Rate constants for Hydrogen abstraction reactions of NO<sub>3</sub> in aqueous solution

Shastri, L.V.; Huie, Robert E.

doi:10.1002/kin.550220507

Cited by 26 publications

(12 citation statements)

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“…3.1 to 3.3, respectively. Furthermore, in a separate process NO 3 is known to abstract hydrogen atoms from the aliphatic tail of organic molecules (Shastri and Huie, 1990;Wayne et al, 1991;Mora-Diez et al, 2002). In order to investigate this effect as well, kinetic data on the saturated surfactant are then presented in Sect.…”

Section: Resultsmentioning

confidence: 99%

“…In addition to adding to the double bond of the unsaturated surfactants discussed in the previous sections, NO 3 may abstract hydrogen atoms from the aliphatic tail (Shastri and Huie, 1990;Wayne et al, 1991;Mora-Diez et al, 2002). In order to investigate the contribution of this hydrogen abstraction, the saturated surfactant stearic acid was exposed to NO 3 .…”

Section: Methyl Oleate (D 33 Mo) Exposed To Nitrate Radicals (No 3 )mentioning

confidence: 99%

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Nighttime oxidation of surfactants at the air–water interface: effects of chain length, head group and saturation

et al. 2018

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Reactions of the key atmospheric nighttime oxidant NO 3 with organic monolayers at the air-water interface are used as proxies for the ageing of organic-coated aqueous aerosols. The surfactant molecules chosen for this study are oleic acid (OA), palmitoleic acid (POA), methyl oleate (MO) and stearic acid (SA) to investigate the effects of chain length, head group and degree of unsaturation on the reaction kinetics and products formed. Fully and partially deuterated surfactants were studied using neutron reflectometry (NR) to determine the reaction kinetics of organic monolayers with NO 3 at the air-water interface for the first time. Kinetic modelling allowed us to determine the rate coefficients for the oxidation of OA, POA and MO monolayers to be (2.8 ± 0.7) × 10 −8 , (2.4 ± 0.5) × 10 −8 and (3.3 ± 0.6) × 10 −8 cm 2 molecule −1 s −1 for fitted initial desorption lifetimes of NO 3 at the closely packed organic monolayers, τ d,NO 3 ,1 , of 8.1 ± 4.0, 16 ± 4.0 and 8.1 ± 3.0 ns, respectively. The approximately doubled desorption lifetime found in the best fit for POA compared to OA and MO is consistent with a more accessible double bond associated with the shorter alkyl chain of POA facilitating initial NO 3 attack at the double bond in a closely packed monolayer. The corresponding uptake coefficients for OA, POA and MO were found to be (2.1±0.5)×10 −3 , (1.7±0.3)×10 −3 and (2.1±0.4)×10 −3 , respectively. For the much slower NO 3 -initiated oxidation of the saturated surfactant SA we estimated a loss rate of approximately (5 ± 1) × 10 −12 cm 2 molecule −1 s −1 , which we consider to be an upper limit for the reactive loss, and estimated an uptake coefficient of ca. (5 ± 1) × 10 −7 . Our investigations demonstrate that NO 3 will contribute substantially to the processing of unsaturated surfactants at the air-water interface during nighttime given its reactivity is ca. 2 orders of magnitude higher than that of O 3 . Furthermore, the relative contributions of NO 3 and O 3 to the oxidative losses vary massively between species that are closely related in structure: NO 3 reacts ca. 400 times faster than O 3 with the common model surfactant oleic acid, but only ca. 60 times faster with its methyl ester MO. It is therefore necessary to perform a case-by-case assessment of the relative contributions of the different degradation routes for any specific surfactant. The overall impact of NO 3 on the fate of saturated surfactants is slightly less clear given the lack of prior kinetic data for comparison, but NO 3 is likely to contribute significantly to the loss of saturated species and dominate their loss during nighttime. The retention of the organic character at the air-water interface differs fundamentally between the different surfactant species: the fatty acids studied (OA and POA) form products with a yield of ∼ 20 % that are stable at the interface while NO 3 -initiated oxidation of the methyl ester MO rapidly and effectively removes the organic character (≤ 3 % surface-active products). The film-forming potential of r...

