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Detailed Reference Information |
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. |
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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. |
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Abstract |
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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 |
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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 |
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