinetics of the decomposition of different samples(different manufacturers and batches) of 3-methyl-4-nitrophenol were investigated by conventional DSC in non-isothermal(few heating rates varying from 0.25 to 8.0K/min) and isothermal(range of 200~260℃) modes.The kinetic parameters obtained with AKTS-Thermokinetics Software were applied for calculating reaction rate and progress under different heating rates and temperatures and verified by comparing simulated and experimental signals.After application of the heat balance to compare the amount of heat generated during reaction and its removal from the system,the knowledge of reaction rate at any temperature profiles allowed the determination of the temperature increase due to the self-heating in adiabatic and pseudo-adiabatic conditions.Applied advanced kinetic approach allowed simulation the course of the Heat-Wait-Search(HWS) mode of operation of adiabatic calorimeters.The thermal safety diagram depicting dependence of Time to Maximum Rate(TMR) on the initial temperature was calculated and compared with the results of HWS experiments carried out in the system with Ф-factor amounting to 3.2.The influence of the Ф-factor and reaction progress reached at the end of the HWS monitoring on the TMR is discussed.Presented calculations clearly indicate that even very minor reaction progress reduces the TMRad of 24h characteristic for a sample with initial reaction progress amounting to zero.Described estimation method can be verified by just one HWS-ARC,or by one correctly chosen ISO-ARC run of reasonable duration by knowing in advance the dependence of the TMR on the initial temperature for any Ф-factor.Prop

关键词： adiabatic condition methyl nitrophenol DSC Ф-factor kinetics thermal runaway,TMR

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