Mechanism of hydrogen transfer in arsane generation by aqueous tetrahydridoborate: Interference effects of AuIII and other noble metals

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DOIResolve DOI: http://doi.org/10.1016/j.sab.2011.09.009
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TypeArticle
Journal titleSpectrochimica Acta - Part B Atomic Spectroscopy
ISSN0584-8547
Volume66
Issue9-Oct
Pages740747; # of pages: 8
SubjectBatch experiments; Continuous flows; Gas chromatography-mass spectrometry; Generation systems; H/D exchange; Hydride generations; Hydrogen transfer; Interference effects; Intermediate specie; Isotopic composition; Metal concentrations; Reaction mechanism; Reaction yields; Tetrahydridoborate; Trace level; Arsenic; Atomic absorption spectrometry; Gas chromatography; Hydrides; Hydrogen; Inert gases; Isotopes; Mass spectrometry; Metal ions; Metals; Platinum; Precious metals; Reaction intermediates; Palladium
AbstractThe generation of arsane by reaction of either NaBH4 (THB) or NaBD4 (TDB) in aqueous solution with AsIII (1 mg L -1) has been studied in the presence of several transition and noble metals at trace levels. A continuous flow generation system coupled with both atomic absorption spectrometry (AAS) and gas chromatography mass spectrometry (GC-MS) were employed to measure the effect of AuIII (0.5 - 20 mg L-1) on reaction yield and isotopic composition of arsane. In a different set of batch experiments, GC-MS was employed to measure the effect of AuIII, PdII, PtII, NiII and Cu II on the isotopic composition of arsane. AuIII, Pd II and PtII induce a significant perturbation in the mechanism of hydride generation, promoting the incorporation of a large amount of hydrogen derived from the solvent into the final arsane. This effect takes place at metal concentration levels which hardly affect the generation efficiency of arsane and can likely be addressed by the action of intermediate species formed in the early stage of the reaction between the metal ion and the TDB-arsenic complex. Nanoparticles and colloids arising from the interaction of the metal and TDB are able to capture the final arsane but they do not promote H/D exchange on the already formed arsane. This evidence reveals the existence of a new type of interference in chemical generation of volatile hydrides - a "mechanistic interference" - in addition to the already known yield interferences. © 2011 Elsevier B.V. All rights reserved.
Publication date
LanguageEnglish
AffiliationNRC Institute for National Measurement Standards; National Research Council Canada
Peer reviewedYes
NPARC number21271755
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Record identifier3013cb3d-ce4d-40e9-aec2-30e6bc3a9ac1
Record created2014-03-24
Record modified2016-05-09
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