Gas chromatography–mass spectrometry study of hydrogen–deuterium exchange reactions of volatile hydrides of As, Sb, Bi, Ge and Sn in aqueous media

D’Ulivo, Alessandro; Mester, Zoltán; Meija, Juris; Sturgeon, Ralph E.

doi:10.1016/j.sab.2006.06.004

Cited by 21 publications

(11 citation statements)

References 21 publications

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“…As reported recently, neither AsH 3 nor AsD 3 undergoes H/D exchange when in contact with acidic solutions (0 < pH, pD < 7) for several minutes [17]. In contrast, methylarsanes undergo fast H/D exchange in acidic media [18].…”

Section: Resultsmentioning

confidence: 76%

Condensation cascades and methylgroup transfer reactions during the formation of arsane, methyl- and dimethylarsane by aqueous borohydride and (methyl) arsenates

et al. 2011

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Access and use of this website and the material on it are subject to the Terms and Conditions set forth at Condensation cascades and methylgroup transfer reactions during the formation of arsane, methyl-and dimethylarsane by aqueous borohydride and (methyl) arsenates D'Ulivo, Alessandro; Meija, Juris; Mester, Zoltán; Pagliano, Enea; Sturgeon, Ralph E.http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/jsp/nparc_cp.jsp?lang=fr L'accès à ce site Web et l'utilisation de son contenu sont assujettis aux conditions présentées dans le site LISEZ CES CONDITIONS ATTENTIVEMENT AVANT D'UTILISER CE SITE WEB. NRC Publications Record / Notice d'Archives des publications de CNRC:http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/ctrl?action=rtdoc&an=21268282&lang=en http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/ctrl?action=rtdoc&an=21268282&lang=fr READ THESE TERMS AND CONDITIONS CAREFULLY BEFORE USING THIS WEBSITE.http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/jsp/nparc_cp.jsp?lang=en Vous avez des questions? Nous pouvons vous aider. Pour communiquer directement avec un auteur, consultez la première page de la revue dans laquelle son article a été publié afin de trouver ses coordonnées. Si vous n'arrivez pas à les repérer, communiquez avec nous à PublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. Questions? Contact the NRC Publications Archive team atPublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. If you wish to email the authors directly, please see the first page of the publication for their contact information. NRC Publications Archive Archives des publications du CNRCThis publication could be one of several versions: author's original, accepted manuscript or the publisher's version. / La version de cette publication peut être l'une des suivantes : la version prépublication de l'auteur, la version acceptée du manuscrit ou la version de l'éditeur. For the publisher's version, please access the DOI link below./ Pour consulter la version de l'éditeur, utilisez le lien DOI ci-dessous.http://doi.org/10.1007/s00216-011-5503-4Analytical and Bioanalytical Chemistry, 402, 2, pp. 921-933, 2011-10-30 ABSTRACTThe formation of volatile products during the reaction of As(III), As(V), MeAsO(OH) 2 and Me 2 AsO(OH) with aqueous NaBH 4 has been investigated and the formation of arsanes, di-and triarsanes has been detected . The presence of triarsanes is reported here for the first time. Di-and triarsanes are likely formed in condensation cascade reactions, whereas trimethylarsane arises via the transfer of a methyl group. The formation of volatile byproducts is considerably reduced by increasing the acidity of the medium and the concentration of NaBH 4 or by the addition of thiols, such as cysteine. A reaction scheme is proposed which reconciles the evidence reported herein and elsewhere in the literature that is valid for both analytical (trace analysis) and non-analytical reaction conditions.

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Section: Resultsmentioning

confidence: 76%

Condensation cascades and methylgroup transfer reactions during the formation of arsane, methyl- and dimethylarsane by aqueous borohydride and (methyl) arsenates

et al. 2011

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“…Arsane and stibane undergo deprotonation in alkaline media (pH > 7) as has been demonstrated by H-D exchange experiments, but the equilibrium concentration of deprotonated species [EH 2 ] -(when E is As or Sb) is negligible [89]. Arsane, in addition, can be protonated to give AsH 4 + under extreme acidic conditions (when [H 3 O + ] is between 3 and 6 mol L -1 ) [89].…”

Section: Protonation or Deprotonation Of The Final Hydridesmentioning

confidence: 88%

“…; Y = H 2 O, OH -, Cl -, etc., and z is the charge) to be converted into its volatile hydrides, EH m . The most informative experiments on the mechanisms are those involving deuterium-labeled reagents, deuterated boranes in H 2 O/H 3 O + , or hydrogenated boranes in D 2 O/D 3 O + , coupled with GC-MS [36,41,[88][89][90]. In general, those reactions led to formation of a mixture of isotopologues, EH m-x D x , which result from the different processes through which H and D can be incorporated into the final hydrides.…”

