Moving from postdictive to predictive kinetics in reaction engineering

Green, William

doi:10.1002/aic.17059

Cited by 35 publications

(32 citation statements)

References 103 publications

(162 reference statements)

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“…Chemical kinetic mechanisms involving complex reactions of numerous intermediates often rely on first-principles calculations as the main source of thermodynamic and rate parameters, especially when the number of important reactions in the real system greatly exceeds the number of available experimental data. , The Automated Rate Calculator (ARC) software automates the process of calculating parameters relevant for chemical kinetic modeling. ARC uses the cheminformatics modules RDKit and OpenBabel , to generate random 3D coordinate conformer guesses for species from the respective 2D structures used in RMG, and has a torsion mapping algorithm to deduce likely lowest energy conformers.…”

Section: Methodsmentioning

confidence: 99%

Section: Automationmentioning

confidence: 99%

See 1 more Smart Citation

Kinetic Modeling of API Oxidation: (1) The AIBN/H₂O/CH₃OH Radical “Soup”

Dana

Ranasinghe

et al. 2021

Mol. Pharmaceutics

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While different flavors of API stress testing systems have been used in experimental investigations for decades, the detailed kinetics of such systems as well as the chemical composition of prominent reactive species, specifically reactive oxygen species, are unknown.As a first step toward understanding and modeling API oxidation in stress testing, we investigated a typical radical "soup" solution an API is subject to during stress testing.Here we applied ab-initio electronic structure calculations to automatically generate and refine a detailed chemical kinetics model, taking a fresh look at API oxidation.We generated a detailed kinetic model for a representative azobisisobutyronitrile (AIBN)/H 2 O/CH 3 OH stress-testing system with varied co-solvent ratio (50%/50% --99.5%/0.5% vol. water/methanol) and for representative pH values (4--10) at 40oC stirred and open to the atmosphere.At acidic conditions hydroxymethyl alkoxyl is the dominant alkoxyl radical, and at basic conditions, for most studied initial methanol concentrations, cyanoisopropyl alkoxyl becomes the dominant alkoxyl radical, albeit at an overall lower concentration.At acidic conditions the levels of cyanoisopropyl peroxyl, hydroxymethyl peroxyl, and hydroperoxyl radicals are relatively high and comparable, while at both neutral and basic pH conditions, superoxide becomes the prominent radical in the system.The present work reveals the prominent species in a common model API stress testing system at various co-solvent and pH conditions, sets the stage for an in-depth quantitative API kinetic study, and demonstrates usage of novel software tools for automated chemical kinetic model generation and ab-initio refinement. File list (2) download file view on ChemRxiv 2021.04.01 a The Soup.pdf (5.01 MiB) download file view on ChemRxiv 2021.01.29 a Soup SI.pdf (1.02 MiB)

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Section: Methodsmentioning

confidence: 99%

Section: Automationmentioning

confidence: 99%

Kinetic Modeling of API Oxidation: (1) The AIBN/H₂O/CH₃OH Radical “Soup”

Dana

Ranasinghe

et al. 2021

Mol. Pharmaceutics

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“…These results point to the a fundamental flaw of this general scheme of "postdictive" 59 of model fitting, where the complexity and coupling of the chemical system make direct measurement or inferral of the relevant pathways and rates extremely difficult.…”

Section: Additional Reactionsmentioning

confidence: 99%

The Impact of NOx Addition on the Ignition Behavior of N-Pentane

Fuller¹,

Morsch²,

Goldsmith³

et al. 2021

Preprint

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This article details new ignition delay time experiments carried out on blends of n-pentane and either NO or NO2 in the rapid compression machine facility at RWTH Aachen University. Further, a new chemical kinetic mechanism is developed which is able to well-reproduce the experiments and significantly improve over recently published mechanisms. This work has particular value for publication as it adopts a systematic, class-based approach to mechanism development for interactions with nitrogenated species.

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“…Chemical kinetic mechanisms involving complex reactions of numerous intermediates often rely on firstprinciples calculations as the main source of thermodynamic and rate parameters, especially when the number of important reactions in the real system greatly exceeds the number of available experimental data. [22,64] The Automated Rate Calculator (ARC) software [65] automates the process of calculating parameters relevant for chemical kinetic modeling. ARC uses the cheminformatics modules RDKit [66] and OpenBabel [67,68] to generate random 3D coordinate conformer guesses for species from the respective 2D structure, and has a mapping algorithm to deduce likely lowest energy conformers.…”

Section: Automationmentioning

confidence: 99%

Kinetic Modeling of API Oxidation: 1. The AIBN/H2O/CH3OH Radical "Soup"

Dana

Wu²,

Ranasinghe³

et al. 2021

Preprint

Self Cite

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While different flavors of API stress testing systems have been used in experimental investigations for decades, the detailed kinetics of such systems as well as the chemical composition of prominent reactive species, specifically reactive oxygen species, are unknown. As a first step toward understanding and modeling API oxidation in stress testing, we investigated a typical radical "soup" solution an API is subject to during stress testing. Here we applied ab-initio electronic structure calculations to automatically generate and refine a detailed chemical kinetics model, taking a fresh look at API oxidation. We generated a detailed kinetic model for a representative azobisisobutyronitrile (AIBN)/H2O/CH3OH stress-testing system with varied co-solvent ratio (50%/50% -- 99.5%/0.5% vol. water/methanol) and for representative pH values (4--10) at 40oC stirred and open to the atmosphere. At acidic conditions hydroxymethyl alkoxyl is the dominant alkoxyl radical, and at basic conditions, for most studied initial methanol concentrations, cyanoisopropyl alkoxyl becomes the dominant alkoxyl radical, albeit at an overall lower concentration. At acidic conditions the levels of cyanoisopropyl peroxyl, hydroxymethyl peroxyl, and hydroperoxyl radicals are relatively high and comparable, while at both neutral and basic pH conditions, superoxide becomes the prominent radical in the system. The present work reveals the prominent species in a common model API stress testing system at various co-solvent and pH conditions, sets the stage for an in-depth quantitative API kinetic study, and demonstrates usage of novel software tools for automated chemical kinetic model generation and ab-initio refinement.

show abstract

Moving from postdictive to predictive kinetics in reaction engineering

Cited by 35 publications

References 103 publications

Kinetic Modeling of API Oxidation: (1) The AIBN/H₂O/CH₃OH Radical “Soup”

Kinetic Modeling of API Oxidation: (1) The AIBN/H₂O/CH₃OH Radical “Soup”

The Impact of NOx Addition on the Ignition Behavior of N-Pentane

Kinetic Modeling of API Oxidation: 1. The AIBN/H2O/CH3OH Radical "Soup"

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Moving from postdictive to predictive kinetics in reaction engineering

Cited by 35 publications

References 103 publications

Kinetic Modeling of API Oxidation: (1) The AIBN/H2O/CH3OH Radical “Soup”

Kinetic Modeling of API Oxidation: (1) The AIBN/H2O/CH3OH Radical “Soup”

The Impact of NOx Addition on the Ignition Behavior of N-Pentane

Kinetic Modeling of API Oxidation: 1. The AIBN/H2O/CH3OH Radical "Soup"

Contact Info

Product

Resources

About

Kinetic Modeling of API Oxidation: (1) The AIBN/H₂O/CH₃OH Radical “Soup”

Kinetic Modeling of API Oxidation: (1) The AIBN/H₂O/CH₃OH Radical “Soup”