Gas-Phase Reactions of Transition-Metal Ions with Molecular Oxygen: Room-Temperature Kinetics and Periodicities in Reactivity
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Bibliographic record
Abstract
An Inductively-Coupled Plasma/Selected-Ion Flow Tube (ICP/SIFT) tandem mass spectrometer has been employed in a systematic survey of room- temperature reactions of O 2 with 29 transition-metal ions. The atomic ions are produced at ca. 5500 K in an ICP source and are allowed to decay radiatively and to thermalize by collisions with Ar and He atoms prior to reaction. Rate coefficients were measured for the reactions of first-row atomic ions from Sc + to Zn +, of second-row atomic ions from Y + to Cd + (excluding Tc + ) and of third-row atomic ions from La + to Hg + . Both O-atom abstraction and O 2 addition were observed as primary reaction channels. Periodicities in reactivity are identified and are compared with periodicities in the O-atom affinity of the atomic ion. O-atom abstraction was observed to be efficient when exothermic and inefficient when endothermic. NbO +, MoO +, TaO +, and WO + reacted further in a second O-atom transfer reaction with O 2 . ReO 2 + produced by direct addition of O 2 to Re + reacted further by both O-atom abstraction and O 2 addition. Sequential O 2 addition was observed to produce the higher oxides: MO 3 + (M = Ti, V, Y, Zr, Hf, Os), MO 4 + (M = Cr, Fe, Co, Ni, Cu, Nb, Mo, Ru, Rh, Hf, Ta, W, Re, Os, Ir, Pt, Au), MO 5 + (M = V, Re, Os), MO 6 + (M = Nb, W, Re) and MO 7 + (M = V). Novel termolecular reactions second-order in oxygen were identified for Os + and ZrO + at high oxygen concentrations to produce O 2 + and OsO + from Os + and a neutral metal oxide from Zr + .
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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 | 0.001 |
| 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