Conversion constants for redox potentials measured versus different reference electrodes in acetonitrile solutions at 25°C

A critical review of light-driven interfacial charge-transfer reactions of transition-metal compounds anchored to mesoporous, nanocrystalline TiO2 (anatase) thin films is described. The review highlights molecular insights into metal-to-ligand charge transfer (MLCT) excited states, mechanisms of interfacial charge separation, inter- and intra-molecular electron transfer, and interfacial charge-recombination processes that have been garnered through various spectroscopic and electrochemical techniques. The relevance of these processes to optimization of solar-energy-conversion efficiencies is discussed (483 references).

Photodriven heterogeneous charge transfer with transition-metal compounds anchored to TiO2 semiconductor surfaces

The electrophilic properties of 34 solvents have been characterized by the Acceptor Number (AN) which has been derived from31P-n.m.r. measurements of triethylphosphine oxide dissolved in the respective solvents. Relationships are found between the acceptor numbers and theZ-values,E
T-values andY-values, as well as the free energies of solvation of anions and the redox potentials of the hexacyanoferrate(III)—hexacyanoferrrate(II) system in different solvents. The new parameter provides—together with the donor number—a useful guide in choosing the most appropriate solvent for a given reaction.

The acceptor number — A quantitative empirical parameter for the electrophilic properties of solvents

Empirical parameters for donor and acceptor properties of solvents

The division of thermodynamic solvation free energies of electrolytes into contributions from individual ionic constituents is conventionally accomplished by using the single-ion solvation free energy of one reference ion, conventionally the proton, to set the single-ion scales. Thus, the determination of the free energy of solvation of the proton in various solvents is a fundamental issue of central importance in solution chemistry. In the present article, relative solvation free energies of ions and ion−solvent clusters in methanol, acetonitrile, and dimethyl sulfoxide (DMSO) have been determined using a combination of experimental and theoretical gas-phase free energies of formation, solution-phase reduction potentials and acid dissociation constants, and gas-phase clustering free energies. Applying the cluster pair approximation to differences between these relative solvation free energies leads to values of −263.5, −260.2, and −273.3 kcal/mol for the absolute solvation free energy of the proton in me...

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Single-Ion Solvation Free Energies and the Normal Hydrogen Electrode Potential in Methanol, Acetonitrile, and Dimethyl Sulfoxide

Solvation of ions. XVI. Solvent activity coefficients of single ions. Recommended extrathermodynamic assumption

Solvation of ions. XII. Changes in the standard chemical potential of anions on transfer from protic to dipolar aprotic solvents

Solvation of ions. XI. Solubility products and instability constants in water methanol, formamide, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, and hexamethylphosphorotriamide

Copper is processed via solutions of copper salts, both cupric and cuprous, in acidified aqueous solutions containing organic nitriles. Methods of producting solutions of cuprous salts include reduction of cupric salts and oxidation of copper and copper sulphides. Solutions of cuprous salts are thermally or electrochemically disproportionated to produce copper and solutions of cupric salts.

Robert Alexander

Papers

Solvation of ions. XVI. Solvent activity coefficients of single ions. Recommended extrathermodynamic assumption

Solvation of ions. XII. Changes in the standard chemical potential of anions on transfer from protic to dipolar aprotic solvents

Solvation of ions. XI. Solubility products and instability constants in water methanol, formamide, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, and hexamethylphosphorotriamide

Method of producing copper and composition therefor

The leaching of copper from sulphur activated chalcopyrite with cupric sulphate in nitrile-water mixtures