EarthRef.org Reference Database (ERR)
Development and Maintenance by the EarthRef.org Database Team

Detailed Reference Information
Nowak et al. 2002
Nowak, J.B., Huey, L.G., Eisele, F.L., Tanner, D.J., Mauldin, R.L., Cantrell, C., Kosciuch, E. and Davis, D.D. (2002). Chemical ionization mass spectrometry technique for detection of dimethylsulfoxide and ammonia. Journal of Geophysical Research 107: doi: 10.1029/2001JD001058. issn: 0148-0227.

A chemical ionization mass spectrometer (CIMS) was used to study reactions of protonated ethanol clusters (C2H5OH)nH+ with dimethylsulfoxide (DMSO), dimethylsulfone (DMSO2), ammonia (NH3), and a series of nonmethane hydrocarbons (NMHCs) and volatile organic compounds (VOCs). The reactivity of the (C2H5OH)nH+ cluster ions is a function of cluster size with reactivity decreasing as cluster size increases. Ethanol cluster ion distributions that formed at atmospheric pressure from 24 ppbv, 900 ppmv, and 1% ethanol/N2 gas mixtures were studied. Small (C2H5OH)nH+ clusters, those formed using the 24 ppbv ethanol/N2 mixture, react at or near the collisional rate with DMSO, NH3, acetone, and methyl vinyl ketone (MVK). The effective ion molecule rate coefficients are 1.8 ¿ 10-9, 1.5 ¿ 10-9, 1.0 ¿ 10-9, and 1.6 ¿ 10-9 cm3 molecule-1 s-1, respectively. Only DMSO and NH3 react efficiently with the two larger (C2H5OH)nH+ cluster ion distributions studied. The effective rate coefficients for DMSO and NH3 with the 900 ppmv ethanol cluster ion distribution are 1.5 ¿ 10-9 and 0.7 ¿ 10-9 cm3 molecule-1 s-1, respectively. The effective rate coefficient for DMSO with the 1% ethanol/N2 mixture is 0.35 ¿ 10-9 cm3 molecule-1 s-1, while NH3 reaches equilibrium with this cluster ion distribution. Experiments show that large (C2H5OH)nH+ ion clusters must be used at relative humidities greater than 50% at 20¿C to prevent formation of and subsequent interferences from H3O+ ions. These results demonstrate that the (C2H5OH)nH+ ion chemistry can selectively detect DMSO and NH3 under most ambient atmospheric conditions with high sensitivity.

BACKGROUND DATA FILES

Abstract

Keywords
Atmospheric Composition and Structure, Aerosols and particles (0345, 4801), Atmospheric Composition and Structure, Troposphere--composition and chemistry, Atmospheric Composition and Structure, Instruments and techniques
Journal
Journal of Geophysical Research
http://www.agu.org/journals/jb/
Publisher
American Geophysical Union
2000 Florida Avenue N.W.
Washington, D.C. 20009-1277
USA
1-202-462-6900
1-202-328-0566
service@agu.org
Click to clear formClick to return to previous pageClick to submit