Studying the behavior with pressure and temperature of thermal expansivity data derived from (p,p,T) measurements of liquids, we found that a previously derived analytical equation of state is inapplicable under certain thermodynamic conditions. The main obstacle is that these conditions are determined by characteristic constants of the liquid under study. Following the same scheme used to derive the original equation of state, we propose a new analytical expression which removes this restriction. Three different substances have been used to test the ability of the new equation of state to represent the volumetric properties of compressed liquids,

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We have investigated the effect of pressure on the hydrogen bonding in liquid methanol using Raman spectroscopy. Specifically, we have measured the OH and CO stretching modes and assigned the bands, in agreement with recent IR and crossed molecular beam experiments on methanol clusters. At about 7 to 8 kbar, we note indications that the intrinsic nature of the methanol clusters in our samples has changed. Our results provide support for and extend conclusions derived from Monte Carlo simulations, explain anomalies observed by previous researchers, and provide new insights into general hydrogen-bonding phenomena.

We analyse here the thermodynamic behaviour of the thermal expansion coefficient for a number of liquids. The purpose of this work is to provide some general rules to develop equations of state models meeting the following criteria: thermodynamic consistency, generality, predictive power and accuracy to represent derived properties over wide ranges of pressure and temperature. The liquids included into our analysis have been selected to meet two criteria: (1) available experimental data over wide ranges of pressure and temperature (from the melting point up to the critical point), and (2) liquids composed of molecules with different geometries and interactions.

The complex [Ph4P]2[Cu(bdt)2] (1(red)) was synthesized by the reaction of [Ph4P]2[S2MoS2CuCl] with H2bdt (bdt = benzene-1,2-dithiolate) in basic medium. 1(red) is highly susceptible toward dioxygen, affording the one electron oxidized diamagnetic compound [Ph4P][Cu(bdt)2] (1(ox)). The interconversion between these two oxidation states can be switched by addition of O2 or base (Et4NOH = tetraethylammonium hydroxide), as demonstrated by cyclic voltammetry and UV-visible and EPR spectroscopies. Thiomolybdates, in free or complex forms with copper ions, play an important role in the stability of 1(red) during its synthesis, since in its absence, 1(ox) is isolated. Both 1(red) and 1(ox) were structurally characterized by X-ray crystallography. EPR experiments showed that 1(red) is a Cu(II)-sulfur complex and revealed strong covalency on the copper-sulfur bonds. DFT calculations confirmed the spin density delocalization over the four sulfur atoms (76%) and copper (24%) atom, suggesting that 1(red) has a "thiyl radical character". Time dependent DFT calculations identified such ligand to ligand charge transfer transitions. Accordingly, 1(red) is better described by the two isoelectronic structures [Cu(I)(bdt2, 4S(3-,)*)](2-) ↔ [Cu(II)(bdt2, 4S(4-))](2-). On thermodynamic grounds, oxidation of 1(red) (doublet state) leads to 1(ox) singlet state, [Cu(III)(bdt2, 4S(4-))](1-).