The binomial distribution of hydrogen and deuterium in arsanes, diarsanes, and triarsanes generated from As(Ιιι)/[BHnD4-n]− and the effect of trace amounts of Rh(Ιιι) ions

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DOIResolve DOI: http://doi.org/10.1007/s13361-012-0489-5
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TypeArticle
Journal titleJournal of The American Society for Mass Spectrometry
ISSN1044-0305
1879-1123
Volume23
Issue12
Pages21782186; # of pages: 9
Subjecthydride generation; statistical modeling; arsane, diarsane and triarsane; mechanistic interference
AbstractRecent studies of the formation of arsane in the borohydride/arsenate reaction demonstrate the occurrence of condensation cascades whereby small quantities of di- and triarsanes are formed. In this study, the isotopic composition of these di- and triarsanes was examined using deuterium labelled borohydrides. A statistical model was employed to construct the mass spectra of all diarsane and triarsane isotopologues (As2H n D4-n and As3H n D5-n) from the mass spectra of isotopically pure compounds (As2H4, As2D4, As3H5, and As3D5). Subsequent deconvolution of the experimental mixed spectra shows that incorporation of hydrogen closely follows the binomial distribution, in accord with arsane formation. The H/D distribution in arsane, diarsane, and triarsane isotopologues is binomial in the absence of any interference. However, this is significantly altered by the presence of some transition metals; presented here, for the first time, are the effects of Rh(Ιιι). The presence of Rh(Ιιι) in the As(Ιιι)/[BD4]− system entails the incorporation of hydrogen into the arsanes arising from the solvent, altering the expected binomial H/D distribution.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada; Measurement Science and Standards
Peer reviewedYes
Identifier489
NPARC number21268627
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Record identifier911f8fa2-3e1d-4563-b484-e8d4033ed746
Record created2013-10-31
Record modified2016-05-09
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