Section: Use Of Deuterium-labeled Reagentsmentioning

confidence: 99%

“…In dedicated studies on H-D exchange using pure hydrogenated and deuterated hydrides [89], it was reported that no significant H-D exchange was detected within the following pH intervals that can be considered free from interference: arsane pH range from 0 to 7, stibane pH range from 0 to 7, bismuthane, germane, and stannane pH range from 0 to 13. Dihydrogen selenide, due to its acidic character, exchanges quickly in solution and precludes the use of deuterium-labeled reagents in mechanistic studies [36].…”

Section: Use Of Deuterium-labeled Reagentsmentioning

confidence: 99%

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Mechanisms of chemical generation of volatile hydrides for trace element determination (IUPAC Technical Report)

D’Ulivo

Dědina

Mester

et al. 2011

Pure and Applied Chemistry

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Aqueous-phase chemical generation of volatile hydrides (CHG) by derivatization with borane complexes is one of the most powerful and widely employed methods for determination and speciation analysis of trace and ultratrace elements (viz. Ge, Sn, Pb, As, Sb, Bi, Se, Te, Hg, Cd, and, more recently, several transition and noble metals) when coupled with atomic and mass spectrometric detection techniques. Analytical CHG is still dominated by erroneous concepts, which have been disseminated and consolidated within the analytical scientific community over the course of many years. The overall approach to CHG has thus remained completely empirical, which hinders possibilities for further development. This report is focused on the rationalization and clarification of fundamental aspects related to CHG: (i) mechanism of hydrolysis of borane complexes; (ii) mechanism of hydrogen transfer from the borane complex to the analytical substrate; (iii) mechanisms through which the different chemical reaction conditions control the CHG process; and (iv) mechanism of action of chemical additives and foreign species. Enhanced comprehension of these different mechanisms and their mutual influence can be achieved in light of the present state of knowledge. This provides the tools to explain the reactivity of a CHG system and contributes to the clarification of several controversial aspects and the elimination of erroneous concepts in CHG.

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“…Experimental conditions are chosen to avoid any unwanted H/D exchange with the solvent (H 2 O) [20].The mole fraction of deuterium in the NaBH 4 and NaBD 4 mixtures was obtained Scheme 1. Formation of di-and triarsanes in a concerted reduction and condensation cascade (R 0 H or OH).…”

Section: Mechanism Of Formation Of Polyarsanesmentioning

confidence: 99%

The Binomial Distribution of Hydrogen and Deuterium in Arsanes, Diarsanes, and Triarsanes Generated from As(Iii)/[BH_nD_4-n]⁻ and the Effect of Trace Amounts of Rh(Iii) Ions

D’Ulivo

Mester

Sturgeon

et al. 2012

J. Am. Soc. Mass Spectrom.

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Recent 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 (As 2 H n D 4-n and As 3 H n D 5-n ) from the mass spectra of isotopically pure compounds (As 2 H 4 , As 2 D 4 , As 3 H 5 , and As 3 D 5 ). 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(III). The presence of Rh(III) in the As(III)/ [BD 4 ] − system entails the incorporation of hydrogen into the arsanes arising from the solvent, altering the expected binomial H/D distribution.

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Gas chromatography–mass spectrometry study of hydrogen–deuterium exchange reactions of volatile hydrides of As, Sb, Bi, Ge and Sn in aqueous media

Cited by 21 publications

References 21 publications

Condensation cascades and methylgroup transfer reactions during the formation of arsane, methyl- and dimethylarsane by aqueous borohydride and (methyl) arsenates

Condensation cascades and methylgroup transfer reactions during the formation of arsane, methyl- and dimethylarsane by aqueous borohydride and (methyl) arsenates

Mechanisms of chemical generation of volatile hydrides for trace element determination (IUPAC Technical Report)

The Binomial Distribution of Hydrogen and Deuterium in Arsanes, Diarsanes, and Triarsanes Generated from As(Iii)/[BH_nD_4-n]⁻ and the Effect of Trace Amounts of Rh(Iii) Ions

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Gas chromatography–mass spectrometry study of hydrogen–deuterium exchange reactions of volatile hydrides of As, Sb, Bi, Ge and Sn in aqueous media

Cited by 21 publications

References 21 publications

Condensation cascades and methylgroup transfer reactions during the formation of arsane, methyl- and dimethylarsane by aqueous borohydride and (methyl) arsenates

Condensation cascades and methylgroup transfer reactions during the formation of arsane, methyl- and dimethylarsane by aqueous borohydride and (methyl) arsenates

Mechanisms of chemical generation of volatile hydrides for trace element determination (IUPAC Technical Report)

The Binomial Distribution of Hydrogen and Deuterium in Arsanes, Diarsanes, and Triarsanes Generated from As(Iii)/[BHnD4-n]− and the Effect of Trace Amounts of Rh(Iii) Ions

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The Binomial Distribution of Hydrogen and Deuterium in Arsanes, Diarsanes, and Triarsanes Generated from As(Iii)/[BH_nD_4-n]⁻ and the Effect of Trace Amounts of Rh(Iii) Ions