| Résumé | The mechanisms of chemical vapor generation (CVG) of transition and noble metals by reaction with tetrahydroborate(III) have been investigated in an effort to reconcile fundamental properties of compounds containing metal–hydride bonds with the experimental evidence collected in the present work and in the recent analytical literature on CVG. Silver, gold and rhodium were investigated in detail. Various materials constituting the wetted surfaces of the reaction apparatus (Ryton, glass, silanized glass) were examined for their effect on the overall process, as was the presence of surface-active agents (Triton X-100TM, antifoam B). Two types of reactions contribute to the formation of volatile species. The first (primary reaction) occurs through homogeneous liquid phase reactions between aqueous analyte complexes (MLn) and hydroboron species (BH4− and its hydrolysis products). The second (secondary reaction) is a surface mediated reaction between reaction intermediates, mostly formed in the primary reaction and chemisorbed by active sites on surfaces, and hydroboron species. The participation of active surface sites generally improves the efficiency of CVG compared with use of an inert surface, but this feature cannot always be usefully employed in analytical applications due to slow reaction kinetics producing memory effects. Reaction intermediates which can be classified as hydrido metal complexes, LnMHx, possess complex chemistry, making interpretation of experimental results difficult. Hydrido metal complexes, in addition to free atoms and nanoparticles, may constitute the volatile species leaving the solution and/or reaching the atomizer. |
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