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Open AccessArticle

pH- and Temperature-Dependent Kinetics of the Oxidation Reactions of OH with Succinic and Pimelic Acid in Aqueous Solution

Atmospheric Chemistry Department (ACD), Leibniz-Institute for Tropospheric Research (TROPOS), Permoserstrasse 15, 04318 Leipzig, Germany
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Atmosphere 2020, 11(4), 320; https://doi.org/10.3390/atmos11040320
Received: 4 March 2020 / Revised: 22 March 2020 / Accepted: 24 March 2020 / Published: 26 March 2020
(This article belongs to the Special Issue Atmospheric Aqueous-Phase Chemistry)
Rate constants for the aqueous-phase reactions of the hydroxyl radical with the dicarboxylic acids, succinic acid and pimelic acid were determined using the relative rate technique over the temperature range 287 K ≤ T ≤ 318 K and at pH = 2.0, 4.6 or 4.9 and 8.0. OH radicals were generated by H2O2 laser flash photolysis while thiocyanate was used as a competitor. The pH values were adjusted to obtain the different speciation of the dicarboxylic acids. The following Arrhenius expressions were determined (in units of L mol−1 s−1):  succinic acid, k(T, AH2) (2.1 ± 0.1) × 1010 exp[(−1530 ± 250 K)/T], k(T, AH) (1.8 ± 0.1) × 1010 exp[(−1070 ± 370 K)/T], k(T, A2−) (2.9 ± 0.2) × 1011 exp[(−1830 ± 350 K)/T] and pimelic acid, k(T, AH2) (7.3 ± 0.2) × 1010 exp[(−1040 ± 140 K)/T], k(T, AH) (1.8 ± 0.1) × 1011 exp[(−1200 ± 240 K)/T], k(T, A2−) (1.4 ± 0.1) × 1012 exp[(−1830 ± 110 K)/T]. A general OH radical reactivity trend for dicarboxylic acids was found as k(AH2) < k(AH) < k(A2−). By using the pH and temperature dependent rate constants, source and sinking processes in the tropospheric aqueous phase can be described precisely. View Full-Text
Keywords: OH radicals; rate constants; dicarboxylic acids; succinic acid; pimelic acid; aqueous phase chemistry OH radicals; rate constants; dicarboxylic acids; succinic acid; pimelic acid; aqueous phase chemistry
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MDPI and ACS Style

Schaefer, T.; Wen, L.; Estelmann, A.; Maak, J.; Herrmann, H. pH- and Temperature-Dependent Kinetics of the Oxidation Reactions of OH with Succinic and Pimelic Acid in Aqueous Solution. Atmosphere 2020, 11, 320.

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