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Section: Resultsmentioning

confidence: 99%

Section: Methyl Oleate (D 33 Mo) Exposed To Nitrate Radicals (No 3 )mentioning

confidence: 99%

Nighttime oxidation of surfactants at the air–water interface: effects of chain length, head group and saturation

et al. 2018

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“…However, considerably less information is available for the reactions of • NO 3 in the condensed phase . There are only a few reports concerning • NO 3 kinetics in aqueous solution . Considerably more kinetic data are available for reactions in acetonitrile where the • NO 3 radical is generated by the laser photolysis of dissolved Ce IV (NO 3 ) 6 2− .…”

Section: Introductionmentioning

confidence: 99%

The Reactivity of the Nitrate Radical (^• NO₃ ) in Aqueous and Organic Solutions

Mezyk

Cullen

Rickman

et al. 2017

Int. J. Chem. Kinet.

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Rate constants for the nitrate ( • NO 3 ) radical reaction with alcohols, alkanes, alkenes, and several aromatic compounds were measured in aqueous and tert-butanol solution for comparison to aqueous and acetonitrile values from the literature. The measured trends provide insight into the reactions of the • NO 3 radical in various media. The reaction with alcohols primarily consists of hydrogen-atom abstraction from the alpha-hydroxy position and is faster in solvents of lower polarity where the diffusivity of the radical is greater. Alkenes react faster than alkanes, and their rate constants are also faster in nonpolar solution. The situation is reversed for the nitrate radical reaction with the aromatic compounds, where the rate constants in tert-butanol are slower. This is attributed to the need to solvate the NO 3 − anion and corresponding tropylium cation produced by the • NO 3 radical electron transfer reaction. A linear correlation was found between measured rate constants in water and acetonitrile, which can be used to estimate aqueous nitrate radical rate constants for compounds having low water solubility.

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“…OVOCs in the aqueous phase taken from the CAPRAM kinetic database (Bräuer et al, 2016). (Shastri and Huie, 1990) Iso-propanol CC(O)C 3.7•10 6 3.1•10 8 1323 (Herrmann et al, 1994) with E A /R of (Ito et al, 1989) Iso-butanol CC(C)CO 1.6•10 6 (Shastri and Huie, 1990) Tert-butanol CC(C)CO 6.6•10 4 (Herrmann et al, 1994) Allyl alcohol C=CCO 2.2•10 8 Average of (Alfassi et al, 1993) and (Ito et al, 1989) et al, 1993) 3-Methyl 3-Buten-1-ol C=C(C)CCO 2.4•10 9 (Alfassi et al, 1993)…”

Section: Table Si-2 Compilation Of Kinetic Data On Reactions Of No 3mentioning

confidence: 99%

“…Chem., 48, 241-260, 2004. Barnes, I., Bastian, V., Becker, K. H., and Tong, Z.: Kinetics and Products of the Reactions of NO 3 with Monoalkenes, Dialkenes, and Monoterpenes, J Phys Chem-Us, 94, 2413-2419, 1990. Benter, T., and Schindler, R. N.: Absolute rate coefficients for the reaction of NO 3 radicals with simple dienes, Chemical Physics Letters, 145, 67-70, 10.1016/0009-2614(88)85134-0, 1988.…”

Section: Diols and Polyolsmentioning

confidence: 99%

Supplementary material to "Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms and organic aerosol"

