A directly-dissociative stepwise reaction mechanism for gas-phase peroxyacetic acid

Keller, Bradley; Wojcik, Michael D.; Fletcher, T. Rick

doi:10.1016/j.jphotochem.2007.09.001

Cited by 14 publications

(16 citation statements)

References 54 publications

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“…As Table 1 shows, PAA has a reduction potential (Eh 0 ) of 1.0−1.96 V versus the standard hydrogen electrode (SHE), 2,74−77 higher than those of hydrogen peroxide (1.78 V), chlorine (1.48 V), chlorine dioxide (1.28 V), and ferrate(VI) (0.9−1.9 V) but lower than that of ozone (2.08 V). 4,8,78,79 Compared to acetic acid, PAA has a higher pK a (8.2 > 4.7), 80 a lower boiling point (110 °C < 118 °C), 81,82 7.36 × 10 4 M atm −1 ). 83 Additionally, PAA is miscible in water, 84 and its log K ow is −0.66 at pH 7.…”

Section: Introductionmentioning

confidence: 99%

“…83 Additionally, PAA is miscible in water, 84 and its log K ow is −0.66 at pH 7. 85 These properties can be largely attributed to PAA's intramolecular hydrogen bonding between the carbonyl oxygen and hydroxyl hydrogen, 81,86 forming a puckering five-membered ring, 87,88 as shown in eq 3. The weakest bond in the PAA molecule is the O−OH bond (38 kcal mol −1 ); 89 thus, the decomposition of PAA is initiated by O−OH bond cleavage.…”

Section: Introductionmentioning

confidence: 99%

“…a lower melting point (0.2 °C < 16.7 °C),81 and a smaller Henry's law constant (4.68 × 10 2 M atm −1 <…”

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confidence: 99%

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Reactivity of Peracetic Acid with Organic Compounds: A Critical Review

2020

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As an emerging oxidant and disinfectant, peracetic acid (PAA) has increasingly been used in wastewater treatment and the food and medical industries and has attracted greater research interest. To better understand reactions initiated by PAA, this paper is among the first to comprehensively review the reactivity of PAA with respect to organic compounds of various structures. The reactivities of PAA with respect to 123 organic compounds are compiled from the literature and new experiments, and possible reaction pathways and products are discussed. Overall, PAA is an electrophile with high selectivity in reaction. The second-order rate constants of PAA oxidation of organic compounds vary by nearly 10 orders of magnitude, from 3.2 × 10 −6 to >1.0 × 10 5 M −1 s −1 , which are much larger than those of H 2 O 2 coexisting in PAA solutions. Electron-donating groups of compounds increase the reactivity with respect to PAA, evidenced by the strong negative correlations between rate constants and substituent constants [Hammett (σ) or Taft (σ*)] of compounds. Sulfur moieties show exceptionally high reactivity with respect to PAA. Limited studies have shown that generally oxygen-added reaction products are formed from PAA oxidation. This critical review provides a useful foundation for advancing our understanding of the fate of organic compounds in wastewater treatment including PAA and identifies further research needs to evaluate a broader range of compounds and their oxidation products and toxicity.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Reactivity of Peracetic Acid with Organic Compounds: A Critical Review

2020

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“…Sinks of PAA include photolysis, reaction with the hydroxy radical (OH), and loss by physical deposition to the ground (Reactions R4, R5) (Jackson and Hewitt, 1999). The photolysis of PAA releases OH (Keller et al, 2008), and the reaction between PAA and OH regenerates CH 3 C(O)OO (Jenkin et al, 1997), so that PAA is involved in the radical balance as both a source and a sink. …”

Section: Introductionmentioning

confidence: 99%

Peroxyacetic acid in urban and rural atmosphere: concentration, feedback on PAN-NO<sub>x</sub> cycle and implication on radical chemistry

Zhang

Chen

et al. 2010

Atmos. Chem. Phys.

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Abstract. Peroxyacetic acid (PAA) is one of the most important atmospheric organic peroxides, which have received increasing attention for their potential contribution to the oxidation capacity of the troposphere and the formation of secondary aerosols. We report here, for the first time, a series of data for atmospheric PAA concentrations at urban and rural sites, from five field campaigns carried out in China in summer 2006, 2007 and 2008. For these five measurements, daytime mean (08:00-20:00 LT) PAA concentrations on sunlit days were 21.4-148.0 pptv with a maximum level of ∼1 ppbv. The various meteorological and chemical parameters influencing PAA concentrations were examined using Principal Factor Analysis. This statistical analysis shows that the local photochemical production was the major source of PAA, and its concentration increased with increasing temperature, solar radiation and ozone but decreased with increasing NO x (NO and NO 2 ), CO, SO 2 , and relative humidity. Based on the dataset, several issues are highlighted in this study: (i) Because PAA is a product from the photochemical oxidation of some specific volatile organic compounds (VOCs) that lead to acetyl peroxy radicals, the importance of various VOCs with respect to the PAA formation is therefore ranked using the incremental reactivity method. (ii) The contribution of PAN thermal degradation to PAA formation under conditions of different NO x concentrations is estimated based on the chemical kinetics analysis. The result shows that PAN seems to play an important role in the formation of PAA when the NO/NO 2 concentration ratio was less than 0.2 and PAA would correspondingly have feedback on the PAN-NO x cycle. (iii) PAA and other peroxides, such as methyl Correspondence to: Z. M. Chen (zmchen@pku.edu.cn) hydroperoxide (MHP) and H 2 O 2 , usually exhibited a similar asymmetric shape typically shifted to the afternoon. However, under some conditions, H 2 O 2 diurnal cycle was out of phase with MHP and PAA. The combination of linear regression and kinetics analysis indicate that the formation and removal processes of H 2 O 2 may be different from those of MHP and PAA. (iv) Considering that PAA is the reservior of free radicals, its fate is expected to have an effect on the free radical budget in the atmosphere. A box model based on the CBM-IV mechanism has been performed to access its influence on the radical budget. We suggest that the detailed information on PAA in the atmosphere is of importance to better understand the free radical chemistry.

