Theoretical study on the reactions of a series of polybromobenzenes with OH radicals: mechanism, kinetics, and QSAR
Bibliographic record
Abstract
Polybromobenzenes are a kind of monocyclic aromatic flame retardants that are used as a substitute for polybrominated diphenyl ethers and hexabromocyclododecane. In this paper, the reaction mechanism and rate constants for the reaction of OH radicals with a series of polybromobenzenes such as hexabromobenzene (HBB), 1,2,4,5-tetrabromobenzenes (1,2,4,5-TeBB), pentabromobenzene (PEBB), pentabromoethylbenzene (PBEB), pentabromotoluene (PBT), and 2,4,5-tribromotoluene (2,4,5-TrBT) have been investigated by quantum chemical method. The reaction mechanism was obtained at the MPWB1K/6-311+g(3df,2p)//MPWB1K/6-31+g(d,p) level of theory and the rate constants were deduced over the temperature range of 200–370 K using canonical variational transition state (CVT) theory with the small curvature tunneling (SCT) method. The rate constants of OH radicals with HBB, 1,2,4,5-TeBB, PEBB, PBEB, PBT, and 2,4,5-TrBT are determined to be 5.72 × 10−13, 1.23 × 10−12, 8.78 × 10−13, 9.23 × 10−13, 6.46 × 10−13, and 1.69 × 10−12, respectively, at 298 K and 1 atm. The estimated atmospheric lifetimes of HBB (20.08 days), 1,2,4,5-TeBB (9.65 days), PEBB (13.5 days), PBEB (12.9 days), PBT (18.4 days), and 2,4,5-TrBT (7.0 days) determined by OH radicals indicate that polybromobenzenes have the potential for long-range transport. The genetic function approximation is used to study the quantitative structure–activity relationship. The coefficients indicate that the ELUMO has the highest correlation to logkOH.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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) | 0.001 | 0.001 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.002 | 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".