Untersuchungen über die Bildung von Persäuren aus organischen Säuren und Hydroperoxyd

D’Ans, J.; Frey, W.

doi:10.1002/zaac.19130840114

Cited by 25 publications

(13 citation statements)

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“…Peroxyformic acid is less stable than peroxyacetic acid. [47][48][49][50][51] During formic acid perhydrolysis reaction, PFA decomposition reactions occur consecutively with the synthesis. 51 The use of peroxyformic acid to epoxidize vegetable oils unsaturation has been treated in different articles.…”

Section: Introductionmentioning

confidence: 99%

Kinetic modeling strategy for an exothermic multiphase reactor system: Application to vegetable oils epoxidation using Prileschajew method

et al. 2015

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Epoxidation of cottonseed oil by peroxyformic acid (PFA) was studied in a semibatch calorimeter. This liquid-liquid reaction system is composed of different exothermic steps. Thus, a kinetic modeling strategy to diminish the number of parameters to estimate was developed by investigating each reaction system: PFA synthesis and decomposition, ringopening and epoxidation. A thermal study was conducted by determining heat capacity of the different organic species, and by analyzing the evolution of global heat-transfer coefficient with the reaction extent. The epoxidation reaction was performed in a semibatch reactor under isoperibolic mode within an initial temperature range of 50-708C, an organic phase of 30-34 wt %, a formic acid molar flow rate of 0.02-0.05 mol/min and an addition time of 25-50 min. The interfacial mass transfer was supposed to be faster than the intrinsic reaction kinetics suppressing the use of mass transfer correlation. Nonlinear regression was used to estimate the kinetic and thermal parameters. The kinetic parameters of epoxidation of the three different fatty acids, namely oleic, linoleic, and its intermediate were estimated. The reaction enthalpy of epoxidation was estimated to 2230 6 3.8 kJ/mol, and the reaction enthalpy of ring-opening was measured to be 290 kJ/mol by Tian-Calvet calorimeter.Kinetic modeling of vegetable oils epoxidation by peroxycarboxylic acids formed in situ in batch and semibatch reactor system has been described by several research groups. This system is complex due to the presence of several consecutive steps. Different approaches have been done such as:Taking into account mass transfer parameters using different correlations or by estimating them, this model is called two-phase kinetic model. Frequently, only carboxylic and peroxycarboxylic acids mass-transfer coefficients were taken into account. [24][25][26] Pseudohomogeneous model by assuming fast mass transfer compared to reaction kinetics, this leads to a simplification of the mass balance equations. [27][28][29][30][31][32] Establishing the mass balance only on the organic phase and assuming steady-state approach on peroxycarboxylic acids formation. 13,[33][34][35][36][37][38][39][40] The advantage of that approach is that graphical method can be used to determine epoxidation rate constants, but one neglects ring-opening reaction. This model is called homogeneous model.Some authors have focused their study only on the ringopening reactions system in batch or semibatch reactor. One can distinguish the two following approaches:Only considering the organic phase and using a pseudofirst-order approach. 41-43 Figure 1. Simplified mechanism of the Prileschajew oxidation of vegetable oils.

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Section: Introductionmentioning

confidence: 99%

Kinetic modeling strategy for an exothermic multiphase reactor system: Application to vegetable oils epoxidation using Prileschajew method

et al. 2015

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“…7-11 [23][24][25][26][27] ), and fluorescence ( 28 ) detection. Titration methods imply hydrogen peroxide titration followed by a iodometric determination of the peroxycarboxylic acid concentration 17,18 or a direct iodometric determination under acidic conditions. 19 All chromatography methods are limited in throughput and detect peroxycarboxylic acid formation directly in chromatograms ( …”

Section: Introductionmentioning

confidence: 99%

“…In general, peroxycarboxylic acids are determined by titration 438464J BXXXX10.1177/1087057112438464Desp otovic et alJournal of Biomolecular Screening 1 RWTH Aachen University, Worringerweg, Aachen, Germany 797 methods (Table 1: no. 1-3 [17][18][19] ), chromatography methods (Table 1: no. 4-6 [20][21][22] ), absorbance (Table 1: no.…”

