ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-11-8307-2011 Thermodynamics and kinetics of the hydrolysis of atmospherically relevant organonitrates and organosulfates Hu K. S. 1 Darer A. I. 1 Elrod M. J. 1 Department of Chemistry and Biochemistry, Oberlin College, Oberlin, Ohio, USA 16 08 2011 11 16 8307 8320 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys.net/11/8307/2011/acp-11-8307-2011.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/11/8307/2011/acp-11-8307-2011.pdf

The presence of alcohol, organonitrate, and organosulfate species related to the gaseous precursor isoprene in ambient secondary organic aerosol (SOA) has stimulated investigations of the nature of SOA-phase chemical processing. Recent work has suggested that certain isoprene-derived organonitrates are able to efficiently convert to organosulfates and alcohols on ambient SOA. In order to better understand the structure activity relationships previously observed for the isoprene-derived organonitrates and organosulfates, the hydrolysis reactions of a number of monofunctional and difunctional organonitrates and organosulfates with varying carbon substitution properties were investigated. Nuclear magnetic resonance techniques were used to study the bulk phase aqueous reactions of these organonitrates and organosulfates in order to determine hydrolysis reaction rate and, in some cases, thermodynamics information. Electronic structure calculations were also carried out to determine the enthalpy of hydrolysis for these species, and for the previously studied isoprene-derived species. The results suggest that while organonitrates and organosulfates are thermodynamically unstable with respect to the corresponding alcohols at standard state, only the tertiary organonitrates (and perhaps some tertiary organosulfates) are able to efficiently hydrolyze on SOA timescales and acidities.

 References % vor jede Referenz Altieri, K. E., Turpin, B. J., and Seitzinger, S. P.: Oligomers, organosulfates, and nitrooxy organosulfates in rainwater identified by ultra-high resolution electrospray ionization FT-ICR mass spectrometry, Atmos. Chem. Phys., 9, 2533–2542, http://dx.doi.org/10.5194/acp-9-2533-2009doi:10.5194/acp-9-2533-2009, 2009. Baker, J. W. and Easty, D. M.: Hydrolytical decomposition of esters of nitric acid. I. General experimental techniques. Alkaline hydrolysis and neutral solvolysis of methyl, ethyl, isopropyl, and tertbutyl nitrates in aqueous alcohol, J. Chem. Soc., 1952, 1193–1207, 1952. Burley, J. D. and Johnston, H. S.: Nitrosyl sulfuric acid and stratospheric aerosols, Geophys. Res. Lett., 19, 1363–1366, 1992. Cappa, C. D. and Elrod, M. J.: A computational investigation of the electron affinity of CO<sub>3</sub> and the thermodynamic feasibility of CO$_3^-$(H<sub>2</sub>O)$_n$ + ROOH reactions, Phys. Chem. Chem. Phys., 3, 2986–2994, 2001. Carlton, A. G., Wiedinmyer, C., and Kroll, J. H.: A review of Secondary Organic Aerosol (SOA) formation from isoprene, Atmos. Chem. Phys., 9, 4987–5005, http://dx.doi.org/10.5194/acp-9-4987-2009doi:10.5194/acp-9-4987-2009, 2009. Casale, M., Richman, A., Elrod, M., Garland, R., Beaver, M., and Tolbert, M.: Kinetics of acid-catalyzed aldol condensation reactions of aliphatic aldehydes, Atmos. Environ., 