Journal of Atmospheric Chemistry

, Volume 45, Issue 3, pp 289–299 | Cite as

Kinetics and Products of the Gas-Phase Reaction of OH Radicals with 5-Hydroxy-2-Pentanone at 296± 2 K

  • Sara M. Aschmann
  • Janet Arey
  • Roger Atkinson
Article

Abstract

The 1,4-hydroxycarbonyl 5-hydroxy-2-pentanone is an important product of the gas-phase reaction of OH radicals with n-pentane in the presence of NO. We have used a relative rate method with 4-methyl-2-pentanone as the reference compound to measure the rate constant for the reaction of OH radicals with 5-hydroxy-2-pentanone at 296 ± 2 K. The carbonyls were sampled by on-fiber derivatization using a Solid Phase Micro Extraction (SPME) fiber coated with O> -(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride with subsequent thermal desorption of the oxime derivatives and quantification by gas chromatography with flame ionization detection. For comparison, the reference compound was also analyzed following sample collection onto a Tenax adsorbent cartridge. Products of the reaction were investigated using coated-fiber SPME sampling with gas chromatography-mass spectrometry analysis as well as by using in situ atmospheric pressure ionization mass spectrometry. A rate constant for the reaction of OH radicals with 5-hydroxy-2-pentanone of (1.6 ± 0.4) × 10−11 cm3 molecule−1 s−1 was obtained at 296 ± 2 K. Two dicarbonyl products, of molecular weight 86 and 100, were observed and are attributed to CH3C(O)CH2CHO and CH3C(O)CH2CH2CHO, respectively. Reaction schemes leading to these products are presented.

