Electrochemical behaviour of ferrocenes in tributylmethylphosphonium methyl sulfate mixtures with water and 1,2-dichloroethane
Bibliographic record
Abstract
Electron transfer (ET) reactions in ionic liquid (IL)|organic solvent (1,2-dichloroethane, DCE) and IL|water mixtures were investigated using a Pt disk ultramicroelectrode (UME) along with ferrocene (Fc) and ferrocenemethanol (FcCH2OH) redox probes as electroactive species dissolved in the respective mixtures. The IL utilized was tributylmethylphosphonium methyl sulfate (P4441CH3SO4). The diffusion coefficient of each redox species was determined at each incremental increase of DCE or water to the IL using a chronoamperometric technique that is concentration independent. The IL|DCE mixture exhibited little change in the Fc diffusion coefficient, DFc, up to a DCE mole fraction (χDCE) of 0.5; the observed value, 2.0 × 10−8 cm2 s−1, agrees well with that typically reported for ILs in the literature. After which, the DFc quickly rose to a value commonly found in conventional molecular solvents, 1.3 × 10−5 cm2 s−1 (at χDCE = 0.8). An analogous result was not observed for IL|water mixtures using FcCH2OH, such that [Formula: see text] varied from 0.2 to 1.2 × 10−9 cm2·s−1 at a [Formula: see text] of 0 to 0.8. It was proposed that a large increase in the DFc in the IL|DCE mixture versus [Formula: see text] in the IL|water series was owing to P4441CH3SO4’s more hydrophobic character. Its hydrophobicity was quantified by measuring the formal ion transfer potentials of the IL component ions at a water|DCE immiscible interface.
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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 | 0.001 |
| Meta-epidemiology (narrow) | 0.001 | 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 | 0.001 | 0.000 |
| Research integrity | 0.001 | 0.001 |
| 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".