Some thermodynamic properties of carboxylato-pentammine cobalt(III) ions

Measurements are reported on the thermodynamic properties for the acid ionisation of various carboxylato-pentammine cobalt(III) ions, where the organic ligand is a dicarboxylate ion ^?OCORCOOH. It is shown that the results can be correlated with the ionisation of the free acids, on the basis of a simple electrostatic model. Results are also reported on the enthalpies of hydrolysis of the same ions, obtained indirectly from the enthalpies of reaction with sodium sulphide. The results for the complexes of the dicarboxylic acids which were studied (maleato, phthalato, fumarato, succinato and malonato) are not very different, while the acetato complex is somewhat more unstable. There is some indication that the complexes which hydrolyse faster are also thermodynamically less stable.     

Recent results from the TCV tokamak

During the first two years of operation, the TCV tokamak has produced a large variety of plasma shapes and magnetic configurations, with 1.0B _tor1.46T,I _p800kA,k2.05, –0.71. A new shape control algorithm, based on a finite element reconstruction of the plasma current in real time, has been implemented. Vertical growth rates up to 1000s^–1 have been stabilized using the external coil system. Ohmic H-modes with Troyon factors ( _tor aB/I _p) up to two and densities up to 2.25×10²⁰m^–3, corresponding to the Greenwald limit, have been obtained in diverted discharges. Limiter H-modes with line averaged electron densities up to 1.7×10²⁰m^–3 have been obtained in elongated D-shaped plasmas with 360 kAI _P600 kA.Presented at 17^th Symposium Plasma Physics and Technology, Prague, June 13–16, 1995.This work was partly supported by the Fonds National Suisse de la Recherche Scientifique.     

The phase change in potassium chloride

Equations for the interaction of ions in an ionic crystal, developed earlier¹, which allow for the variation of compressibility with pressure, have been applied to calculation of properties connected with the phase transition of potassium chloride under pressure. The data used were only for the high pressure form of the compound. It was found that the calculated transition pressure was much closer to the observed value, if these equations were used; but simpler equations which use a constant compressibility were somewhat better in their calculated values for the lattice energy, molar volume, and change of volume with pressure for the low pressure form of potassium chloride (NaCl structure). It is concluded that, while calculations on these equations form a sensitive test of these equations, the fitting of the equation to the structure needs to be more elaborate.     

Theoretical calculation of electrode potentials: Electron-withdrawing compounds

The electrode potential of 2,3-dicyanobenzoquinone in aqueous solution has been calculated relative to parabenzoquinone using a thermodynamic cycle approach that includes accurate gasphase ab initio calculations and calculation of differences in free energies of hydration using the free-energy perturbation method. The discrepancy between the calculated and experimental electrode potential is disappointingly large (99 mV) compared to previous studies using this approach. This, along with the experimental evidence, suggests that the experimental value itself is too large and that theoretical approaches may indeed be as reliable as experimental ones for determining redox properties of molecules such as 2,3-dicyanobenzoquinone. In the light of this discrepancy we have examined the variation of the results with the basis set, inclusion of electron correlation and changes in the parameters used in the molecular dynamics free-energy simulations. The results are shown to be dependent upon the torsional parameters and especially dependent upon the basis set or semiempirical method used to obtain the electrostatic potential-derived charges. The best charge set was determined using the ab initio criteria of completeness—as far as it can be applied to large molecules—and also by studying the effect of hydration on these charges. This was done by allowing the solvent to perturb the wave function prior to the electrostatic potential determination. Thus, 3-21G and 6-31G * basis sets were found to give satisfactory results. Similar results were obtained using semiempirical and ab initio geometries.     

Experimental and Modeling Investigation of Radical Homopolymerization of 2‐(Methacryloyloxyethyl) Trimethylammonium Chloride in Aqueous Solution

The radical homopolymerization kinetics of 2‐(methacryloyloxyethyl) trimethylammonium chloride (TMAEMC) in aqueous solution is investigated across a wide range of initial monomer contents (5–35 wt%), ionic strengths, and pH levels using an in‐situ NMR technique to track monomer consumption over the complete conversion range. Molar mass distributions (MMD) of the final homopolymers are also examined, with additional batch and semi‐batch experiments conducted in a stirred vessel. The rates of monomer conversion and polymer MMDs are dependent on initial monomer content but almost entirely independent of pH and the presence of salts, with some acceleration of rate observed for low monomer levels at very high salt concentration. To aid with the interpretation of these results, the conductivity and counterion activity of monomer and polymer mixtures are measured to determine the extent of electrostatic interactions at various levels of conversion. These results are combined with recently reported measurements of TMAEMC homopropagation kinetics to develop a TMAEMC homopolymerization model that captures the systematic decrease in rates of monomer conversion observed with increased initial monomer content during batch polymerization as well as provides a good representation of semi‐batch polymerization.     

In-beam spectroscopy of 253, 254No

In-beam conversion electron spectroscopy experiments have been performed on the transfermium nuclei ^{253, 254}No using the conversion electron spectrometer SACRED in nearly collinear geometry in conjunction with the gas-filled separator RITU at the University of Jyv?skyl?. The experimental setup is discussed and the spectra are compared to Monte Carlo simulations. The implications for the ground-state configuration of ²⁵³No are discussed. Received: 21 March 2002 / Accepted: 16 May 2002 / Published online: 31 October 2002 RID="a" ID="a"e-mail: rdh@ns.ph.liv.ac.uk RID="b" ID="b"Present address: GANIL, F-14021 Caen, France. RID="c" ID="c"Permanent address: IReS Strasbourg, IN2P3-CNRS, F-67037-Strasbourg, France. RID="d" ID="d"Present address: CEA/DIF DCRE/SDE/LDN F-91680 Bruyeres-le-Chatel. RID="e" ID="e"Present address: Daresbury Laboratory, Daresbury WA4 4AD, UK. RID="f" ID="f"Permanent address: IPN Lyon, IN2P3-CNRS, F-69037 Lyon, France.