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Section: Introductionmentioning

confidence: 99%

Peroxyacetic acid in urban and rural atmosphere: concentration, feedback on PAN-NO<sub>x</sub> cycle and implication on radical chemistry

Zhang¹,

Chen²,

He³

et al. 2009

Preprint

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Abstract. Peroxyacetic Acid (PAA) is one of important atmospheric organic peroxides, which have received increasing attention for their potential contribution to the oxidation capacity of the troposphere and the formation of secondary aerosols. We report here that, for the first time, a series of data for atmospheric PAA concentrations at urban and rural sites, from five field campaigns carried out in China in summer 2006, 2007 and 2008. For these five measurements, daytime mean PAA concentrations on sunlit days were 0.02–0.14 ppbv with a maximum level of ~1 ppbv. The various meteorological and chemical parameters influencing PAA concentrations were examined using the Principal Factor Analysis. This statistical analysis shows that the local photochemical production was the major source of PAA, and its concentration increased with increasing temperature, solar radiation and ozone but decreased with increasing NOx (NO and NO2), CO, SO2, and relative humidity. Based on the dataset, several issues are highlighted in this study: (i) because PAA is a product from the photochemical oxidation of some specific volatile organic compounds (VOCs) that lead to acetyl peroxy radicals, the importance of various VOCs with respect to the PAA formation is therefore ranked using the incremental reactivity method. (ii) The contribution of PAN thermal degradation to PAA formation under conditions of different NOx concentrations is estimated based on the chemical kinetics analysis. The result shows that PAN seems to play an important role in the formation of PAA when the NO/NO2 concentration ratio was less than 0.2 and PAA would correspondingly have feedback on the PAN-NOx cycle. (iii) PAA and other peroxides, such as methyl hydroperoxide (MHP) and H2O2, usually exhibited a similar asymmetric shape typically shifted to the afternoon. However, at a high SO2 level, H2O2 showed a profile different from those of MHP and PAA. The combination of linear regression and chemical kinetics analysis reveals that a possible unknown pathway results in the significant removal of H2O2 and the extent of H2O2 undergoing this pathway needs a further study. (iv) Considering that PAA is the reservior of free radicals, its fate is expected to have an effect on the free radical budget in the atmosphere. A box model based on the CBM-IV mechanism has been performed to access its influence on the radical budget. We suggest that the detailed information on PAA in the atmosphere is of importance to better understand the free radical chemistry.

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A directly-dissociative stepwise reaction mechanism for gas-phase peroxyacetic acid

Cited by 14 publications

References 54 publications

Reactivity of Peracetic Acid with Organic Compounds: A Critical Review

Reactivity of Peracetic Acid with Organic Compounds: A Critical Review

Peroxyacetic acid in urban and rural atmosphere: concentration, feedback on PAN-NO<sub>x</sub> cycle and implication on radical chemistry

Peroxyacetic acid in urban and rural atmosphere: concentration, feedback on PAN-NO<sub>x</sub> cycle and implication on radical chemistry

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A directly-dissociative stepwise reaction mechanism for gas-phase peroxyacetic acid

Cited by 14 publications

References 54 publications

Reactivity of Peracetic Acid with Organic Compounds: A Critical Review

Reactivity of Peracetic Acid with Organic Compounds: A Critical Review

Peroxyacetic acid in urban and rural atmosphere: concentration, feedback on PAN-NO&lt;sub&gt;x&lt;/sub&gt; cycle and implication on radical chemistry

Peroxyacetic acid in urban and rural atmosphere: concentration, feedback on PAN-NO&lt;sub&gt;x&lt;/sub&gt; cycle and implication on radical chemistry

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Peroxyacetic acid in urban and rural atmosphere: concentration, feedback on PAN-NO<sub>x</sub> cycle and implication on radical chemistry

Peroxyacetic acid in urban and rural atmosphere: concentration, feedback on PAN-NO<sub>x</sub> cycle and implication on radical chemistry