The Thermal Decomposition of Peracetic Acid in the Vapor Phase

Abstract

The thermal decompositioil of peracetic acid i11 a stream of toluene was studied over the temperature range 127-360" C . The main products of the reaction were C02, CHpCOOH, C2H8, C H I , H C H O , 0 2 , and traces of CO. Dibenzyl was also formed.The overall decomposition of peracetic acid was partly heterogeneous and was represented by the two parallel primary reactions(ii)The dissociation energy of the 0-0 bond in peracetic acid was estimated to be 30-34 kcal/mole. I N T R O D U C T I O NThe importance of hydroxyl radical reactions in oxidation processes of hydrocarbons is now widely accepted but very few studies have been made on the kinetics of the reactions between these radicals and different hydrocarbons. This is due in part to the lack of a suitable source of hydroxyl radicals. Several methods have been used to produce t h e radicals, e.g, electric discharge through water vapor (I), electron transfer reactions in aqueous solution (2), and the thermal and photochemical decomposition of hydrogen peroxide (3) and alkyl hydroperoxide (4), but all of these methods have many disadvantages. -I t was considered possible that peracetic acid might be a convenient source of hydroxyl radicals both in the gas phase and in solution, the radicals being formed by the sequence of reactionsIf the decomposition took place by this mechanism the rate of formation of hydroxyl radicals could readily be followed by measuring the rate of production of carbon dioxide.In the present study the mechanism of the decomposition of peracetic acid was investigated in the gas phase using the "toluene-carrier technique" (5). I t was also hoped that this study would lead to the evaluation of the 0-0 bond dissociation energy, D(CH,.C02--OH).The primary difficulty in the preparation of peracetic acid is the extremely explosive nature of the compound. This hazard can be minimized by preparing small quantities of about 1 g and by maintaining the compound in solution a t all times apart from two stages in its preparation.

Continuous Platform To Generate Nitroalkanes On-Demand (in Situ) Using Peracetic Acid-Mediated Oxidation in a PFA Pipes-in-Series Reactor

“…It was noted that in the PFA reactor fitted with a back pressure regulator large amounts of gas generated in a process would be trapped inside the reaction mixture, but could otherwise easily escape in a batch scenario with headspace. The literature also confirmed that peracetic acid can spontaneously decompose, generating oxygen 23 that might over-oxidize the reaction intermediates leading to increased amounts of benzoic acid. A test reaction conducted in a closed vessel (port connector) 24 with a limited amount of the overhead space supported this hypothesis as evidenced by an improved nitroalkane yield relative to the regular metal PFR.…”

Influence of Intramolecular Hydrogen Bonding on OH-Stretching Overtone Intensities and Band Positions in Peroxyacetic Acid

“…Peroxyacetic acid is known to be a potentially dangerous and explosive substance. 39,53 It can be generated by the reaction of hydrogen peroxide with acetic acid. The process is described by the following reaction scheme:…”

“…Peroxyacetic acid is known to be a potentially dangerous and explosive substance. , It can be generated by the reaction of hydrogen peroxide with acetic acid. The process is described by the following reaction scheme: CH 3 normalC ( O ) OH + normalH 2 normalO 2 ⇌ CH 3 normalC ( O ) OOH + normalH 2 normalO Both the forward and reverse reactions are fairly slow at room temperature, and a long time is necessary for equilibrium to be established .…”

Quantification of peroxynitric acid and peroxyacyl nitrates using an ethane-based thermal dissociation peroxy radical chemical amplification cavity ring-down spectrometer

“…The RO x (= OH + HO 2 + RO 2 ) radicals and the nitrogen oxides (NO x = NO + NO 2 ) are important trace constituents of the atmosphere that drive diverse processes such as the photochemical production of ozone (O 3 ) in the troposphere (Kirchner and Stockwell, 1996;Fleming et al, 2006), the catalytic destruction of O 3 in the stratosphere (Bates and Nicolet, 1950;Stenke and Grewe, 2005;Solomon, 1999;Portmann et al, 1999), and the chemistry of organic aerosol formation (Ziemann and Atkinson, 2012;Ehn et al, 2014;Crounse et al, 2013). In the troposphere, the concentrations of these species are frequently buffered by RO x and NO x reservoir species, of which peroxynitric acid (PNA, HO 2 NO 2 ), alkyl peroxy nitrates such as methyl peroxynitrate (CH 3 O 2 NO 2 , MPN), and peroxyacyl nitrates (PANs, RC(O)O 2 NO 2 ) are important examples (Singh et al, 1992;Roberts, 1990). Much insight into RO x and NO x chemistry has been gained by measuring the atmospheric abundances of these reservoirs.…”