Mechanisms of chemical generation of volatile hydrides for trace element determination (IUPAC Technical Report)
Bibliographic record
Abstract
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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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.002 | 0.001 |
| Meta-epidemiology (narrow) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.001 |
| Bibliometrics | 0.002 | 0.001 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.001 | 0.002 |
| Open science | 0.003 | 0.001 |
| Research integrity | 0.001 | 0.002 |
| Insufficient payload (model declined to judge) | 0.005 | 0.004 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".