Section: Introductionmentioning

confidence: 99%

“…12 28 ) detection. Titration methods imply hydrogen peroxide titration followed by a iodometric determination of the peroxycarboxylic acid concentration 17,18 or a direct iodometric determination under acidic conditions. 19 All chromatography methods are limited in throughput and detect peroxycarboxylic acid formation directly in chromatograms ( , followed by iodometric determination of peroxycarboxylic acids (iodide reacts with peroxycarboxylic acids, forming iodine; generated iodine is titrated with thiosulfate solution).…”

Section: Introductionmentioning

confidence: 99%

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Fluorescent Assay for Directed Evolution of Perhydrolases

et al. 2012

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Directed evolution offers opportunities to improve promiscuous activities of hydrolases in rounds of diversity generation and high-throughput screening. In this article, we developed and validated a screening platform to improve the perhydrolytic activity of proteases and likely other hydrolases (e.g., lipases or esterases). Key was the development of a highly sensitive fluorescent assay (sensitivity in the µM range) based on 3-carboxy-7-hydroxycoumarin (HCC) formation. HCC is released through an hypobromite-mediated oxidation of 7-(4′-aminophenoxy)-3-carboxycoumarin (APCC), which enables for the first time a continuous measurement of peroxycarboxylic acid formation with a standard deviation of 11% in microtiter plates with a wide pH range window (5-9). As example, subtilisin Carlsberg was subjected to site saturation mutagenesis at position G165, yielding a variant T58A/G165L/L216W with 5.4-fold increased k cat for perhydrolytic activity compared with wild type.

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“…Analysis of the reagent indicated 37-42% peracetic acid depending upon the time of storage. Three methods of analysis were tested (2)(3)(4). A modification of the method of Greenspan gave the most satisfactory results which had the highest precision.…”

Section: Methodsmentioning

confidence: 99%

A two‐phase second‐order reaction: Kinetics of epoxidation of methyl 12,13‐epoxyoleate

Rothbart¹,

Snook²,

Rusling³

et al. 1969

J Americ Oil Chem Soc

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The kinetics of epoxidation of methyl 12,13epoxyoleate with peracetic acid have been studied. Chloroform and benzene solvents were used at 25, 30 and 40 C. A second-order equation was developed to determine the rate constants in this two-phase system. Variation of the relative phase volumes provides a convenient method for controlling the rate of reaction. Differences in the ±S ° of activation for the formation of the two isomeric diepoxides were greater than 1 eu in all cases. If the usual integrated second-order equation is used, the rate constant will be in error. The magnitude of the error is related to the partition coefficient of the species distributed between the phases and the volume ratios of the two phases. Other errors in the rate constant were determined by expressing K as a function of time, temperature and the concentration of reactants at any time in the reaction. The total differential of K divided by K, to get the relative error, was evaluated at various reaction times. The choice of best times for the determination of the rate constant was dictated from the error analysis.

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Untersuchungen über die Bildung von Persäuren aus organischen Säuren und Hydroperoxyd

Abstract: 1. Es wurde die Bildung der Perameisensäure, Peressigsäure, Perpropionsäure und Perbuttersäure aus den entsprechenden Säuren H2O2 ohne und mit Katalysatoren verfolgt und die sich einstellenden Gleichgewichte bestimmt.

Cited by 25 publications

References 1 publication

Kinetic modeling strategy for an exothermic multiphase reactor system: Application to vegetable oils epoxidation using Prileschajew method

Kinetic modeling strategy for an exothermic multiphase reactor system: Application to vegetable oils epoxidation using Prileschajew method

Fluorescent Assay for Directed Evolution of Perhydrolases

A two‐phase second‐order reaction: Kinetics of epoxidation of methyl 12,13‐epoxyoleate

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