The Determination of Proton Affinities of Secondary Alcohols from the Dissociation of Proton-Bound Molecular Trios. A New Application of the Kinetic Method
Why this work is in the frame
A frame that forgets how it found something cannot be audited. These are the routes that admitted this work.
Bibliographic record
Abstract
The kinetic method for determining proton affinity ( PA) values requires that the competing dissociations of proton-bound pairs of bases, AH + B n , essentially only lead to AH + and B n H + ions. The method fails for secondary alcohols because other reactions, involving rearrangement of the AH + B n ion, are dominant. It was found that proton-bound trios of bases, A 2 H + B n , (which incorporate secondary alcohols B n with a primary alcohol, A) do not suffer from this disadvantage. The proton-bound trios decomposed cleanly, to yield only A 2 H + and AH + B n ions. Application of the kinetic method to these competing reactions allowed the PA values for the secondary alcohols to be determined using the appropriate molecular-pair proton affinity [ MPPA] values. The MPPA is the negative of the enthalpy change, [–Δ H], accompanying the formation of a proton-bound pair from the component alkanols and a proton. These were readily estimated using known binding energies, D[AH + –B n ] and established PA values for n-alkanols. In the present brief study, PA values for isopropanol, cyclobutanol and cyclopentanol were measured to be 796, 792 and 798, all ± 6 kJ mol −1 . The results for the cyclic alcohols relate well with the available data from similar compounds, where the C 3 –C 5 rings display lower PA values than their acyclic analogues. This effect is attributed to restricted charge delocalization in the small rings.
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.
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 | 0.001 | 0.001 |
| 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 | 0.001 | 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 it