A general kinetic model framework for the interpretation of adiabatic calorimeter rate data

Bhattacharya, Arijit

doi:10.1016/j.cej.2005.05.003

Cited by 15 publications

(6 citation statements)

References 12 publications

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“…The ARC apparatus is a commercial adiabatic calorimeter that is used to assess the thermal hazard potential of energetic chemicals or materials [12,13]. For each ARC experiment, 1-3 g of sample material was placed in a spherical, carbon steel vessel (0.1% carbon), and the vessel was subsequently attached to the apparatus to form part of a closed, leak-tight system.…”

Section: Accelerating Rate Calorimetry (Arc)mentioning

confidence: 99%

Thermal hazard assessment of nitrobenzene/dinitrobenzene mixtures

Badeen

Turcotte

Hobenshield

et al. 2011

Journal of Hazardous Materials

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Section: Accelerating Rate Calorimetry (Arc)mentioning

confidence: 99%

Thermal hazard assessment of nitrobenzene/dinitrobenzene mixtures

Badeen

Turcotte

Hobenshield

et al. 2011

Journal of Hazardous Materials

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“…Both of these unique features bring challenges in fitting the kinetic parameters of decomposition reactions from ARC results, especially when additional testing is not feasible. Reliable and accurate kinetic modeling is important since it is often used to simulate different scenarios for process safety evaluation or even used for sizing of relief venting. , As an example, vent sizing based on such an ARC result that yields inaccurate kinetic parameters might either put property in danger by undersizing the vent or waste money by oversizing the vent.…”

Section: Introductionmentioning

confidence: 99%

Heat Loss in Accelerating Rate Calorimetry Analysis and Thermal Lag for High Self-Heat Rates

Sheng

Valco

Tucker

2020

Org. Process Res. Dev.

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Accelerating rate calorimetry (ARC) is a common tool used in thermal stability evaluation of hazardous materials to provide self-heat rate and pressure data that are used to model the kinetics of a reaction and even calculate relief vent sizing. The ARC accomplishes a conservative approach by maintaining adiabatic conditions. However, an issue with ARC instrument heating occurs when a reaction with a high self-heat rate is analyzed that results in nonadiabatic conditions and a "thermal lag". Testing was conducted to determine the self-heat rate threshold for the ARC instrument and to better understand telltale features that occur during analysis of samples with high self-heat rates. The results indicate that while the oven cannot maintain adiabatic conditions, the convective heat loss from the sample container to the ARC oven does not have a significant effect on either the measured self-heat rate or the calculated overall heat of reaction. However, the conductive heat loss from the sample container to the connection fitting does, causing the total heat measured in ARC analysis to be lower by 16% for an adiabatic ARC test, 33% for a nonadiabatic ARC test, and ∼20% for a typical ARC test in comparison with DSC measurements. A corrected phi estimation is proposed with a correction factor to take into consideration the conductive heat loss to address this issue. In addition, the thermal lag caused by the ARC temperature measurement does create a significant difference between the measured peak pressure rate and peak self-heat rate occurrences. Analysis of the results showed that a simple linear correction can be applied to high self-heat rate results for liquid samples, while the pressure rate is still increasing, to correct for these peak rate differences. The pressure rate after correction matches the self-heat rate and better agrees with the prediction from kinetic modeling. Such corrections can be applied to solid samples, where there is an additional thermal lag due to resistance to heat transfer in the solid sample itself. Accounting for the thermal lag in reactions with high self-heat rates is important when modeling of the data is used for kinetic parameters and especially for relief vent sizing.

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“…23 The establishment of such kinetic model for an adiabatic reactor is scarce in the literature. 24,25 A comparison then is done between the values of TMR ad (T p ), T D24 , and T D8 at different process temperatures obtained from the intrinsic kinetic model and the zero-order kinetic model.…”

Section: Introductionmentioning

confidence: 99%

“…A kinetic model was built to estimate the intrinsic kinetic parameters based on the work of Perez-Benito . The establishment of such kinetic model for an adiabatic reactor is scarce in the literature. , A comparison then is done between the values of TMR ad ( T p ), T D24 , and T D8 at different process temperatures obtained from the intrinsic kinetic model and the zero-order kinetic model.…”

Section: Introductionmentioning

confidence: 99%

“…Different calorimeters can be used to determine these safety parameters: accelerating rate calorimeters (ARC), ,,, vent sizing package (VSP), − Phi-Tech II, , differential scanning calorimetry, ,− , or the Advanced Reactive System Screening Tool (ARSST). ,,− Experiments performed with this calorimeter can be done under adiabatic or near-adiabatic conditions with a low Φ-factor. , …”

Section: Introductionmentioning

confidence: 99%

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Zero-Order Versus Intrinsic Kinetics for the Determination of the Time to Maximum Rate under Adiabatic Conditions (TMR_ad): Application to the Decomposition of Hydrogen Peroxide

Vernières‐Hassimi

Dakkoune

Abdelouahed

et al. 2017

Ind. Eng. Chem. Res.

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The thermal safety of chemical processes requires knowledge of the safety parameters that quantify the probability, such as time to maximum rate under adiabatic conditions (TMR ad ), and the severity, such as adiabatic temperature rise under adiabatic conditions (ΔT ad ). The zero-order approximation is used to ease the determination of TMR ad values at different process temperatures; but how can one be sure that this approximation is acceptable, compared to the use of an intrinsic kinetic model? In the literature, there are no such studies that compare the values of TMR ad by using zero-order and intrinsic kinetic models. For that, decomposition of hydrogen peroxide in the presence (and in the absence) of copper sulfate was studied in an advanced reactive system screening tool (ARSST) unit. This calorimeter operates under near-adiabatic conditions, based on heat loss compensation principle, and by using a background heating rate (β). In a first stage, a kinetic model was built to estimate the intrinsic kinetic constants. Then, a comparison between the values of TMR ad from the zero-order and the intrinsic kinetic model was performed. It was found that the difference of TMR ad values obtained by these two models can be significant. The influence of β and reactant concentrations were found to play an important role in this difference. As good practice, in the case of missing kinetic and thermodynamic data, a user should test different background heating rates to verify their influence on TMR ad values obtained from the zero-order model.

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A general kinetic model framework for the interpretation of adiabatic calorimeter rate data

Cited by 15 publications

References 12 publications

Thermal hazard assessment of nitrobenzene/dinitrobenzene mixtures

Thermal hazard assessment of nitrobenzene/dinitrobenzene mixtures

Heat Loss in Accelerating Rate Calorimetry Analysis and Thermal Lag for High Self-Heat Rates

Zero-Order Versus Intrinsic Kinetics for the Determination of the Time to Maximum Rate under Adiabatic Conditions (TMR_ad): Application to the Decomposition of Hydrogen Peroxide

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A general kinetic model framework for the interpretation of adiabatic calorimeter rate data

Cited by 15 publications

References 12 publications

Thermal hazard assessment of nitrobenzene/dinitrobenzene mixtures

Thermal hazard assessment of nitrobenzene/dinitrobenzene mixtures

Heat Loss in Accelerating Rate Calorimetry Analysis and Thermal Lag for High Self-Heat Rates

Zero-Order Versus Intrinsic Kinetics for the Determination of the Time to Maximum Rate under Adiabatic Conditions (TMRad): Application to the Decomposition of Hydrogen Peroxide

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Zero-Order Versus Intrinsic Kinetics for the Determination of the Time to Maximum Rate under Adiabatic Conditions (TMR_ad): Application to the Decomposition of Hydrogen Peroxide