Formation of Two Chromium(III) Dithiocarbamates from Cr(VI) in Solvent Extraction System and Origin of Oxygen Atom in Bis(1-pyrrolidinecarbodithioato)[1-pyrrolidinecarbothio(thioperoxoato)]chromium(III)
Bibliographic record
Abstract
Abstract In order to explore the cause of a distinctive extraction behavior of Cr(VI) in the dithiocarbamate formation-solvent extraction systems, extracted chromium compounds were investigated and relationships between the formation of the compounds and the extraction behavior were studied. Chromatographic separation and spectroscopic analyses showed that two kinds of chromium(III) dithiocarbamates (i.e. tris(1-pyrrolidinecarbodithioato)chromium(III) and bis(1-pyrrolidinecarbodithioato)[1-pyrrolidinecarbothio(thioperoxoato)]chromium(III)) were formed and extracted in an ammonium 1-pyrrolidinecarbodithioate (APCD)/diisobutyl ketone (DIBK) solvent extraction system. The two products comprised most of the extracted chromium. Concentrations of the two dithiocarbamates in extracts were determined using double wavelengths analysis. The dependence of concentration ratio of the two complexes on pH was also investigated. The results of the investigation clarified that a major extract obtained under high pH condition was the thioperoxo complex and that the percentage of the tris complex increased with decreasing pH. Furthermore, it was clarified that the unusual extraction behavior of chromate was distinguished by the formation of thioperoxo complex. In order to elucidate the formation mechanism of the thioperoxo complex, the origin of an oxygen atom in the molecule of the thioperoxo complex was determined with an isotope labeling technique. The labeling experiments clarified that the source of the oxygen atom of the complex molecule was chromate ion and that the oxygen atom was fixed to chromium atom prior to the rate determination step of the formation of the thioperoxo complex.
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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 | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.001 | 0.000 |
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".