Decomposition Of Peracetic Acid Research Articles

Modelling of organic liquid-phase decomposition reactions through gas-phase product analysis: Model systems and peracetic acid

A new method for modelling of liquid-phase decomposition reactions was developed. The method is based on rapid on-line mass spectrometric analysis of liberated products in gas phase. The experimental set-up and the generalized modelling principles were introduced. The approach was demonstrated with first and zero order as well as for complex decomposition kinetics (decomposition of peracetic acid). The interaction of decomposition kinetics and mass-transfer effects was illustrated with theoretical and real reaction conditions. The approach is generally applicable to any liquid-phase decomposition, provided that gaseous products can be quantitatively analyzed.

Mechanism of decomposition of peracetic acid by manganese ions and diethylenetriaminepentaacetic acid (DTPA)

Abstract The decomposition mechanism of peracetic acid by free Mn2+ ions and by Mn2+-diethylenetriaminepentaacetic acid complexes was studied by UV/Vis, electrospray ionization-time of flight-mass spectrometry (ESI-TOF-MS), electron spin resonance (ESR), and Raman spectroscopy. The experimental results demonstrate that a number of different oxidation states of manganese are involved in the decomposition reaction. Furthermore, the kinetics observed show oscillatory features that are characteristic of autocatalytic processes. Radical pathways were found to play a negligible role in the reaction. Based on the experimental observations, an overall reaction scheme for the decomposition process is proposed.

Disinfection of wastewater with peracetic acid: a review

Peracetic acid is a strong disinfectant with a wide spectrum of antimicrobial activity. Due to its bactericidal, virucidal, fungicidal, and sporicidal effectiveness as demonstrated in various industries, the use of peracetic acid as a disinfectant for wastewater effluents has been drawing more attention in recent years. The desirable attributes of peracetic acid for wastewater disinfection are the ease of implementing treatment (without the need for expensive capital investment), broad spectrum of activity even in the presence of heterogeneous organic matter, absence of persistent toxic or mutagenic residuals or by-products, no quenching requirement (i.e., no dechlorination), small dependence on pH, short contact time, and effectiveness for primary and secondary effluents. Major disadvantages associated with peracetic acid disinfection are the increases of organic content in the effluent due to acetic acid (AA) and thus in the potential microbial regrowth (acetic acid is already present in the mixture and is also formed after peracetic acid decomposition). Another drawback to the use of peracetic acid is its high cost, which is partly due to limited production capacity worldwide. However, if the demand for peracetic acid increases, especially from the wastewater industry, the future mass production capacity might also be increased, thus lowering the cost. In such a case, in addition to having environmental advantages, peracetic acid may also become cost-competitive with chlorine.

The influence of temperature on the decomposition kinetics of peracetic acid in solutions

Peracetic acid is a powerful sanitizer that has only recently been introduced in the Brazilian food industry. The main disadvantage of this sanitizer is its decomposition rate. The main purpose of this paper is to present results obtained in experiments carried out to study the decomposition kinetics of peracetic acid in aqueous solutions at 25, 35, 40 and 45 °C. The decompositon of peracetic acid is a first-order reaction. The decomposition rate constants are between 1.71x10-3 h -1 for 25 °C and 9.64x10-3 h-1 for 45 °C. The decomposition rate constant is affected by temperature according to the Arrhenius equation, and the activation energy for the decomposition of peracetic acid in aqueous solutions prepared from the commercial formulation used in this work is 66.20 kJ/mol.

Decomposition of peracetic acid catalyzed by cobalt(II) and vanadium(V)

