Analysis of Asymmetric Sigmoid Kinetic Curves of Autocatalytic Reactions

Fazekáš, Tomáš; Nagy, Arpád; Treindl, Ľ.

doi:10.1135/cccc19930775

Cited by 3 publications

(3 citation statements)

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“…10 Despite the practical inconvenience of dye photofading, there have been relatively few detailed studies describing the kinetics of lightinduced degradation under controlled conditions. 11−16 Such studies might be complicated by self-catalysis 17 and invariably require multiple numbers of photons for complete bleaching of an individual molecule. Mechanistic studies are especially difficult in those cases where the quantum yields are very low.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Indeed, photodegradation can be a serious limitation for certain classes of dye, although engineering (e.g., the omission of molecular oxygen and introduction of screens or filters) can provide important levels of relief . Despite the practical inconvenience of dye photofading, there have been relatively few detailed studies describing the kinetics of light-induced degradation under controlled conditions. − Such studies might be complicated by self-catalysis and invariably require multiple numbers of photons for complete bleaching of an individual molecule. Mechanistic studies are especially difficult in those cases where the quantum yields are very low.…”

Section: Introductionmentioning

confidence: 99%

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Effects of Temperature and Concentration on the Rate of Photobleaching of Erythrosine in Water

et al. 2017

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Erythrosine, a popular food dye, undergoes fast O-sensitive bleaching in water when subjected to visible light illumination. In dilute solution, erythrosine undergoes photobleaching via first-order kinetics, where the rate of bleaching depends critically on the rate of photon absorption and on the concentration of dissolved oxygen. Kinetic studies indicate that this inherent bleaching is augmented by self-catalysis at higher concentrations of erythrosine and on long exposure times. Under the conditions used, bleaching occurs by way of geminate attack of singlet molecular oxygen on the chromophore. Despite the complexity of the overall photobleaching process, the rate constants associated with both inherent and self-catalytic bleaching reactions follow Arrhenius-type behavior, allowing the activation parameters to be resolved. Bleaching remains reasonably efficient in the solid state, especially if the sample is damp, and provides a convenient means by which to construct a simple chemical actinometer.

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Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Effects of Temperature and Concentration on the Rate of Photobleaching of Erythrosine in Water

et al. 2017

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“…Thus, (a,b,M) reflect the physical reality of each aging mechanism, and these terms could be compared for similar batteries experiencing different aging conditions, and for different types of batteries experiencing identical aging conditions. Sigmoidal-based rate expressions such as Eqs.. (9a,b) and those below are well suited to describe the batch reaction kinetics that are observed in working batch reactors, where a near infinite variety of both hyperbolic and sigmoidal responses can be observed[42][43][44][45], and are feasible for interpretation within the MSM approach. Especially salient between MSM and batch reaction kinetics is the plateauing of the extent of forward reaction, which is a function of temperature and molar proportions of reactants [e.g.,42,43].…”

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confidence: 99%

Novel Method for Evaluation and Prediction of Capacity Loss Metrics in Li-Ion Electrochemical Cells

Gering

2017

Electrochimica Acta

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Practical methods and metrics are needed to assist battery development and end-user communities in the area of battery aging, in particular, understanding capacity loss in Li-ion cells. Tools are sought that offer both diagnostic and prognostic benefits, while minimizing the need for prolonged testing or undue commitment of tangible resources. Based on a chemical engineering batch reactor approach to cell aging, this work is a move in the direction to meet such needs. Capacity loss is interpreted by a combination of sigmoidal rate expressions, having physically-meaningful parameters, which cover chief mechanisms that affect loss of available lithium and loss of active host material. A lithium source term is also accommodated by the modeling approach. Development is shown to identify reversible and irreversible capacity loss contributions, as well as calculate molar-based terms for lithium and active sites, and how these change over time due to cell aging. The method is demonstrated on NCA/graphite cell chemistries, where conditions of cycle-life, calendar-life, and temperature are considered. The resultant capability adds value toward deepening our understanding of aging contributions that impact capacity, and provides a foundation for improving Li-ion cell design and management through diagnostic and predictive elements.

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An Autocatalytic Constant Sensitivity Detection System for Catalysts and Infectors

Ishihara¹,

Endo²,

Igarashi³

et al. 1995

Chemistry Letters

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Mathematical model calculation shows that the shape of the reactant concentration-time curves of autocatalytic reaction system at their inflection time is similar to each other even for different initial concentrations of catalysts. It should be of great value as a theoretically infinite sensitivity detection system for catalysts or its infectors. This model has been demonstrated by the use of oxidative destruction of cobalt complexes of 2,4-(2-pyridylazo)benzenediolate and phthalocyaninetetrasulfonate with peroxomonosulfate in aqueous phosphate buffer solution (pH 7) at 25 °C.

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Analysis of Asymmetric Sigmoid Kinetic Curves of Autocatalytic Reactions

Cited by 3 publications

References 0 publications

Effects of Temperature and Concentration on the Rate of Photobleaching of Erythrosine in Water

Effects of Temperature and Concentration on the Rate of Photobleaching of Erythrosine in Water

Novel Method for Evaluation and Prediction of Capacity Loss Metrics in Li-Ion Electrochemical Cells

An Autocatalytic Constant Sensitivity Detection System for Catalysts and Infectors

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