Nonlinear instabilities in photochemical oxidations of 1,4-cyclohexanedione and its derivatives.
Bibliographic record
Abstract
In the closed 1,4-cyclohexanedione(CHD) bromate oscillatory reaction, we discovered that stirring can induce transitions between simple and period-doubled oscillations. When illumination was employed to characterize the importance of micro fluctuations of concentrations, the threshold stirring rate for inducing a bifurcation was found to increase proportionally to the intensity of the applied light. Numerical simulations with an existing model illustrate that the experimental phenomena could be qualitatively reproduced by considering effects of mixing on diffusion-limited radical reactions, namely, the disproportion reaction of hydroquinone radicals. A novel light-mediated chemical oscillator, i.e. 1,4-benzoquione(Q-bromate oscillator, was uncovered and investigated systematically in a batch reactor. Dependence of the oscillatory dynamics on the intensity of illumination was characterized. Quenching experiments suggest that the bromate - 1,4-Q oscillator is not only Br- controlled, but also radical-controlled. Oscillations were also investigated in a CSTR system. A mechanism was proposed, which successfully reproduced the experimental phenomena.Dept. of Chemistry and Biochemistry. Paper copy at Leddy Library: Theses & Major Papers - Basement, West Bldg. / Call Number: Thesis2006 .Z44. Source: Masters Abstracts International, Volume: 45-01, page: 0330. Thesis (M.Sc.)--University of Windsor (Canada), 2006.
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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".