Determination of the entropy of formation of the Pt(111)∣ perchloric acid solution interface. Estimation of the entropy of adsorbed hydrogen and OH species

The entropy of formation of the interface between a Pt(111) electrode and a 0.1-M HClO₄ solution is calculated here for the first time from the temperature dependence of total charge vs potential curves following a thermodynamic analysis based on the electrocapillary equation. From this quantity, the absolute entropies of specifically adsorbed species (hydrogen and OH) can be estimated. The present method is an alternative treatment of data that overcomes some of the limitations involved in the approach that uses a generalized isotherm. However, it requires additional experimental data: the temperature coefficient of the potential of zero total charge of the working electrode and the temperature coefficient of the reference electrode. Comparison of the results obtained by both approaches shows that, for hydrogen adsorption, the agreement is reasonable, but the differences are larger for OH adsorption, thus showing the limitations inherent in the treatment based on the generalized isotherm. Dedicated to Professor Oleg Petrii on the occasion of his 70th birthday on August 24, 2007.     

Asymmetric Hydrogenation of Disubstituted Furans

An enantioselective hydrogenation of disubstituted furans has been developed by using a chiral ruthenium catalyst with N‐heterocyclic carbene ligands. This reaction converts furans into valuable enantioenriched disubstituted tetrahydrofurans.