Reduction of the Aqueous Mercuric Ion by Sulfite: UV Spectrum of HgSO<sub>3</sub> and Its Intramolecular Redox Reaction
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Bibliographic record
Abstract
Aqueous hydrogen sulfite reacts with Hg 2+ to form, in the absence of excess HSO 3 -, the HgSO 3 complex, observed here for the first time. Its UV spectrum is described by ε(234 nm) = (1.57 ± 0.05) × 10 4 M -1 cm -1 . HgSO 3 decomposes in an intramolecular redox reaction which is kinetically first-order. The rate constant is independent of [Hg 2+ ], [HSO 3 - ], [O 2(aq) ], and ionic strength. An acid-assisted pathway becomes significant at pH ≤ 1, attributed to the contribution of HgSO 3 H + . The rate of the intramolecular reaction of HgSO 3 was measured by trapping the Hg 0 product as Hg 2 2+; the value of the rate constant is k 0 = (0.0106 ± 0.0009) s -1 at 25.0 °C, pH 3. The activation parameters for pH 3, Δ H ‡ and Δ S ‡, are (105 ± 2) kJ/mol and (68 ± 6) J/mol·K, respectively, consistent with a unimolecular bond cleavage mechanism. A pathway involving H 2 O-induced concerted 2e - transfer is proposed.
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Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| 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) | 0.000 | 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 it