25 Aug 2022
25 Aug 2022
Status: this preprint is currently under review for the journal ACP.

Measurement of Henry's law and liquid-phase loss rate constants of peroxypropionic nitric anhydride (PPN) in deionized water and in n-octanol

Kevin Douglas Easterbrook, Mitchell Anthony Vona, Kiana Nayebi-Astaneh, Amanda McKenzie Miller, and Hans Dieter Osthoff Kevin Douglas Easterbrook et al.
  • Department of Chemistry, University of Calgary, 2500 University Drive N.W., Calgary, Alberta, Canada T2N 1N4

Abstract. The Henry's law solubility (HS) and liquid-phase loss rate constants (kl) of the tropospheric trace gas constituents peroxyacetic nitric anhydride (PAN, CH3C(O)O2NO2; commonly known as peroxyacetyl nitrate) and peroxypropionic nitric anhydride (PPN, C2H5C(O)O2NO2; also known as peroxypropionyl nitrate) in deionized (DI) water and of PPN in n-octanol were measured using a flow bubble apparatus at temperatures between 5.0 °C and 25.0 °C. For PAN in DI water, the observed values for HS,aq are consistent with literature, whereas the solubility of PPN in DI water is slightly lower than literature values, ranging from HSCP (PNN)aq =  (1.49±0.05) M atm-1 at 25.0 °C to HSCP (PNN)aq = (7.01±0.25) M atm-1 at 5.0 °C (stated uncertainties are at the 1σ level). The data are best described by ln(HSCP (PAN)aq/[M atm-1]) = -(17.8±0.3) + (5620±85)/T  and ln(HSCP (PNN)aq/[M atm-1]) = -(19.5±1.7) + (5955±480)/T , where T is in Kelvin. For n-octanol, the PPN solubility ranges from HSCP (PNN)oct = (88±5) M atm-1 at 25.0 °C to HSCPoct = (204±16) M atm-1 at 5.0 °C and is best described by ln(HSCP (PNN)oct/[M atm-1]) = -(6.92±0.75) + (3390±320)/T. n-Octanol-water partition coefficients (KOW) for PPN were determined for the first time, ranging from 59±4 at 25.0 °C to 29±3 at 5.0 °C. Observed loss rate constants in DI water are consistent with recent literature and larger than the thermal dissociation rates for both PAN and PPN, consistent with a hydrolysis mechanism, whereas kl values in n-octanol are significantly smaller than gas-phase dissociation rate constants, likely owing to a "cage effect" in the organic liquid. The results imply that uptake of either PAN or PPN on cloud water and organic aerosol is negligible but that uptake of PPN may constitute an overlooked source of peroxy radicals in organic aerosol.

Kevin Douglas Easterbrook et al.

Status: open (until 06 Oct 2022)

Comment types: AC – author | RC – referee | CC – community | EC – editor | CEC – chief editor | : Report abuse
  • RC1: 'Comment on acp-2022-587', Anonymous Referee #1, 01 Sep 2022 reply
  • RC2: 'Comment on acp-2022-587', Rolf Sander, 06 Sep 2022 reply

Kevin Douglas Easterbrook et al.

Kevin Douglas Easterbrook et al.


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Short summary
The trace gas peroxypropionyl nitrate (PPN) is generated in photochemical smog, phytotoxic, a strong eye irritant, and possibly mutagenic. Here, its solubility and reactivity in water and in octanol was investigated using a bubble flow apparatus, yielding its Henry's law constant and octanol-water partition coefficient (Kow). The results allow the fate of PPN to be more accurately constrained in atmospheric chemical transport models, including its uptake on clouds, organic aerosol, and leaves.