atmospheric reactions 5-hydroxy-2-pentanone hydroxyl radical reaction products SPME 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. Arey, J., Aschmann, S. M., Kwok, E. S. C., and Atkinson, R., 2001: Alkyl nitrate, hydroxyalkyl nitrate, and hydroxycarbonyl formation from the NOx-air photooxidations of C5-C8 n-alkanes, J. Phys. Chem. A 105, 1020-1027.Google Scholar
  2. Aschmann, S. M., Chew, A. A., Arey, J., and Atkinson, R., 1997: Products of the gas-phase reaction of OH radicals with cyclohexane: Reactions of the cyclohexoxy radical, J. Phys. Chem. A 101, 8042-8048.Google Scholar
  3. Aschmann, S. M. and Atkinson, R., 1999: Products of the gas-phase reactions of the OH radical with n-butyl methyl ether and 2-isopropoxyethanol: Reactions of ROC(O(su▪))<radicals, Int. J. Chem. Kinet. 31, 501-513.Google Scholar
  4. Aschmann, S. M., Arey, J., and Atkinson, R., 2001: Atmospheric chemistry of three C10 alkanes, J. Phys. Chem. A 105, 7598-7606.Google Scholar
  5. Atkinson, R., 1994: Gas-phase tropospheric chemistry of organic compounds, J. Phys. Chem. Ref. Data Monograph 2, 1-216.Google Scholar
  6. Atkinson, R. and Aschmann, S. M., 1995: Products of the gas-phase OH radical-initiated reactions of 4-methyl-2-pentanone and 2,6-dimethyl-4-heptanone, Int. J. Chem. Kinet. 27, 261-275.Google Scholar
  7. Atkinson, R., 1997: Gas-phase tropospheric chemistry of volatile organic compounds: 1. alkanes and alkenes, J. Phys. Chem. Ref. Data 26, 215-290.Google Scholar
  8. Atkinson, R., 2000: Atmospheric chemistry of VOCs and NOx, Atmos. Environ. 34, 2063-2101.Google Scholar
  9. Atkinson, R., Tuazon, E. C., and Aschmann, S. M., 2000: Atmospheric chemistry of 2-pentanone and 2-heptanone, Environ. Sci. Technol. 34, 623-631.Google Scholar
  10. Bethel, H. L., Atkinson, R., and Arey, J., 2001: Kinetics and products of the reactions of selected diols with the OH radical, Int. J. Chem. Kinet. 33, 310-316.Google Scholar
  11. Chew, A. A., Atkinson, R., and Aschmann, S. M., 1998: Kinetics of the gas-phase reactions of NO3 radicals with a series of alcohols, glycol ethers, ethers and chloroalkenes, J. Chem. Soc. Faraday Trans. 94, 1083-1089.Google Scholar
  12. Eberhard, J., Müller, C., Stocker, D.W., and Kerr, J. A., 1995: Isomerization of alkoxy radicals under atmospheric conditions, Environ. Sci. Technol. 29, 232-241.Google Scholar
  13. Koziel, J. A., Noah, J., and Pawliszyn, J., 2001: Field sampling and determination of formaldehyde in indoor air with solid-phase microextraction and on-fiber derivatization, Environ, Sci. Technol. 35, 1481-1486.Google Scholar
  14. Kramp, F. and Paulson, S. E., 1998: On the uncertainties in the rate coefficients for OH reactions with hydrocarbons, and the rate coefficients of the 1,3,5-trimethylbenzene and m-xylene reactions with OH radicals in the gas phase, J. Phys. Chem. A 102, 2685-2690.Google Scholar
  15. Krol, M., van Leeuwen, P. J., and Lelieveld, J., 1998: Global OH trend inferred from methylchloroform measurements, J. Geophys. Res. 103, 10697-10711.Google Scholar
  16. Kwok, E. S. C. and Atkinson, R., 1995: Estimation of hydroxyl radical reaction rate constants for gasphase organic compounds using a structure-reactivity relationship: an update, Atmos. Environ. 29, 1685-1695.Google Scholar
  17. Kwok, E. S. C., Arey, J., and Atkinson, R., 1996: Alkoxy radical isomerization in the OH radicalinitiated reactions of C4-C8 n-alkanes, J. Phys. Chem. 100, 214-219.Google Scholar
  18. Martin, P., Tuazon, E. C., Aschmann, S. M., Arey, J., and Atkinson, R., 2002: Formation and atmospheric reactions of 4,5-dihydro-2-methylfuran, J. Phys. Chem. A 106, 11492-11501.Google Scholar
  19. Martos, P. A. and Pawliszyn, J., 1998: Sampling and determination of formaldehyde using solid-phase microextraction with on-fiber derivatization, Anal. Chem. 70, 2311-2320.Google Scholar
  20. Prinn, R. G., Huang, J., Weiss, R. F., Cunnold, D. M., Fraser, P. J., Simmonds, P. G., McCulloch, A., Harth, C., Salameh, P., O'Doherty, S., Wang, R. H. J., Porter, L., and Miller, B. R., 2001: Evidence for substantial variations of atmospheric hydroxyl radicals in the past two decades, Science 292, 1882-1888.Google Scholar
  21. Reisen, F., Aschmann, S. M., Atkinson, R., and Arey, J., 2003: Hydroxyaldehyde products from hydroxyl radical reactions of Z-3-hexen-1-ol and 2-methyl-3-buten-2-ol quantified by SPME and API-MS, Environ. Sci. Technol., submitted for publication.Google Scholar
  22. Streitwieser, A., Jr. and Heathcock, C. H., 1976: Introduction to Organic Chemistry,Macmillan, New York, NY, p. 679.Google Scholar
  23. Taylor,W. D., Allston, T. D., Moscato, M. J., Fazekas, G. B., Kozlowski, R., and Takacs, G. A., 1980: Atmospheric photodissociation lifetimes for nitromethane, methyl nitrite, and methyl nitrate, Int. J. Chem. Kinet. 12, 231-240.Google Scholar
  24. Tuazon, E. C., Aschmann, S. M., and Atkinson, R., 1999: Products of the gas-phase reaction of the OH radical with the dibasic ester CH3OC(O)CH2CH2CH2C(O)OCH3, Environ. Sci. Technol. 33, 2885-2890.Google Scholar

Copyright information

© Kluwer Academic Publishers 2003

Authors and Affiliations

  • Sara M. Aschmann
    • 1
  • Janet Arey
    • 1
    • 2
  • Roger Atkinson
    • 1
    • 2
    • 3
  1. 1.Air Pollution Research CenterUniversity of CaliforniaRiversideU.S.A
  2. 2.Department of Environmental Sciences and Interdepartmental Graduate Program in Environmental ToxicologyUSA
  3. 3.Department of ChemistryUSA

Personalised recommendations