41, 6212–6224, http://dx.doi.org/10.1016/j.atmosenv.2007.04.002doi:10.1016/j.atmosenv.2007.04.002, 2007. Chan, M. N., Surratt, J. D., Claeys, M., Edgerton, E. S., Tanner, R. L., Shaw, S. L., Zheng, M., Knipping, E. M., Eddingsaas, N. C., Wennberg, P. O., and Seinfeld, J. H.: Characterization and quantification of isoprene-derived epoxydiols in ambient aerosol in the southeastern United States, Environ. Sci. Technol., 44, 4590–4596, 2010. Claeys, M., Graham, B., Vas, G., Wang, W., Vermeylen, R., Pashynska, V., J., C., Guyon, P., Andreae, M. O., Artaxo, P., and Maenhaut, W.: Formation of secondary organic aerosols through photooxidation of isoprene, Science, 303, 1173–1176, http://dx.doi.org/10.1126/science.1092805doi:10.1126/science.1092805, 2004. Clark, D. J. and Williams, G.: Esterification by sulphuric acid, J. Chem. Soc., 4218–4221, 1957. Cole-Filipiak, N. C., O'Connor, A. E., and Elrod, M. J.: Kinetics of the hydrolysis of atmospherically relevant isoprene-derived hydroxy epoxides, Environ. Sci. Technol., 44, 6718–6723, 2010. Cox, R. A. and Yates, K.: Excess acidities. A generalized method for the determination of basicities in aqueous acid mixtures, J. Am. Chem. Soc., 100, 3861–3867, 1978. Curtiss, L. A., Raghavachari, K., Redfern, P. C., and Pople, J. A.: Assessment of Gaussian-2 and density functional theories for the computation of enthalpies of formation, J. Chem. Phys., 106, 1063–1079, 1997. Darer, A. I., Cole-Filipiak, N. C., O'Connor, A. E., and Elrod, M. J.: Formation and stability of atmospherically relevant isoprene-derived organosulfates and organonitrates, Environ. Sci. Technol., 45, 1895–1902, 2011. Day, D. A., Liu, S., Russell, L. M., and Ziemann, P. J.: Organonitrate group concentrations in submicron particles with high nitrate and organic fractions in coastal southern California, Atmos. Environ., 44, 1970–1979, http://dx.doi.org/10.1016/j.atmosenv.2010.02.045doi:10.1016/j.atmosenv.2010.02.045, 2010. Eddingsaas, N. C., VanderVelde, D. G., and Wennberg, P. O.: Kinetics and products of the acid-catalyzed ring-opening of atmospherically relevant butyl epoxy alcohols, J. Phys. Chem. A, 114, 8106–8113, http://dx.doi.org/10.1021/Jp103907cdoi:10.1021/Jp103907c, 2010. Frisch, M. J. T., Schlegel, G. W., Scuseria, H. B., Robb, G. E., Cheeseman, M. A., Montgomery Jr., J. R., Vreven, J. A., Kudin, T., Burant, K. N., Millam, J. C., Iyengar, J. M., Tomasi, S. S., Barone, J., Mennucci, V., Cossi, B., Scalmani, M., Rega, G., Petersson, N., Nakatsuji, G. A., Hada, H., Ehara, M., Toyota, M., Fukuda, K., Hasegawa, R., Ishida, J., Nakajima, M., Honda, T., Kitao, Y., Nakai, O., Klene, H., Li, M., Knox, X., Hratchian, J. E., Cross, H. P., Bakken, J. B., Adamo, V., Jaramillo, C., Gomperts, J., Stratmann, R., Yazyev, R. E., Austin, O., Cammi, A. J., Pomelli, R., Ochterski, C., Ayala, J. W., Morokuma, P. Y., Voth, K., Salvador, G. A., Dannenberg, P., Zakrzewski, J. J., Dapprich, V. G., Daniels, S., Strain, A. D., Farkas, M. C., Malick, O., Rabuck, D. K., Raghavachari, A. D., Foresman, K., Ortiz, J. B., Cui, J. V., Baboul, Q., Clifford, A. G., Cioslowski, S., Stefanov, J., Liu, B. B., Liashenko, G., Piskorz, A., Komaromi, P., Martin, I., Fox, R. L., Keith, D. J., Al-Laham, T., Peng, M. A., Nanayakkara, C. Y., Challacombe, A., Gill, M., Johnson, P. M. W., Chen, B., Wong, W., Gonzalez, C., and