NaAg3S2, ein Thioargentat mit dem Clusteranion [Ag6S4]2−

NaAg₃S₂, a Thioargentate Containing the Anionic Cluster [Ag₆S₄]^2? . Dark-red octahedrally shaped crystals of NaAg₃S₂ could be obtained by the reaction of NaAg(CN)₂ and NaCN in a stream of hydrogen sulfide at 630 K. NaAg₃S₂ crystallizes cubic, a=12.358(1) Å, space group Fd3 m, Z=16. The structure was determined from four-circle diffractometer data. NaAg₃S₂ contains the anionic cluster [Ag₆S₄]^2?. The structure can be traced back to the spinel structure typ. An extended Hückel calculation for the cluster anion, which is considered to be isolated, shows weak bonding silver-silver interactions. NaAg₃S₂ is diamagnetic at room temperature.     

Hygrometric Determination of Water Activities and Osmotic and Activity Coefficients of NH4Cl–LiCl–H2O at 25°C

The mixed aqueous electrolyte system of ammonium and lithium chlorides has been studied by the hygrometric method at 25°C. The relative humidities of this system are measured at total molalities from 0.3 to 6 mol-kg^{– 1} for different ionic-strength fractions y of NH₄Cl with y = 0.33, 0.50, and 0.67. The data obtained allow the deduction of new water activities and osmotic coefficients. The experimental results are compared with the predictions of the ECA (extended composed additivity) law proposed in our previous work. The Zdanovskii–Stokes–Robinson (ZSR), the Robinson–Stokes (RS), Reilly–Wood–Robinson (RWR), the Pitzer, and the Lietzke–Stoughton (LS II) models are also compared with our results. Predictions made using these models are, in general, consistent with our results. From these measurements, new Pitzer mixing ionic parameters are determined and used to predict the solute activity coefficients in the mixture for different ionic-strength fractions.     

Determination of thermodynamic properties of macroporous glycidyl methacrylate‐based copolymers by inverse gas chromatography

Macroporous crosslinked poly(glycidyl methacrylate‐co‐ethylene glycol dimethacrylate) (PGME) was synthesized by suspension copolymerization and modified by ring‐opening reaction of the pendant epoxy groups with ethylene diamine (EDA). Inverse gas chromatography (IGC) at infinite dilution was applied to determine the thermodynamic interactions of PGME and modified copolymer, PGME‐en. The specific surface areas of the initial and modified copolymer samples were determined by the BET method, from low‐temperature nitrogen adsorption isotherms. The specific retention volumes, V, of 10 organic compounds of different chemical nature and polarity (nonpolar, donor, or acceptor) were determined in the temperature range 333–413 K. The weight fraction activity coefficients of test sorbates, , and Flory–Huggins interaction parameters, , were calculated and discussed in terms of interactions of sorbates with PGME and PGME‐en. Also, the partial molar free energy, , partial molar heat of mixing, , sorption molar free energy, ΔG, sorption enthalpy ΔH, and sorption entropy, ΔS, were calculated. Glass transitions in PGME and PGME‐en, determined from IGC data, were observed in the temperature range 373–393 K and 363–373 K, respectively. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2524–2533, 2005     

CO吸附在过渡金属铂表面的微观动力学研究

建立了处理双原子分子-表面相互作用的推广的LEPS势.借助推广的LEPS势,系统研究了一氧化碳分子在铂低指数表面吸附的动力学特性,重现了低指数表面的分子吸附热、吸附几何及本征振动等实验数据；鉴定了某些不合理的文献信息,预测了实验尚未探测到的重要信息:预测到Pt(100)表面四重洞位的C－O伸缩振动频率为1 962.60 cm－1;预测到Pt(110)表面吸附态的C－O及C－Pt键长分别为115.1、147 pm.     

分块算子矩阵的加权EP

本文在加权广义Schur补的基础上, 引入并研究了Hilbert空间上分块算子矩阵的加权Moore-Penrose逆和加权EP. 进一步, 给出了加权EP算子在算子方程中的一个应用.     

