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• W2000775346 abstract "Cross-correlations of rate constants between a system of interest and a better-defined one have become popular as a tool in studying transformations of organic pollutants. A slope of unity (if the correlation is conducted on a log-log basis) in such plots has been invoked as evidence of a common mechanism. To explore this notion, benzotrichloride and several of its substituted analogues were reacted with Cr(H2O)6(2+), an iron(II) porphyrin (iron meso-tetra(4-carboxyphenyl)porphine chloride, Fe(II)TCP), and granular iron. The first two reductants react with organohalides by dissociative inner sphere single-electron transfer, while mechanism(s) for organohalide reduction by granular iron are still debated. Apartfrom sterically hindered compounds, good correlations were obtained in comparing any two systems, although slopes (on a log-log basis) deviated from unity. We argue that a slope of unity is neither necessary nor sufficient evidence of a common mechanism. Overall rate constants may be composite entities, consisting in part of rate or equilibrium constants for adsorption onto surfaces or for precursor formation in solution; these components may differ between systems in their susceptibility to substituent effects. Cross-correlations may prove useful in predicting reactivity in the absence of steric effects, but additional evidence is required in deducing reaction mechanisms." @default.
• W2000775346 created "2016-06-24" @default.
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• W2000775346 date "2006-06-07" @default.
• W2000775346 modified "2023-09-23" @default.
• W2000775346 title "Reactivity of Substituted Benzotrichlorides toward Granular Iron, Cr(II), and an Iron(II) Porphyrin: A Correlation Analysis" @default.
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• W2000775346 doi "https://doi.org/10.1021/es051737x" @default.
• W2000775346 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/16856743" @default.
• W2000775346 hasPublicationYear "2006" @default.
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