Ng¹,

Brown²,

Archibald³

et al. 2016

Preprint

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Alkenes 1-octadecene [17] CWFT, (l) 1.6 ± 0.3 (293 K) (Moise et al., 2002) 1-hexadecene [18] CWFT, (l) 2.3 ± 0.9 (277 K) (Moise et al., 2002) 7-tetradecene [19] CWFT, (l) 5.8 ± 2.0 (246 K) (Moise et al., 2002) Methyl oleate [20] CWFT, (l) 140 !!" !!!"# (278 K) (Xiao and Bertram, 2011) Methyl oleate (in DES) CWFT, (l) 15-95 (278 K) ~ 0.3-2.3 wt % methyl oleate (Xiao and Bertram, 2011) Methyl oleate (in DOS) CWFT, (l) 15-30 (278 K) ~ 0.6-2.6 wt % methyl oleate (Xiao and Bertram, 2011) methyl oleate (in squalane) CWFT, (l) 10-25 (278 K) ~ 0.7-3.1 wt % methyl oleate (Xiao and Bertram, 2011) Undec-10-ene-1-thiol [21] CWFT, (SAM) 34 !!" !!!! !(298 K) γ decreased (> factor 10) with reaction time as number of double bonds were depleted. Condensed phase products were organonitrates and carbonyls. (Gross and Bertram, 2009) Squalene [22] AFT, in N 2 (lp) VUV-MS 180 ± 30 (293 K) γ (calculated assuming that only NO 3 was lost to surface) increased (to 820 ± 110) with reaction time. (Lee et al., 2013) 17-octadecene-1-thiol [23] UHV, (SAM) RAIRS, XPS 2.3 ± 0.5 Reaction at terminal double bond to form organic nitrate via addition. N3 (Zhang et al., 2014c) Unsaturated Acids Abietic [25] CWFT, (s) ~3 (298 K) RH < 0.5 % N5 (Knopf et al., 2011) (Shiraiwa et al., 2012) Linoleic (conj.) [26] CWFT, (l) 7.9 ± 1.2 (273 K) (Moise et al., 2002) Linoleic (unconj.) [27] CWFT, (l) 15.0 ± 2.0 (288 K) (Moise et al., 2002) Linoleic (conj.) [28] AFT, (lp) 1010 ± 180 (295 K) (Zhao et al., 2011) Linoleic [29] CWFT, (l) 400 !!"# !!!"# (298 K) RH ~ 0 %, In the absence of O 2 (Knopf et al., 2011) Linoleic (unconj.) [30] AFT, (lp) 530 ± 120 (295 K) (Zhao et al., 2011) Linoleic (conj.) [31] CWFT, (l) >120 (278-298 K) (Gross et al., 2009a) Linoleic (unconj.) [32] CWFT, (l) >130 (288 K) (Gross et al., 2009a) Linolenic [33] AFT, (lp) 720 ± 170 (295 K) (Zhao et al., 2011) Oleic ATR-IR, GC-MS, LC-MS (l)

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Rate constants for Hydrogen abstraction reactions of NO₃ in aqueous solution

Cited by 26 publications

References 14 publications

Nighttime oxidation of surfactants at the air–water interface: effects of chain length, head group and saturation

Nighttime oxidation of surfactants at the air–water interface: effects of chain length, head group and saturation

The Reactivity of the Nitrate Radical (^• NO₃ ) in Aqueous and Organic Solutions

Supplementary material to "Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms and organic aerosol"

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Rate constants for Hydrogen abstraction reactions of NO3 in aqueous solution

Cited by 26 publications

References 14 publications

Nighttime oxidation of surfactants at the air–water interface: effects of chain length, head group and saturation

Nighttime oxidation of surfactants at the air–water interface: effects of chain length, head group and saturation

The Reactivity of the Nitrate Radical (• NO3 ) in Aqueous and Organic Solutions

Supplementary material to &quot;Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms and organic aerosol&quot;

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Product

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Rate constants for Hydrogen abstraction reactions of NO₃ in aqueous solution

The Reactivity of the Nitrate Radical (^• NO₃ ) in Aqueous and Organic Solutions

Supplementary material to "Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms and organic aerosol"