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

Aqueous-phase chemical generation of volatile hydrides (CHG) by derivatization with borane complexes is one of the most powerful and widely employed methods for deter- mination 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 trans- fer 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 knowl- edge. 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.