Kinetics of Reduction of Aqueous Hexaammineruthenium(III) Ion at Pt and Au Microelectrodes: Electrolyte, Temperature, and Pressure Effects
Bibliographic record
Abstract
Rate constants kel obtained by impedance spectroscopy for the reduction of Ru(NH3)6(3+) at polycrystalline Pt and Au ultramicroelectrodes depend strongly on the identity and concentration of the anion present in the order CF3SO3(-) < Cl(-) < ClO4(-), but not on the cation of the supporting electrolyte (Na(+), K(+), H(+)). For Cl(-) as the sole anion present, kel is directly proportional to the total [Cl(-)], such that kel would be zero if Cl(-) were hypothetically absent, indicating that Cl(-) is directly involved in mediation of the Ru(NH3)6(3+/2+) electron transfer. For CF3SO3(-) as the sole counterion, the dependence of kel on the total [CF3SO3(-)] is not linear, possibly because blocking of the available electrode surface becomes dominant at high triflate concentrations. Volumes of activation ΔVel(⧧) for reduction of Ru(NH3)6(3+) at an electrode in presence of Cl(-) or CF3SO3(-) are much more negative than predictions based on theory (Swaddle, T. W. Chem. Rev.2005, 105, 2573) that has been successful with other electron transfer reactions but which does not take into account the involvement of the anions in the activation process. The strongly negative ΔVel(⧧) values probably reflect solvation increases peculiar to activation processes of Ru(III/II) am(m)ine complexes, possibly together with promotion of desorption of surface-blocking Cl(-) or CF3SO3(-) from electrodes by applied pressure. Frumkin corrections for Ru(NH3)6(3+) within the diffuse double layer would make ΔVel(⧧) even more negative than is observed, although the corrections would be small. The strongly negative ΔVel(⧧) values are inconsistent with reduction of Ru(NH3)6(3+) in direct contact with the metallic electrode surface, which would entail substantial dehydration of both the electrode and Ru(NH3)6(3+). Reduction of Ru(NH3)6(3+) can be regarded as taking place in hard contact with adsorbed water at the outer Helmholtz plane.
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How this classification was reachedexpand
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 itClassification
machine, unvalidatedMachine predicted; a candidate call from one teacher head, 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".