Isentropic partial molal compressibilities of alcohols in propylene carbonate at 25°C

The isentropic coefficients of compressibility of the homologous series of alcohols and diols R _n CH₂OH (n=2–6), CH₃CHOHR _n (n=1–5), 1,2-propanediol, 1,3- 1,4- and 2,3-butanediol, 1,5-pentanediol, and 1,7-heptanediol dissolved in propylene carbonate have been measured at 25°C. Isentropic partial molal compressibilities and group partial molal compressibilities at infinite dilution have been evaluated. The isentropic partial molal compressibilities of these alcohols and diols have been compared with the corresponding values in water. This comparison shows that the values in propylene carbonate are higher than in water by a factor of 10 due to an increased compressibility of the solvation sheath around nonpolar groups in PC.     

Monolayer adsorption isotherms and a disordered medium model

A model of disordered medium is proposed to describe the monolayer adsorption isotherm on heterogeneous surfaces. The model is based on the premise that adsorption medium consists of separate regions in each of which there is a permanent local equilibrium constant, the character of the changes of which is determined by the disorder parameter of the medium. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 3, pp. 189–193, May–June, 2006.     

Quantitative volatilization of tin as mixed halides and its application in metal analysis

Proposed in this paper is an improved method for removal of tin as the matrix element by volatilization in an anhydrous medium as mixed halides of different composition. Any one of them boils at a lower temperature than SnBr₄. This ternary system enhances the eventual recombination of temporarily dissociated species to volatile ones, thus making the process quicker and more efficient. The presence of 2 mg of Pb(II) suffices to prevent Bi(III) from loss due to volatilization.     

A parallel implementation of the COLUMBUS multireference configuration interaction program

Summary In this work a parallel implementation of the COLUMBUS MRSDCI program system is presented. A coarse grain parallelization approach using message passing via the portable toolkit TCGMSG is used. The program is very well portable and runs on shared memory machines like the Cray Y-MP, Alliant FX/2800 or Convex C2 and on distributed memory machines like the iPSC/860. Further implementations on a network of workstations and on the Intel Touchstone Delta are in progress. Overall, results are quite satisfactory considering the complexity and the prodigious requirements, especially the I/O bandwidth, of MRCI programs in general. For our largest test case we obtain a speedup of a factor of 7.2 on an eight processor Cray Y-MP for that section of the program (hamiltonian matrix times trial vector product) which has been parallelized. The speedup for one complete diagonalization iteration amounts to 5.9. An absolute speed close to 1 GFLOPS is found. Results for the iPSC/860 show that ordinary disk I/O is certainly not sufficient in order to guarantee a satisfactory performance. As a solution for that problem, the implementation of a fully asynchronous distributed-memory model for certain data files is in preparation. On leave from: Bereich Informatik, Universität Leipzig, Augustusplatz 10/11, O-7010 Leipzig, Germany     

The domain of partial attraction of a Poisson law

Groshev gave a characterization of the union of domains of partial attraction of all Poisson laws in 1941. His classical condition is expressed by the underlying distribution function and disguises the role of the mean of the attracting distribution. In the present paper we start out from results of the recent probabilistic approach and derive characterizations for any fixed >0 in terms of the underlying quantile function. The approach identifies the portion of the sample that contributes the limiting Poisson behavior of the sum, delineates the effect of extreme values, and leads to necessary and sufficient conditions all involving . It turns out that the limiting Poisson distributions arise in two qualitatively different ways depending upon whether >1 or <1. A concrete construction, illustrating all the results, also shows that in the boundary case when =1 both possibilities may occur.     

