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Record W4321791230 · doi:10.1002/cjce.24885

Free‐radical propagation rate coefficients

2023· article· en· W4321791230 on OpenAlexvenueno aff
Michael Buback

Bibliographic record

VenueThe Canadian Journal of Chemical Engineering · 2023
Typearticle
Languageen
FieldChemistry
TopicMass Spectrometry Techniques and Applications
Canadian institutionsnot available
Fundersnot available
KeywordsChemistryMonomerAqueous solutionCounterionPolymerizationIonizationRadical polymerizationPolymer chemistryPolarIonOrganic chemistryPolymer

Abstract

fetched live from OpenAlex

Abstract The pulsed laser polymerization‐size‐exclusion chromatography (PLP‐SEC) technique has become the International Union of Pure and Applied Chemistry (IUPAC)‐recommended method for the accurate determination of propagation rate coefficients, kp, for radical polymerization. The fundamental insight provided by Heuts, Gilbert, and Radom into the relevance of transition state dynamics allows for an adequate understanding of the dependence of kp on radical chain length, solvent environment, and monomer conversion. The associated entropic effects are particularly pronounced in aqueous solution, but are also found in less polar media and with non‐polar monomers. Moreover, these arguments are applicable towards the interpretation of copolymerization reactivity ratios. The addition of sodium hydroxide to aqueous solutions of (meth)acrylic acid yields partially and even fully ionized systems with clearly reduced kp, which indicates the action of repulsive forces between the equally charged monomer and radical species. Increasing the concentration of monomer as well as the addition of salts may reverse this effect and increase kp due to counterion activity.

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 imitation

Not 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.

metaresearch head score (Codex)0.002
metaresearch head score (Gemma)0.005
Version: metacan-v3-hybrid-931329e0061cValidation status: machine_predicted_unvalidated
Candidate categoriesnone
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Bench or experimental · Consensus signal: Bench or experimental
GenreCandidate signal: Empirical · Consensus signal: Empirical
Teacher disagreement score0.016
Threshold uncertainty score0.053

Distilled classifier scores by category (both heads)

CategoryCodexGemma
Metaresearch0.0020.005
Meta-epidemiology (narrow)0.0010.000
Meta-epidemiology (broad)0.0000.001
Bibliometrics0.0020.001
Science and technology studies0.0000.000
Scholarly communication0.0010.002
Open science0.0010.001
Research integrity0.0010.002
Insufficient payload (model declined to judge)0.0160.006

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.

Opus teacher head0.009
GPT teacher head0.210
Teacher spread0.201 · how far apart the two teachers sit on this one work
Validation statusscore_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it

Classification

machine, unvalidated

Machine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.

The models applied no category: nothing in the taxonomy fit this work.
Study designBench or experimental
Domainnot available
GenreEmpirical

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".

Quick stats

Citations10
Published2023
Admission routes1
Has abstractyes

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