This review presents a critical assessment of the available experimental information ͑contained in ϳ90 literature references͒ on the thermochemistry of the O-H bond in phenol and substituted phenols. The analysis led to a set of recommended values for the O-H bond dissociation enthalpies, which in turn allowed us to discuss several empirical and theoretical methodologies used to estimate these data.

Time-resolved photoacoustic calorimetry (TR-PAC) and quantum chemistry calculations were used to investigate the energetics of sulfur-hydrogen bonds in thiophenol and four para-substituted thiophenols, 4-XC 6 H 4 SH (X ) CH 3 , OCH 3 , Cl, and CF 3 ). The result obtained for the PhS-H gas-phase bond dissociation enthalpy, derived from the PAC experimental results in solution, is 349.4 ( 4.5 kJ mol -1 . This value is significantly higher than recent literature values but agrees with a value suggested some 20 years ago in a widely used review. The PAC result also concurs with the value computed at a high theory level, G3(MP2), 346.8 kJ mol -1 . The data obtained for the substituted thiophenols support the idea that substituent effects are less pronounced on the S-H bond dissociation enthalpy than on the O-H bond dissociation enthalpy of the corresponding phenols. † Part of the special issue "Jack Beauchamp Festschrift".

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The photolysis reaction of di-tert-butylperoxide was studied in various solvents by photoacoustic calorimetry (PAC). This technique allows the determination of the enthalpy of this homolysis reaction, which by definition corresponds to the O-O bond dissociation enthalpy of the peroxide in solution, DHsin(degrees)(O-O). The derived value from these experiments in benzene, 156.7 +/- 9.9 kJ mol(-1), is very similar to a widely accepted value for the gas-phase bond dissociation enthalpy, DH(degrees)(O-O) = 159.0 +/- 2.1 kJ mol(-1). However, when the PAC-based value is used together with auxiliary experimental data and Drago's ECW model to estimate the required solvation terms, it leads to 172.3 +/- 10.2 kJ mol(-1) for the gas-phase bond dissociation enthalpy. This result, significantly higher than the early literature value, is however in excellent agreement with a recent gas-phase determination of 172.5 +/- 6.6 kJ mol(-1). The procedure to derive the gas-phase DH(degrees)(O-O) was tested by repeating the PAC experiments in carbon tetrachloride and acetonitrile. The average of the values thus obtained was DH(degrees)(O-O) = 179.6 +/- 4.5 kJ mol(-1), confirming that the early gas-phase result is a lower limit. More importantly, the present study questions the usual assumption that the solvation terms of homolysis reactions producing free radicals in solution should cancel, and suggests a methodology to estimate solvation enthalpies of free radicals.

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Aim:The knowledge of a species biogeographical patterns greatly enhances our understanding of geographical ecology, which can improve identifying key conservation needs. Yet, this knowledge is still scarce for many marine top predators. Here, we aim to analyse movement patterns and spatial structuring of a large predator, the short-finned pilot whale Globicephala macrorhynchus, over a wide geographical area.Location: North-east Atlantic, in Macaronesian archipelagos (Azores, Madeira and Canaries) and Iberian Peninsula (Sagres). Methods:We used likelihood techniques to estimate residency times and transition probabilities and carried out social analysis from individual photographic

Monte Carlo statistical mechanics simulations, density-functional theory calculations, time-resolved photoacoustic calorimetry, and isoperibol reaction-solution calorimetry experiments were carried out to investigate the solvation enthalpies and solvent effects on the energetics of the phenol O-H bond in benzene and acetonitrile. A good agreement between theoretical and experimental results is obtained for the solvation enthalpies of phenol in benzene and acetonitrile. The theoretical calculations also indicate that the differences between the solvation enthalpies of phenol (PhOH) and phenoxy radical (PhO • ) in both benzene and acetonitrile are significantly smaller than previous estimations based on the ECW model. The results for the solvation enthalpies are used to obtain the O-H bond dissociation enthalpies in benzene and acetonitrile. For benzene and acetonitrile, the theoretical results of 89.4 ( 1.2 and 90.5 ( 1.7 kcal mol . A detailed analysis of the solvent contributions to the differential solvation enthalpy is made in terms of the hydrogen bonds and the solute-solvent interactions. Both PhOH and PhO• induce a significant, although equivalent, solvent reorganization enthalpy. Finally, the convergence of the solute-solvent interaction is analyzed as a function of the distance to the solute and illustrates the advantages and limitations of local models such as microsolvation and hydrogen-bond-only models.

The gas-phase C-H bond dissociation enthalpy (BDE) in 1,3-cyclopentadiene has been determined by time-resolved photoacoustic calorimetry (TR-PAC) as 358 +/- 7 kJ mol(-1). Theoretical results from ab initio complete basis-set approaches, including the composite CBS-Q and CBS-QB3 procedures, and basis-set extrapolated coupled-cluster calculations (CCSD(T)) are reported. The CCSD(T) prediction for the C-H BDE of 1,3-cyclopentadiene (353.3 kJ mol(-1)) is in good agreement with the TR-PAC result. On the basis of the experimental and the theoretical values obtained, we recommend 355 +/- 8 kJ mol(-1) for the C-H BDE of 1,3-cyclopentadiene and 271 +/- 8 kJ mol(-1) for the enthalpy of formation of cyclopentadienyl radical.