Pople, J. A.: Gaussian 03, Gaussian, Inc., Wallingford, CT, 2003. Froese, R. D. J., Humbel, S., Svensson, M., and Morokuma, K.: IMOMO(G2MS): A new high-level G2-like method for large molecules and its applications to Diels-Alder reactions, J. Phys. Chem. A, 101, 227–233, 1997. Froyd, K. D., Murphy, S. M., Murphy, D. M., De Gouw, J. A., Eddingsaas, N. C., and Wennberg, P. O.: Contribution of isoprene-derived organosulfates to free tropospheric aerosol mass, P. Natl. Acad. Sci., 107, 21360–21365, 2010. Gómez-González, Y., Surratt, J. D., Cuyckens, F., Szmigielski, R., Vermeylen, R., Jaoui, M., Lewandowski, M., Offenberg, J. H., Kleindienst, T. E., Edney, E. O., Blockhuys, F., Van Alsenoy, C., Maenhaut, W., and Claeys, M.: Characterization of organosulfates from the photooxidation of isoprene and unsaturated fatty acids in ambient aerosol using liquid chromatography/(-) electrospray ionization mass spectrometry, J. Mass Spectrom., 43, 371–382, http://dx.doi.org/10.1002/jms.1329doi:10.1002/jms.1329, 2008. Guenther, A., Karl, T., Harley, P., Wiedinmyer, C., Palmer, P. I., and Geron, C.: Estimates of global terrestrial isoprene emissions using MEGAN (Model of Emissions of Gases and Aerosols from Nature), Atmos. Chem. Phys., 6, 3181–3210, http://dx.doi.org/10.5194/acp-6-3181-2006doi:10.5194/acp-6-3181-2006, 2006. Hallquist, M., Wenger, J. C., Baltensperger, U., Rudich, Y., Simpson, D., Claeys, M., Dommen, J., Donahue, N. M., George, C., Goldstein, A. H., Hamilton, J. F., Herrmann, H., Hoffmann, T., Iinuma, Y., Jang, M., Jenkin, M. E., Jimenez, J. L., Kiendler-Scharr, A., Maenhaut, W., McFiggans, G., Mentel, Th. F., Monod, A., Prévôt, A. S. H., Seinfeld, J. H., Surratt, J. D., Szmigielski, R., and Wildt, J.: The formation, properties and impact of secondary organic aerosol: current and emerging issues, Atmos. Chem. Phys., 9, 5155–5236, http://dx.doi.org/10.5194/acp-9-5155-2009doi:10.5194/acp-9-5155-2009, 2009. Iraci, L. T., Riffel, B. G., Robinson, C. B., Michelsen, R. R., and Stephenson, R. M.: The acid catalyzed nitration of methanol: formation of methyl nitrate via aerosol chemistry, J. Atmos. Chem., 58, 253–266, 2007. Kua, J., Hanley, S. W., and De Haan, D. O.: Thermodynamics and kinetics of glyoxal dimer formation: a computational study, J. Phys. Chem. A, 112, 66–72, 2008. Lockwood, A. L., Shepson, P. B., Fiddler, M. N., and Alaghmand, M.: Isoprene nitrates: preparation, separation, identification, yields, and atmospheric chemistry, Atmos. Chem. Phys., 10, 6169–6178, http://dx.doi.org/10.5194/acp-10-6169-2010doi:10.5194/acp-10-6169-2010, 2010. Loudon, G. M.: Organic Chemistry, Addison-Wesley, Reading, Massachusetts, 1984. Matsunaga, A. and Ziemann, P. J.: Atmospheric Chemistry Special Feature: Yields of -hydroxynitrates, dihydroxynitrates, and trihydroxynitrates formed from OH radical-initiated reactions of 2-methyl-1-alkenes, P. Natl. Acad. Sci., 107, 6664–6669, http://dx.doi.org/10.1073/pnas.0910585107doi:10.1073/pnas.0910585107, 2010. Minerath, E. C. and Elrod, M. J.: Assessing the potential for diol and hydroxy sulfate ester formation from the reaction of epoxides in tropospheric aerosols, Environ. Sci. Technol., 43, 