Surface characterization of cellulose fibres by XPS and inverse gas chromatography

Inverse gas chromatography (IGC) was used to determine the dispersive component of the free energy as well as the acid-base properties of cellulose fibre surfaces, before and after modification by corona treatment. It was found that the corona treatment increases both the dispersive contribution to surface energy and its acidic character, whereas only a slight increase in its basicity was observed. It was also found that some chemical degradation of the surface occurs at high corona currents. The extent of modification of the surface properties, as revealed by IGC, was correlated to the surface chemical composition deduced from XPS analysis as well as with the electrical conductance and the pH of the water suspensions of the cellulose fibres.     

Essential spectrum and -solutions of one-dimensional Schrödinger operators

In 1949, Hartman and Wintner showed that if the eigenvalue equations of a one-dimensional Schrödinger operator possess square integrable solutions, then the essential spectrum is nowhere dense. Furthermore, they conjectured that this statement could be improved and that under this condition the essential spectrum might always be void. This is shown to be false. It is proved that, on the contrary, every closed, nowhere dense set does occur as the essential spectrum of Schrödinger operators which satisfy the condition of existence of -solutions. The proof of this theorem is based on inverse spectral theory.

     

Synthesis and Electrochemical Studies of Spinel LiNi1−xMnxVO4

Spinel compound LiNi_1−xMn_xVO₄ (0≤x≤0.4) had been prepared by using the moist chemical method. X-ray diffraction spectra showed that the lattice constant increased with x in the LiNi_1−xMn_xVO₄, XPS spectra indicating that Li1s had a chemical shift towards lesser binding energy, and manganese in LiNi_1−xMn_xVO₄ existing as the mixed valence of Mn²⁺ and Mn³⁺. The electrochemical charge and discharge testing at a current density of 0.1 mA/cm² between the potentials of 4.0 and 3.0 V vs Li/Li⁺ in 1 mol/dm³ LiPF₆/EC+DEC (1:1 by volume) at 25°C showed that LiNi_1−xMn_xVO₄ cell has a better rechargeability, but a lower cell voltage of 4.0 V vs Li/Li⁺ than that without the doping sample, and the capacity and the cycle efficiency of the Li/LiNi_1−xMn_xVO₄ cells increased with x in the LiNi_1−xMn_xVO₄.     

Conjugate-gradient method for computing the Moore-Penrose inverse and rank of a matrix

A conjugate-gradient method is developed for computing the Moore-Penrose generalized inverseA of a matrix and the associated projectors, by using the least-square characteristics of both the method and the inverseA . Two dual algorithms are introduced for computing the least-square and the minimum-norm generalized inverses, as well asA . It is shown that (i) these algorithms converge for any starting approximation; (ii) if they are started from the zero matrix, they converge toA ; and (iii) the trace of a sequence of approximations multiplied byA is a monotone increasing function converging to the rank ofA. A practical way of compensating the self-correcting feature in the computation ofA is devised by using the duality of the algorithms. Comparison with Ben-Israel's method is made through numerical examples. The conjugate-gradient method has an advantage over Ben-Israel's method.After having completed the present paper, the author received from Professor M. R. Hestenes his paper entitledPseudo Inverses and Conjugate Gradients. This paper treated the same subject and appeared in Communications of the ACM, Vol. 18, pp. 40–43, 1975.     

反相悬浮聚合法合成超强吸水剂

以两性高分子作悬浮稳定剂，用反相悬浮聚合法合成了聚（丙烯酸盐－丙烯酰胺）类超强吸水剂．研究了交联剂、稳定剂、引发剂等用量、中和程度、单体组成及链转移剂等聚合条件对吸水剂吸水性能的影响．得到了吸蒸馏水１０５０ｍＬ／ｇ及吸０．９％ＮａＣｌ溶液８６ｍＬ／ｇ的超强吸水剂．此外，还比较了含不同反离子的聚丙烯酸类吸水剂的吸水性能