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Kinetic Study of Esterification of Sulfuric Acid with Alcohols

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Kinetic Study of Esterification of Sulfuric Acid with Alcohols EGU Journal Logos (RGB) Open Access Open Access Open Access Advances in Annales Nonlinear Processes Geosciences Geophysicae in Geophysics Open Access Open Access Natural Hazards Natural Hazards and Earth System and Earth System Sciences Sciences Discussions Open Access Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Open Access Atmos. Chem. Phys. Discuss., 13, 23217–23250,Atmospheric 2013 Atmospheric www.atmos-chem-phys-discuss.net/13/23217/2013/Chemistry Chemistry doi:10.5194/acpd-13-23217-2013 ACPD © Author(s) 2013. CC Attribution 3.0 License.and Physics and Physics Discussions 13, 23217–23250, 2013 Open Access Open Access Atmospheric Atmospheric This discussion paper is/hasMeasurement been under review for the journal AtmosphericMeasurement Chemistry Kinetic study of and Physics (ACP). Please referTechniques to the corresponding final paper in ACP ifTechniques available. esterification of Discussions sulfuric acid with Open Access Kinetic study of esterification of sulfuricOpen Access alcohols Biogeosciences Biogeosciences acid with alcohols in aerosol bulkDiscussions phase J. Li and M. Jang Open Access Open Access J. Li and M. Jang Climate Climate Title Page of the Past of the Past Department of Environmental Engineering Sciences, P.O. Box 116450, UniversityDiscussions of Florida, Abstract Introduction Gainesville, FL 32611, USA Open Access Open Access Conclusions References Received: 15 August 2013 – Accepted: 20 August 2013 – Published: 4 September 2013 Earth System Earth System Correspondence to: M. Jang (mjang@ufl.edu)Dynamics Dynamics Tables Figures Discussions Published by Copernicus Publications on behalf of the European Geosciences Union. J I Open Access Geoscientific Geoscientific Open Access Instrumentation Instrumentation J I Methods and Methods and Data Systems Data Systems Back Close Discussions Open Access Open Access Full Screen / Esc Geoscientific Geoscientific Model Development Model Development Printer-friendly Version Discussions Interactive Discussion Open Access Open Access Hydrology and Hydrology and Earth System23217 Earth System Sciences Sciences Discussions Open Access Open Access Ocean Science Ocean Science Discussions Open Access Open Access Solid Earth Solid Earth Discussions Open Access Open Access The Cryosphere The Cryosphere Discussions Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Abstract ACPD In this study, we hypothesize that the formation of organosulfates through the reac- tions between sulfuric acid and alcohols in the aerosol bulk phase is more efficient 13, 23217–23250, 2013 than that in solution chemistry. To prove this hypothesis, the kinetics of the organosul- 5 fate formation was investigated for both aliphatic alcohol with single OH group (e.g., Kinetic study of 1-heptanol) and the multialcohols ranging from semivolatiles (e.g., hydrated-glyoxal esterification of and glycerol) to nonvolatiles (e.g., sucrose) using analytical techniques directly moni- sulfuric acid with toring aerosol bulk phase. Both the forward (k1) and the backward (k−1) reaction rate alcohols constants of organosulfate formation via the particle phase esterification of 1-heptanol 10 with sulfuric acid were estimated using a Fourier Transform Infrared (FTIR) spectrom- J. Li and M. Jang eter equipped with a flow chamber under varying humidities. Both k1 and k−1 are in orders of 10−3 L mol−1 min−1, which are three orders of magnitude higher than the re- ported values obtained in solution chemistry. The formation of organosulfate in the Title Page H2SO4 aerosol internally mixed with multialcohols was studied by measuring the pro- Abstract Introduction 15 ton concentration of the aerosol collected on the filter using a newly developed Col- orimetry integrated with a Reflectance UV-Visible spectrometer (C-RUV). The forma- Conclusions References tion of organosulfate significantly decreases aerosol acidity due to the transformation Tables Figures of H2SO4 into dialkylsulfates. The forward reaction rate constants for the dialkylsul- fate formation in the multialcohol-H2SO4 aerosols were also three orders of magnitude J I 20 greater than the reported values in solution chemistry. The water content (M ) in the H2O multialcohol-H2SO4 particle was monitored using the FTIR spectrometer. A large re- J I duction of M accords with the high yield of organosulfate in aerosol. Based on this H2O study, we conclude that organosulfate formation in atmospheric aerosol, where both Back Close alcohols and sulfuric acid are found together, is significant. Full Screen / Esc Printer-friendly Version Interactive Discussion 23218 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | 1 