Heats and Entropies of Ionization of Phenol and Some Substituted Phenols

Standard partial molal properties of aqueous alkylphenols and alkylanilines over a wide range of temperatures and pressures

“…Their values are in good agreement with those published by Gillet (1990) for phenol and aniline at 298 K, using the same type of calorimeter. These data were complemented by earlier determinations of Fernandez and Hepler (1959) and Parsons et al (1971Parsons et al ( , 1972) that were obtained using relatively simple instrumentation but agree reasonably well with the above data. The values of Arnett et al (1976) for phenol and three cresols have been omitted because they are systematically lower by at least 10% compared to other data.…”

Hartree-Fock and density functional theory study of remote substituent effects on gas-phase heterolytic Fe-O and Fe-S bond energies of p -G-C6 H4 OFe(CO)2 (η 5 -C5 H5 ) and p -G-C6 H4 SFe(CO)2 (η 5 -C5 H5 )

“…The substituent effects [ΔΔ H het (Fe–O)'s] of the theoretical Fe–O heterolytic energies for series 1 calculated by the TPSSTPSS/6‐311 + G(d,p)//B3LYP/6‐31G(d) method are also correlated with the experimental and computational substituent effects on acidities of p ‐G‐C 6 H 4 OH . The correlation coefficients are 0.99(48.9%EtOH, Δp K a , acid–base titration), 1.00(95.0%EtOH, Δp K a , acid–base titration), 1.00(H 2 O, Δp K a , solution calorimetry), 0.99(H 2 O, Δp K a , spectrophotometric method), 1.00(H 2 O, Δp K a ), 1.00(MeOH, Δp K a , ultraviolet spectrophotometry, equilibrium equations), 0.99(H 2 O, ΔΔ G 0 ), 1.00(H 2 O, Δp K a ), 0.96(g, δΔ G , pulsed ion cyclotron resonance), 1.00(H 2 O, δΔ G i 0 , solution calorimetry), 0.99(DMSO, δΔ G i 0 , solution calorimetry), 0.99(DMSO, δΔ H i 0 , solution calorimetry), 1.00(g, δΔ G , pulsed electron beam high‐pressure mass spectrometer), 0.99(H 2 O et al ., Δp K a , light absorbance measurements combined with electrometric measurements of pH, measurements of pH changes during titrations using glass electrodes et al . ), 0.99(g, δ x Δ E a 0 (OH), ab initio molecular orbital calculations/STO‐3G//standard model geometries), 1.00(g, δΔ G 0 (g), ion cyclotron resonance equilibrium constant method)(Table , Fig.…”

Linear Free Energy Relationships.

“…The situation has been examined by Leffler (166), who finds for numerous reaction series a linear relation between enthalpy and entropy, or activation energy and pre-exponential factors. Taft (93) and for the acid dissociation of some phenols (86). At least one reaction series has been observed in which log k is linear with sigma although neither AH* nor AS* is (272).…”