Peracetic acid (Pa) is now being used for totally chlorine-free delignification and bleaching of wood pulps. During the process, metals desorb from the pulp fibers into the aqueous solution. Of the relevant metals in bleaching systems, cobalt(II) and vanadium(V) are the most potent in wastefully decomposing Pa to O2. In the present study, radical scavenging by N,N'-(5-nitro-1,3-phenylene)-bisglutaramide (GAMID) indicates that free-radical mechanisms are operative. Kinetic data support a free-radical decomposition mechanism previously described for Co(II). A similar type of mechanism, involving VO(OH)2(aq) and VO(OH)3(aq), is postulated to partially explain catalysis by vanadium. Resume : L'acide peracetique (aP) est maintenant utilise pour la delignification et le blanchiment de pulpes de bois en absence totale de chlore. Durant ce processus, les metaux se desorbent des fibres de la pulpe et se retrouvent dans la solution aqueuse. De tous les metaux les plus importants pour les systemes de blanchiment, le cobalt(II) et le vanadium(V) sont les plus puissants pour la decomposition inutile de l'aP en O2. Dans le present travail, des piegeages de radicaux a l'aide de N,N'-(5-nitro-1,3-phenylene)-bisglutaramide (GAMID) indiquent que des mecanismes radicalaires sont impliques. Les donnees cinetiques sont en accord avec le mecanisme de decomposition radicalaire decrit anterieurement pour le Co(II). Pour expliquer la catalyse par le vanadium, on suggere un mecanisme semblable impliquant du VO(OH)2(aq) et VO(OH)3(aq). Mots cles : acide peracetique, acide peroxymonosulfurique, metaux de transition, radicaux libres, radical acetoxy, radi- cal peracetoxy. (Traduit par la redaction) Zhang et al. 1069

Kinetics of the peracetic acid decomposition: Part II: pH effect and alkaline hydrolysis

AbstractThe effect of pH on the decomposition of peracetic acid in an aqueous solution was studied. It was found that three potential reactions, namely i) the spontaneous decomposition, ii) the hydrolysis and iii) the transition metal catalysed decomposition, are responsible for the consumption of peracetic acid. The spontaneous decomposition reaches its maximum at pH 8.2, while both the hydrolysis and metal ion catalysed decomposition increase as the pH increases. At pH 10.5 and higher, the hydrolysis becomes dominant when the metal ion catalysed decomposition is minimized by the addition of DTMPA. The kinetics of the peracetic acid hydrolysis was developed, which can very well predict the development of peracetic acid and hydrogen peroxide during the decomposition reaction.

Kinetics of peracetic acid decomposition: Part I: Spontaneous decomposition at typical pulp bleaching conditions

AbstractPeracetic acid may become one of alternative non‐chlorine bleaching chemicals in the production of fully bleached chemical pulps. In this paper, the stability of peracetic acid was studied in an aqueous solution under conditions most likely encountered in the industrial processes. It was found that three potential reactions, namely i) the spontaneous decomposition, ii) the hydrolysis and iii) the transition metal catalyzed decomposition, are responsible for the consumption of peracetic acid. Furthermore, the kinetics of the spontaneous decomposition was developed. It was found that the reaction follows a second‐order kinetics with the maximum rate at pH 8.2, which is the pKa of peracetic acid. Finally, the developed kinetic equation can describe very well the experimental results obtained in this study as well as the earlier data from Koubek (1964).

2,2'-Bipyridine Catalyzed Bleaching of Cotton Fibers with Peracetic Acid Part III: Effect of Chain Length of Alkyl Sulfate Surfactants

Peracetic acid can be catalyzed to bleach cotton fibers at 30°C by incorporating 2,2'-bipyridine and an alkyl sulfate surfactant in the bleach solution. The 2,2'-bipyridine is sorbed from solution and forms the tris-2,2'-bipyridine ferrous ion trischelate with ferrous ions in the fibers, and it is the trischelate that catalyzes bleaching. Alkyl sulfate surfactants reduce the rate of decomposition of the peracid by forming an association compound with the trischelate. We have investigated the effect of the chain length of alkyl sulfate surfactants on the interaction of the surfactant with the trischelate using sodium octyl, decyl, dodecyl, and tetradecyl sulfate. We report the effect on the rate of decomposition of peracetic acid in the presence of the trischelate, the visible and ultraviolet spectra of the trischelate, and bleaching of cotton. The results indicate that interaction of the surfactant molecules with the trischelate is hydrophobic in nature.