Introduction ACPD Sulfuric acid, which is typically produced from the photooxidation of sulfur dioxide, is one of the major inorganic components for the ambient aerosol. It can either be neu- 13, 23217–23250, 2013 tralized by ammonia forming ammonium salt, or react with certain atmospheric organic 5 compounds (e.g., alcohols and aldehydes) producing organosulfates in aerosol (Eqs. 1 Kinetic study of and 2) (Deno and Newman, 1950; Minerath et al., 2008). esterification of sulfuric acid with ROH + H SO ROSO H + H O (1) 2 4 3 2 alcohols J. Li and M. Jang ROH + ROSO3H ROSO2OR + H2O (2) 10 Field studies have shown that organosulfate is ubiquitous in ambient aerosols col- Title Page lected at various locations in US (Surratt et al., 2007a; Hatch et al., 2011), Asia (Maria Abstract Introduction et al., 2003; Stone et al., 2012), and Europe (Gomez-Gonzalez et al., 2008; Iinuma et al., 2007; Kristensen and Glasius, 2011). For example, Hatch et al. (2011) have re- Conclusions References ported that organosulfate signal was detected in negative-ion spectra of most ambient Tables Figures 15 submicron aerosols collected during the 2002 Aerosol Nucleation and Characterization Experiment (ANARChE) and the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS). Organosulfates have also been identified in free tropospheric aerosols J I characterized by single particle mass spectrometry in airborne field campaigns (Froyd J I et al., 2010). 20 In order to identify the source of organosulfates in aerosol and their reaction mech- Back Close anisms, laboratory studies have been conducted using both model compounds and Full Screen / Esc laboratory generated secondary organic aerosol (SOA). Some studies suggested that organosulfates form through the direct reactions of sulfuric acid with organic com- Printer-friendly Version pounds such as alcohols, aldehydes, and epoxides. For example, Liggio et al. (2005) 25 have reported organosulfate formation from the reactive uptake of glyoxal onto acidic Interactive Discussion sulfate particles. Using the HPLC/(-)ESI-IMS-QTOFMS analysis, Iinuma et al. (2009) 23219 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | identified orgnaosulfates from the reactive uptake of monoterpene oxides on acidic sul- fate particles. Surratt et al. (2010) showed organosufates formation through the acid- ACPD catalyzed reactive uptake of isoprene epoxydiols (IEPOX). Lal et al. (2012) detected 13, 23217–23250, 2013 organosulfate produced from the reaction of α-pinene oxide with sulfuric acid solution 5 using NMR. In addition to the mechanisms via the direct reactions between sulfuric acid and organic compounds, organosulfates can also be formed through the reaction Kinetic study of − of organic compounds (e.g., aldehydes and oxygenated alkenes) with SO4 radicals esterification of produced from photo-irradiation of sulfate. For example, Galloway et al. (2009) found sulfuric acid with irreversible organosulfate products when glyoxal was photoirradiated in the presence alcohols 10 of wet ammonium sulfate aerosol. The structures of resulting irreversible organosul- fate products (e.g., glycolic acid sulphate) in their study are different from reversible J. Li and M. Jang organosulfate products (sulfate esters) found by Liggio et al. (2005). Noziere et al. (2010) also suggested that radical reactions would be a plausible origin for the atmo- Title Page spheric organosulfates. 15 Most kinetic studies for organosulfate formation using model compounds (e.g., alco- Abstract Introduction hols) have been conducted in solution. Among organic compounds, the reaction rates of epoxides with sulfuric acid are considerably fast while those of both alcohols and Conclusions References aldehydes with sulfuric acid in solution chemistry are relatively too slow to produce Tables Figures organosulfates within the atmospheric lifetime of aerosol. For example, the reported 20 forward reaction rate constant for esterification of alcohols in high concentration of sul- J I furic acid solution (65 wt %) is slow (e.g., 5.7 × 10−6 L mol−1 min−1 for 1-butanol) (Min- erath et al., 2008) suggesting that the lifetime of alcohol for sulfate esterification is 4600 J I days at pH = 1.5. Back Close However, it is disputable whether the reaction rate constants observed in solution 25 chemistry are applicable to the aerosol bulk phase. Foremost, water molecules pro- Full Screen / Esc duced as by-products of organosulfate formation (Eqs. 1 and 2) can be evaporating from the aerosol leaving less volatile organosulfates in aerosol. Both water evapora- Printer-friendly Version tion and the formation of hydrophobic organosulfates (compared to sulfuric acid) would possibly promote the forward reactions, increasing organosulfate yields (Eqs. 1 and 2). Interactive Discussion 23220 Discussion Paper | Discussion Paper
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