Kinetics of Formation of Peroxyacetic Acid

Dul'neva, Larisa V.; Moskvin, A. V.

doi:10.1007/s11176-005-0378-8

Cited by 67 publications

(53 citation statements)

References 8 publications

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“…PAA aqueous solution was synthesized by mixing H 2 O 2 aqueous solution with acetic acid aqueous solution, using H 2 SO 4 as a catalyst (Dul'neva and Moskvin, 2005;Zhao et al, 2007). The mixing aqueous solution was kept in the dark for 24 h at room temperature to make sure PAA reached its maximum balanced concentration.…”

Section: Generation Of Gaseous Paa and H 2 Omentioning

confidence: 99%

Heterogeneous reaction of peroxyacetic acid and hydrogen peroxide on ambient aerosol particles under dry and humid conditions: kinetics, mechanism and implications

Huang

Liang

et al. 2015

Atmos. Chem. Phys.

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Abstract.Hydrogen peroxide (H 2 O 2 ) and organic peroxides play important roles in the cycle of oxidants and the formation of secondary aerosols in the atmosphere. Recent field observations have suggested that the budget of peroxyacetic acid (PAA, CH 3 C(O)OOH) is potentially related to the aerosol phase processes, especially to secondary aerosol formation. Here, we present the first laboratory measurements of the uptake coefficient of gaseous PAA and H 2 O 2 onto ambient fine particulate matter (PM 2.5 ) as a function of relative humidity (RH) at 298 K. The results show that the PM 2.5 , which was collected in an urban area, can take up PAA and H 2 O 2 at the uptake coefficient (γ ) of 10 −4 , and both γ PAA and γ H 2 O 2 increase with increasing RH. The value of γ PAA at 90 % RH is 5.4 ± 1.9 times that at 3 % RH, whereas γ H 2 O 2 at 90 % RH is 2.4 ± 0.5 times that at 3 % RH, which suggests that PAA is more sensitive to the RH variation than H 2 O 2 is. Considering the larger Henry's law constant of H 2 O 2 than that of PAA, the smaller RH sensitivity of the H 2 O 2 uptake coefficient suggests that the enhanced uptake of peroxide compounds on PM 2.5 under humid conditions is dominated by chemical processes rather than dissolution. Considering that mineral dust is one of the main components of PM 2.5 in Beijing, we also determined the uptake coefficients of gaseous PAA and H 2 O 2 on authentic Asian Dust storm (ADS) and Arizona Test Dust (ATD) particles. Compared to ambient PM 2.5 , ADS shows a similar γ value and RH dependence in its uptake coefficient for PAA and H 2 O 2 , while ATD gives a negative dependence on RH. The present study indicates that, in addition to the mineral dust in PM 2.5 , other components (e.g., soluble inorganic salts) are also important to the uptake of peroxide compounds. When the heterogeneous reaction of PAA on PM 2.5 is considered, its atmospheric lifetime is estimated to be 3.0 h on haze days and 7.1 h on non-haze days, values that are in good agreement with the field observations.

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Section: Generation Of Gaseous Paa and H 2 Omentioning

confidence: 99%

Heterogeneous reaction of peroxyacetic acid and hydrogen peroxide on ambient aerosol particles under dry and humid conditions: kinetics, mechanism and implications

Huang

Liang

et al. 2015

Atmos. Chem. Phys.

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“…[10,[19][20] In a formic acid-autocatalyzed reaction system, the hydrogen ions in the aqueous phase are mainly from the dissociation of FA. The hydrogen ion concentration in this paper was calculated using equations adopted by Sun et al: [10] …”

mentioning

confidence: 99%

Mass transfer and reaction kinetics of soybean oil epoxidation in a formic acid‐autocatalyzed reaction system

Nie

Chen

et al. 2016

Can J Chem Eng

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In this study, the mass transfer and reaction kinetics of soybean oil epoxidation using concentrated hydrogen peroxide in a formic acidautocatalyzed reaction system were studied in detail. Studying the mass transfer of formic acid showed that the influence of reactant diffusion near the interface is eliminated when the stirring rate is > 120 rpm in a double-stirred cell, and the mass transfer rate decreases greatly with the conversion of double bonds and a decrease of reaction temperature. A temperature increase has little impact on the equilibrium of formic acid in the oil/water system, while an increase of epoxidized soybean oil significantly increases the value of the partition coefficient of formic acid. Another important aspect in the kinetic study is the decomposition of performic acid, which can cause the reduction of H 2 O 2 and formic acid during the reaction. Finally, a biphasic model, which considers all reactions in oil and aqueous phases, the equilibrium and mass transfer of reagents and products between the phases, and the evolution of proton concentrations with time, was developed to describe the epoxidation process.

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“…reactant concentrations and reaction time). Available studies of the hydrolysis of peracetic acid show that its hydrolysis kinetics strongly depend on the reaction conditions, such as temperature and pH (Dul'neva and Moskvin, 2005;Yuan et al, 1997), leading to large variations in decomposition rates. The main factors limiting precision of the measurement are low signal intensity, uncertainty of the 5 measurement of filter mass loading and peroxypinic acid degradation on the filter, as described in the following section.…”

Section: Humid Vs Dry Conditionsmentioning

confidence: 99%

Synthesis and characterization of peroxypinic acids as proxies for highly oxygenated molecules (HOMs) in secondary organic aerosol

Steimer¹,

Delvaux²,

Campbell³

et al. 2018

Preprint

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Abstract. Peroxy acids might contribute significantly to particle toxicity and were recently found to be involved in new particle formation in the atmosphere. However, a lack of suitable analytical methods for the detection and characterization of peroxy acids in the particle phase is currently hindering the quantitative investigation of their contribution to these important 10 atmospheric processes. Further development of appropriate techniques and relevant standards is therefore urgently needed.In this study, we synthesized three peroxypinic acids, developed a liquid chromatography separation method and characterised them with tandem mass spectrometry. The observed fragmentation patterns clearly distinguish the different peroxypinic acids from both the acid and each other, showing several neutral losses previously already observed for other peroxy acids. Both monoperoxypinic acids were found to be present in secondary organic aerosol generated from ozonolysis 15 of α-pinene in laboratory experiments. The yield of monoperoxypinic acid formation was not influenced by humidity.Monoperoxypinic acid quickly degrades on the filter, with about 60% lost within the first 5 hours. This fast degradation shows that time delays in traditional off-line analysis will likely lead to severe underestimates of peroxy compound concentrations in ambient particles.

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Kinetics of Formation of Peroxyacetic Acid

Cited by 67 publications

References 8 publications

Heterogeneous reaction of peroxyacetic acid and hydrogen peroxide on ambient aerosol particles under dry and humid conditions: kinetics, mechanism and implications

Heterogeneous reaction of peroxyacetic acid and hydrogen peroxide on ambient aerosol particles under dry and humid conditions: kinetics, mechanism and implications

Mass transfer and reaction kinetics of soybean oil epoxidation in a formic acid‐autocatalyzed reaction system

Synthesis and characterization of peroxypinic acids as proxies for highly oxygenated molecules (HOMs) in secondary organic aerosol

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