2,2î-Bipyridine Catalyzed Bleaching of Cotton Fibers with Peracetic Acid

Peracetic acid can be catalyzed to bleach cotton fibers at temperatures as low as 30°C by incorporating 2,2î-bipyridine in the bleach solution. Treatment of the fibers with HCl prior to bleaching reduces bleaching effectiveness by removing trace transition metal ions from the fibers. Sorption of individual ions (Cr+3 Mn+2, Fe+2, Fe+3 Co+2, Ni+2, Cu+2, and Zn+2) by HCl treated cotton fibers prior to bleaching indicates that the ferrous ion produces the greatest catalytic effect, and it is only effective when the metal ion is in the fiber as opposed to in solution. Ferrous ions in the fibers sorb 2,2î-bipyridine from solution to form the tris-2,2î-bipyridine ferrous ion complex that is associated with the fibers, and it is the trischelate associated with the fibers that catalyzes bleaching. The effects of pH, temperature, and concentrations of 2,2î-bipyridine, sodium lauryl sulfate, and transition metal ions (in the fibers and in solution) on bleaching effectiveness and peracetic acid decomposition have been studied, and a bleaching mechanism is proposed.

2,2î-Bipyridine Catalyzed Bleaching of Cotton Fibers with Peracetic Acid

Peracetic acid can be catalyzed to bleach cotton fibers at temperatures as low as 30°C by incorporating 2,2î-bipyridine in the bleach solution if the appropriate concentration of ferrous ions is present in the cotton fibers. The tris-2,2î-bipyridine ferrous ion complex (trischelate) is the catalytically active species, and sodium lauryl sulfate functions as a stabilizer for the peracid in the presence of the trischelate. The effects of pH, temperature, and concentrations of 2,2î-bipyridine, sodium lauryl sulfate, and ferrous ions on the kinetics and mechanism of peracetic acid decomposition have been investigated. Peracetic acid decomposition in the bleach solution is due mainly to alkaline hydrolysis without added ferrous ions and catalysis by the trischelate complex in solutions containing added ferrous ions. Overall decomposition follows the rate expression where k1 is the specific rate constant for alkaline hydrolysis and k3 is the specific rate constant for catalytic decomposition by the trischelate in the presence of sodium lauryl sulfate.

アセト酢酸エチルの酸触媒過酢酸酸化の速度論的研究

The oxidation of ethyl acetoacetate with peracetic acid in the presence of sulfuric acid in acetic acid has been followed by iodometry. The rate satisfied the following equation; -dCPAA/dt={kd+ktCH2SO4}CPAA+{k2+k2'CH2SO4}CPAACEAA. The first and the second terms correspond to the decomposition of peracetic acid and the acid-catalyzed reversible transformation to acetyl peroxide, while the third and the fourth terms represent the neutral and the acid-catalyzed oxidation of ethyl acetoacetate, respectively, with peracetic acid. Hammett plots of the third and the fourth terms for the oxidation of substituted phenyl acetoacetates gave straight lines with slopes of -0.91 and -1.36, respectively. As products, acetic and oxalic acids, acetaldehyde, ethanol, ethyl glyoxylate, ethyl glycolate, ethyl acetate and diethyl oxalate were confirmed by means of gaschromatography and/or thin layer chromatography. No Baeyer-Villiger reaction product was formed at all. From these findings, a mechanisms is postulated and discussed which involves an epoxidation of enol form of ethyl acetoacetate, as the rate determining step, by an attack of the positive oxygen atom of peracetic acid and/or of protonated one.

Decomposition of peracetic acid catalyzed by vanadium complexes

1. Peractic acid in acetic acid solutions of ammonium vanadate decomposes with the predominant formation of O2 and small amounts of CO2, the yield of which increases with increasing temperature and peracetic acid concentration. 2. Both these reactions proceed without the formation of free radicals in amounts detectable by ESR spectroscopy. 3. The rate of oxygen release under conditions in which the formation of CO2 is insignificant obeys a kinetic equation indicating the intermediate formation of a complex between V5+ ions and peracetic acid and the slow conversion of this complex into the observed products.

