Standard molar free energies, enthalpies and entropies of transfer of some uni-univalent electrolytes from water to methanol, N-methylformamide, formamide, dimethyl sulphoxide, N,N-dimethyl- formamide, propylene carbonate, sulpholane, N-methylpyrrolidone and acetonitrile are presented. They have been divided into the corresponding thermodynamic properties for single ions by means of extrathermodynamic assumptions. Changes in the chemistry of anions on transfer from protic to dipolar aprotic solvents are mainly a function of enthalpy changes. There is a substantial loss of entropy on transferring both anions and cations from water to non-aqueous solvents. Entropies of transfer can be interpreted in terms of ordering and disordering solvent molecules and a uniquely extensive water structure. Evidence for solvation of the first and second kind in water is presented. Enthalpies of transfer from water are exothermic for cations but endothermic for many anions.

From a potentiometric and visible spectrophotometric study of the nickel(II)-citric acid (H3L) system in the pH range 3-6, four complexes, NiL-, NiHL, NiH2L+ and NiL24-, have been characterized. Stability constants for the formation of these complexes have been determined at 25°C in 0.1 mol dm-3 KCl. The results suggest that the hydroxy group of citric acid is coordinated in the nickel-citrate complexes.

The preparations are reported for copper(11) complexes with the ligand 4,4,9,9-tetramethyl-5,s-diazadodecane-2,l-dione dioxime, LH2. Syntheses from the syn (methyl) and anti isomers of the ligand give the same products. The complexes characterized are Cu(LH2)X2,yH2O (X = Cl-, ClO4-; y = 0, 1, 2) and Cu(LH)X (X = Cl-, Br-, ClO4-). The complex Cu(LH)Br is shown by X-ray structure analysis to contain dimeric units (Cu(LH))22+ with crystallographic C2 symmetry and with the copper atom in a trigonal bipyramidal coordination environment. Stability constants for the reactions Cu2+ + LH2 ←→ Cu(LH2)2+ (log K = 13.24 � 0.05) and Cu(LH2)2+ ←→ Cu(LH)+ + H+ (log K = -3.24 � 0.08) are reported, as well as the magnetic susceptibilities, i.r. spectra, and electronic absorption spectra of the complexes.

The preparations and visible and ultraviolet absorption spectra are reported for a series of copper(11) complexes with linear and cyclic aliphatic ligands which each have four nitrogen donor atoms. Data are compared with that for 16 analogous complexes. For linear polyamines of different chain length the ligand field strength, as denoted by vmax (visible), is found to increase with increasing thermodynamic stability of the copper(11) complex in aqueous solution. For linear and cyclic ligands the ligand field strength is a maximum for complexes containing a combination of five- and six-membered chelate rings.

The enthalpies of dilution at 298 K of aqueous solutions of the tripeptides glycylglycylglycine, glycylglycylalanine and alanylglycylglycine have been determined by flow microcalorimetry. From these data the partial molar enthalpies of the solvent in the solutions have been calculated. The results indicate that water side-chain interactions make an important contribution to the solvation of peptides.