1386–1392, http://dx.doi.org/10.1021/es8029076doi:10.1021/es8029076, 2009. Minerath, E. C., Casale, M. T., and Elrod, M. J.: Kinetics feasibility study of alcohol sulfate esterification reactions in tropospheric aerosols, Environ. Sci. Technol., 42, 4410–4415, 2008. Minerath, E. C., Schultz, M. P., and Elrod, M. J.: Kinetics of the reactions of isoprene-derived epoxides in model tropospheric aerosol solutions, Environ. Sci. Technol., 43, 8133–8139, http://dx.doi.org/10.1021/es902304pdoi:10.1021/es902304p, 2009. Muthuramu, K., Shepson, P. B., and O'Brien, J. M.: Preparation, analysis, and atmospheric production of multifunctional organic nitrates, Environ. Sci. Technol., 27, 1117–1124, 1993. Ng, N. L., Kwan, A. J., Surratt, J. D., Chan, A. W. H., Chhabra, P. S., Sorooshian, A., Pye, H. O. T., Crounse, J. D., Wennberg, P. O., Flagan, R. C., and Seinfeld, J. H.: Secondary organic aerosol (SOA) formation from reaction of isoprene with nitrate radicals (NO<sub>3</sub>), Atmos. Chem. Phys., 8, 4117–4140, http://dx.doi.org/10.5194/acp-8-4117-2008doi:10.5194/acp-8-4117-2008, 2008. Nguyen, T. B., Roach, P. J., Laskin, J., Laskin, A., and Nizkorodov, S. A.: Effect of humidity on the composition of isoprene photooxidation secondary organic aerosol, Atmos. Chem. Phys., 11, 6931–6944, http://dx.doi.org/10.5194/acp-11-6931-2011doi:10.5194/acp-11-6931-2011, 2011. Nozière, B., Ekström, S., Alsberg, T., and Holmström, S.: Radical-initiated formation of organosulfates and surfactants in atmospheric aerosols, Geophys. Res. Lett., 37, L05806, http://dx.doi.org/10.1029/2009gl041683doi:10.1029/2009gl041683, 2010. Paulot, F., Crounse, J. D., Kjaergaard, H. G., Kurten, A., St. Clair, J. M., Seinfeld, J. H., and Wennberg, P. O.: Unexpected epoxide formation in the gas-phase photooxidation of isoprene, Science, 325, 730–733, http://dx.doi.org/10.1126/science.1172910doi:10.1126/science.1172910, 2009. Perring, A. E., Bertram, T. H., Wooldridge, P. J., Fried, A., Heikes, B. G., Dibb, J., Crounse, J. D., Wennberg, P. O., Blake, N. J., Blake, D. R., Brune, W. H., Singh, H. B., and Cohen, R. C.: Airborne observations of total RONO<sub>2</sub>: new constraints on the yield and lifetime of isoprene nitrates, Atmos. Chem. Phys., 9, 1451–1463, http://dx.doi.org/10.5194/acp-9-1451-2009doi:10.5194/acp-9-1451-2009, 2009a. Perring, A. E., Wisthaler, A., Graus, M., Wooldridge, P. J., Lockwood, A. L., Mielke, L. H., Shepson, P. B., Hansel, A., and Cohen, R. C.: A product study of the isoprene+NO<sub>3</sub> reaction, Atmos. Chem. Phys., 9, 4945–4956, http://dx.doi.org/10.5194/acp-9-4945-2009doi:10.5194/acp-9-4945-2009, 2009b. Pope III, C. A. and Dockery, D. W.: Health effects of fine particulate air pollution: lines that connect, J. Air Waste Manage., 56, 709–742, 2006. Ranschaert, D. L., Schneider, N. J., and Elrod, M. J.: Kinetics of the C<sub>2</sub>H$_5$O<sub>2</sub> + NO<sub>x</sub> reactions: temperature dependence of the overall rate constant and the C<sub>2</sub>H$_5$ONO<sub>2</sub> Branching Channel of C<sub>2</sub>H$_5$O<sub>2</sub> + NO, J. Phys. Chem. A, 104, 5758–5765, 2000. Rudzinski, K. J., Gmachowski, L., and Kuznietsova, I.: Reactions of isoprene and sulphoxy radical-anions – a possible source of atmospheric organosulphites and organosulphates, Atmos. Chem. Phys., 