Photoinduced decomposition of peracetic acid in xylenes. Orientation in aromatic substitution of methyl and hydroxyl radicals

Photoinduced decomposition of peracetic acid in xylenes. Orientation in aromatic substitution of methyl and hydroxyl radicals

Photoinduced decomposition of peracetic acid in ethylbenzene

Photoinduced decomposition of peracetic acid in ethylbenzene

Photoinduced decomposition of peracetic acid in benzene

Photoinduced decomposition of peracetic acid in benzene

Photoinduced decomposition of peracetic acid in toluene

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPhotoinduced decomposition of peracetic acid in tolueneYoshiro Ogata and Kohtaro TomizawaCite this: J. Org. Chem. 1978, 43, 2, 261–267Publication Date (Print):January 1, 1978Publication History Published online1 May 2002Published inissue 1 January 1978https://doi.org/10.1021/jo00396a018RIGHTS & PERMISSIONSArticle Views105Altmetric-Citations8LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (753 KB) Get e-Alerts Get e-Alerts

The use of ESR measurements to study the role of the surface in acetaldehyde oxidation

The effect of vessel surface on the kinetics and mechanism of acetaldehyde oxidation has been examined by combining low temperature trapping of radicals with ESR measurements over a wide range of temperature (150°–375°C). In salt-coated vessels (e.g., KCl and KBr) at low temperatures, degenerate branching arises from the heterogeneous decomposition of peracetic acid and the transfer of free radical chain centres back into the gas phase. The ESR measurements for the heterogeneous decomposition of peracetic acid show that as the concentration of peracetic acid falls there is a corresponding increase in the concentration of acetylperoxy radicals. Above 300°C, however, the destruction of both peracetic acid and acetylperoxy radicals is rapid on the salt coatings so that the rate of oxidation in a boric acid-coated vessel becomes faster than that in the salt-coated vessels, whereas at the lower temperatures the faster rate occurs in the salt-coated vessels.

Radical-induced decomposition of peracetic acid

Radical-induced decomposition of peracetic acid

ChemInform Abstract: RADICALS GENERATED BY THE HETEROGENEOUS DECOMPOSITION OF PERACETIC ACID STUDIED BY ELECTRON SPIN RESONANCE SPECTROSCOPY

Chemischer InformationsdienstVolume 6, Issue 24 Preparative Organic Chemistry ChemInform Abstract: RADICALS GENERATED BY THE HETEROGENEOUS DECOMPOSITION OF PERACETIC ACID STUDIED BY ELECTRON SPIN RESONANCE SPECTROSCOPY AZAM B. NALBANDYAN, AZAM B. NALBANDYANSearch for more papers by this authorELIA A. OGANESSYAN, ELIA A. OGANESSYANSearch for more papers by this authorIRMA A. VARDANYAN, IRMA A. VARDANYANSearch for more papers by this authorJOHN F. GRIFFITHS, JOHN F. GRIFFITHSSearch for more papers by this author AZAM B. NALBANDYAN, AZAM B. NALBANDYANSearch for more papers by this authorELIA A. OGANESSYAN, ELIA A. OGANESSYANSearch for more papers by this authorIRMA A. VARDANYAN, IRMA A. VARDANYANSearch for more papers by this authorJOHN F. GRIFFITHS, JOHN F. GRIFFITHSSearch for more papers by this author First published: June 17, 1975 https://doi.org/10.1002/chin.197524142AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume6, Issue24June 17, 1975 RelatedInformation

Radicals generated by the heterogeneous decomposition of peracetic acid studied by electron spin resonance spectroscopy

Peracetic acid, a branching agent commonly associated with low temperature organic oxidations, is decomposed in flowing conditions over extensive surfaces coated with KCl, KBr or BaBr2 at temperatures in the range 300–560 K.Free radicals generated from the surface decomposition are pumped, at low pressure, to a cold finger within the cavity of an e.s.r. spectrometer, where thay are trapped in a solid matrix. Electron spin resonance spectra become more intense as radicals accumulate on the finger. Greater yields accumulate as the temperature of each surface is increased: these yields correspond to increasing extents of decomposition of peracetic acid within its residence time at each surface. Surface activity leading to generation of radicals varies roughly in the concentration ratios KCl : KBr : BaBr2= 3 : 2 : 1. Beyond the temperature at which all peracetic acid is decomposed, the radical yields fall, indicating that some radicals are removed by surface termination.Evidence for the surface generation of free radicals suggests that surface reactions may contribute to chain branching in some organic oxidations.