Partial molal volumes of ions in organic solvents from ultrasonic vibration potential and density measurements. III. Dimethylsulfoxide

The partial molal volumes of Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Cl^–, Br^–, I^–, and NO ₃ ^- in DMSO at 25°C have been determined from ultrasonic vibration potential data and density data for solutions of uni-univalent electrolytes. Hepler's semiemprirical equation has been used to split ionic partial molal volumes into geometric and electrostrictive contributions. The results obtained in this work confirm the conclusion of our previous studies, namely, that the contribution of electrostriction is essentially determined by the properties of that layer of atoms, 0.3 to 0.4 nm thick, in contact with the ion and by the degree of steric hindrance of the poles of the dipole of the solvent molecule. On the other hand, the geometric contribution depends on the size of the solvent molecule and also on the arrangement of the solvent molecules about the ions. It is shown that the geometric contribution to the partial molal volume of ions is largely increased when ions cannot come close enough to the poles of the solvent-molecule dipole, owing to steric hindrance.     

Vinyl polymerization of acrylonitrile by the Ce(IV)-glucose redox system

Aqueous polymerization of acrylonitrile (M) initiated by the Ce(IV)-glucose (R) redox system has been studied under nitrogen in the temperature range of 30–40 °C. The rate of polymerization (Rp) is proportional to [M]², [R] and inversely proportional to [Ce(IV)]. The rate of ceric ion disappearance is proportional to [R] and [Ce(IV)]. The end group in the polymer is characterised by IR spectra. A suitable kinetic scheme has been proposed and explained in the light of these experimental findings.     

Anomalies of the partition coefficient and properties of crystals in the region of low concentrations of an isomorphous admixture. 1. Unusual decomposition of solid solutions of the NaCl—CdCl2 system

Solid solutions NaCl—CdCl₂ were studied in an interval of CdCl₂ concentrations of 0.05—3 mol.% by Raman spectroscopy. The molecular form Na₂CdCl₄ decomposes: Na₂CdCl₄ 2Na⁺ + Cd²⁺ + 2Cl₂ ^– + 2e^–; 2Na + 2e^– 2Na⁰. Free sodium atoms form color centers of crystal (F centers) in the region of jumpwise changing the partition coefficient of CdCl₂ in NaCl (K jump).     

Thermodynamique des melanges binaires LiPO3-Pb(PO3)2: Diagramme de phases et étude thermodynamique du liquide

Study of solid-liquid phase diagram of LiPO₃-Pb(PO₃)₂ binary system, in certain calcination conditions, shows the existence of several metastable phasis. When heated at a temperature of 723 K the binary mixtures lead uncompletely to a defined compound Pb₂Li(PO₃). On heating these ternary solid mixtures, three eutectic reactions have been observed: LiPO₃+Pb(PO₃)₂→Liquid at a temperature of 793 K(1) LiPO₃+Pb₂Li(PO₃)₅→Liquid at a temperature of 843 K (2) Pb₂Li(PO₃)₅+Pb(PO₃)₂→Liquid at a temperature of 891 K (3) The metastable liquid phase appears in the system at temperature of 793 K. DTA experiments performed on the binary LiPO₃-Pb(PO₃)₂ mixtures, show a superposition of two diagrams. The first one is metastable and the second represents the stable equilibrium phase diagram. Measurements of liquid enthalpy of binary LiPO₃-Pb(PO₃)₂ system at temperature of 979.65 K were reported. The corresponding values were very small and so the binary system can be considered as athermal. Assuming an ideal behaviour, the liquidus curves in the metastable diagram were calculated and the eutectic reaction (LiPO₃-Pb(PO₃)₂→Liquid) was confirmed at 793 K. This revised version was published online in August 2006 with corrections to the Cover Date.     

神光-Ⅱ装置三倍频实验中靶场单元技术的改进

 主要介绍为了满足神光-Ⅱ高功率激光装置三倍频光（351nm，3ω）的物理实验要求，靶场三倍频模拟光源和瞄准监视系统两个主要单元技术的改进，即三倍频模拟光源由基频光（1 053nm，3ω）通过腔外的KTP+BBO晶体倍频获得，再经八路分光系统和主激光耦合；瞄准监视系统由透射式光学系统改进为反射式光学系统，避免原系统存在较大的色差，提高瞄准精度。