9, 2129–2140, http://dx.doi.org/10.5194/acp-9-2129-2009doi:10.5194/acp-9-2129-2009, 2009. Shen, C. Y. and Ruest, D. A.: Production of diglycolic acid by nitric acid oxidation of diethylene glycol, Ind. Eng. Chem. Process Des. Dev., 19, 401–404, 1980. Shimizu, A., Tanaka, K., and Fujimori, M.: Abatement technologies for N<sub>2</sub>O emissions in the adipic acid industry, Chemosphere, 2, 425–434, 2000. Surratt, J. D., Lewandowski, M., Offenberg, J. H., Jaoui, M., Kleindienst, T. E., Edney, E. O., and Seinfeld, J. H.: Effect of acidity on secondary organic aerosol formation from isoprene, Environ. Sci. Technol., 41, 5363–5369, 2007. Surratt, J. D., Gómez-González, Y., Chan, A. W. H., Vermeylen, R., Shahgholi, M., Kleindienst, T. E., Edney, E. O., Offenberg, J. H., Lewandowski, M., Jaoui, M., Maenhaut, W., Claeys, M., Flagan, R. C., and Seinfield, J. H.: Organosulfate formation in biogenic secondary organic aerosol, J. Phys. Chem. A, 112, 8345–8378, 2008. Surratt, J. D., Chan, A. W. H., Eddingsaas, N. C., Chan, M., Loza, C. L., Kwan, A. J., Hersey, S. P., Flagan, R. C., Wennberg, P. O., and Seinfeld, J. H.: Reactive intermediates revealed in secondary organic aerosol formation from isoprene, P. Natl. Acad. Sci., 107, 6640–6645, 2010. Szmigielski, R., Vermeylen, R., Dommen, J., Metzger, A., Maenhaut, W., Baltensperger, U., and Claeys, M.: The acid effect in the formation of 2-methyltetrols from the photooxidation of isoprene in the presence of NO<sub>x</sub>, Atmos. Res., 98, 183–189, http://dx.doi.org/10.1016/j.atmosres.2010.02.012doi:10.1016/j.atmosres.2010.02.012, 2010. Tomasi, J., Mennucci, B., and Cammi, R.: Quantum mechanical continuum solvation models, Chem. Rev., 105, 2999–3093, 2005. van Asselt, W. J. and van Krevelen, D. W.: The preparation of adipic acid by oxidation of cyclohexanol and cyclohexanone with nitric acid. I. Reaction mechanism, Recl. Trav. Chim. Pay B, 82, 51–67, 1963. Wang, W., Kourtchev, I., Graham, B., Cafmeyer, J., Maenhaut, W., and Claeys, M.: Characterization of oxygenated derivatives of isoprene related to 2-methyltetrols in Amazonian aerosols using trimethylsilylation and gas chromatography/ion trap mass spectrometry, Rapid Commun. Mass Spectrom., 19, 1343–1351, http://dx.doi.org/10.1002/rcm.1940doi:10.1002/rcm.1940, 2005. Wexler, A. S. and Clegg, S. L.: Atmospheric aerosol models for systems including the ions H$^+$, NH$_4^+$\underline , Na$^+$, SO$_4^2-$, NO$_3^-$, Cl$^-$, Br$^-$, and H<sub>2</sub>O, J. Geophys. Res., 107, D000451, http://dx.doi.org/10.1029/2001JD000451doi:10.1029/2001JD000451, 2002. Wiesen, P., Kleffmann, J., Kurtenback, R., and Becker, K. H.: Mechanistic study of the heterogeneous converison of NO<sub>2</sub> into HONO and N<sub>2</sub>O on acid surfaces, Faraday Discuss., 100, 121–127, 1995. Wolfenden, R. and Yuan, Y.: Monoalkyl sulfates as alkylating agents in water, alkylsulfatase rate enhancements, and the "energy-rich" nature of sulfate half-esters, P. Natl. Acad. Sci, 104, 83–86, http://dx.doi.org/10.1073/pnas.0609644104doi:10.1073/pnas.0609644104, 2007. Zhang, Q., Jimenez, J. L., Worsnop, D. R., and Canagaratna, M.: A case study of urban particle acidity and its influence on secondary organic aerosol, Environ. Sci. Technol., 41, 3213–3219, 2007.