Statistical thermodynamics of polynuclear linear complexes with mixed valence states by means of the correlated walk

Expressions for the equilibrium electrode potential of linear N-nuclear complexes with homoredox centers were derived by the theory of the correlated walk as a function of the molar fraction of the oxidized moiety, the nearest-neighbor interaction energies and N. When the interaction energy was large in two-, three- and four-nuclear complexes, the expressions predicted two, three and four voltammetric peaks respectively owing to the formation of mixed valence states. The intuitive extension that the N-nuclear complex might exhibit N peaks was invalid. There were three peaks for any odd number of N. In contrast, four peaks appeared for any even number of N more than 4. For a polynuclear complex with N → ∞, the number of the peaks was reduced to two, as if the complex might be a binucleus. The log plot for the fraction vs. potential curve at large values of N deviated from a straight line. The averaged inverse slope was ca. 90 mV at 25°C. From the concentration distribution of a predominant species varying with the potential, the deviation of the log plot was ascribed to the coexistence of various isomers with different interaction energies. The difference in the voltammetric peak potential was approximately linear with the interaction energy for any N. Approximate equations for the potential difference for N= 2, 3 and 4 were obtained, and were applied to the experimental data available for polyferrocenes.     

A New Imaging Method with a Spatial Filter for Incoherent Stream

A new imaging method using an incoherent-type pupil filter: SFINCS (Spatial Filter for INCoherent Stream) is presented. The new filter divides the imaging beam into several incoherent beams at the pupil plane thereby enlarging the depth-of-focus (DOF). The capabilities of SFINCS are studied by simulations and several ways to realize the method are also discussed. The experimental results show that SFINCS has excellent DOF expanding capabilities for a point-image such as a hole pattern in VLSI lithography, and that 1.7 μm DOF is obtained with a 0.30 μm hole pattern by an i-line projection lens with 0.57 NA (numerical aperture).Presented at the International Commission for Optics Topical Meeting, Kyoto, 1994.     

Application of a novel large-volume injection method using a stomach-shaped inlet liner in capillary gas chromatographic trace analysis of dioxins in human milk and plasma.

A newly developed large-volume injection (LVI) technique that employs a unique stomach-shaped inlet liner (SSIL) inside of a programmable temperature vaporizer was used for the determination of trace amounts of dioxins in human milk and plasma. The initial temperature and the initial dwelling time of the inlet and the kind of solvent used were found to be critical in determining the analytical sensitivity of dioxins due to the loss of these relatively volatile compounds during solvent vaporization. Human milk and plasma were purified and fractionated by pre-packed multi-layered silica-gel chromatography and activated carbon silica-gel column chromatography. A 20-microL aliquot of the fraction collected from the chromatography with toluene was directly applied to the LVI system in high-resolution gas chromatography/high-resolution mass spectrometry. Excellent correlation (r > 0.97) between the values obtained by the LVI method using the SSIL device and those by the conventional regular-volume splitless injection method was obtained for PCDDs, PCDFs and non-ortho PCBs in human milk and plasma samples.     

A trifluoromethanesulfonic acid-catalyzed reaction of arylhydrazines with benzene

Arylhydrazines reacted with benzene in the presence of trifluoromethanesulfonic acid (TFSA) to give aminobiphenyls. This is a general method for the synthesis of aminobiphenyls.     

Effective Hamiltonian for polyatomic linear molecules

The leading terms of an effective Hamiltonian for a linear molecule in a given vibrational state are presented up to κ¹⁰T_v order of magnitude, whereby higher-order l-dependent terms such as $\text{H}\text{?}{}_{12.0}$, $\text{H}\text{?}{}_{8.0}$, and $\text{H}\text{?}{}_{8.2}$ have been neglected because in spectroscopic application they are of minor importance. This Hamiltonian therefore includes all those l-type interactions which could contribute to the fitting procedure, within a vibrational state where one or more bending vibrations are excited.     

Selective cleavage of polycyclic cyclopropanes by electrochemical oxidation

Anodic oxidation in acetic acid of polycyclic cyclopropanes, namely tricyclene, cyclofenchene, and longicyclene, followed by hydrolysis brought about stereo- and regioselective formation of the corresponding homoallylic alcohols as the main product in good yields.     

Coulometric titration of copper in CuxMo6S8−y(0⩽y⩽0.4) with solid Cu-electrolyte Rb4Cu16I7Cl13

In order to determine the copper content x of copper Chevrel compound Cu_xMo₆S_8?y(0?y?0.4) as a function of copper activity a_Cu and sulfur deficit y, a solid state electrochemical cell, Cu/Rb₄Cu₁₆I₇Cl₁₃/Cu_xMo₆S_8?y/Pt, was constructed and coulometric titration studies were made at 400 K. For the evaluation of the coulometric titration data, measurements were made on the electronic conductivity of copper-ion conductor Rb₄Cu₁₆I₇Cl₁₃. Also, a brief investigation was made on the condition of formation of single phase Chevrel Cu_xMo₆S_8?y with varying x and y at 1000°C. The structural change of Cu_xMo₆S_8?y with a change in x and y was studied by the X-ray diffraction method. It was found that x for constant a_Cu decreases with increasing y. The maximum value x_max of x in Cu_xMo₆S_8?y in equilibrium with metallic copper was found to be expressed by $\text{x}{}_{\mathrm{<mtext>max</mtext>}}\text{=-(}\text{10}\text{3}\text{)y+5}$. In the region of y<0.3, x_max exceeded 4, contrary to a presupposition that x_max is less than 4. X-ray analysis revealed that most of the copper Chevrel compounds denoted by Cu_xMo₆S₈ so far were sulfur deficient ones with y?0.4. The importance of sulfur deficit on the properties of the copper Chevrel compound was emphasized.     

Flow pattern,void fraction and pressure drop of refrigerant two-phase flow in a horizontal pipe—I. Experimental data

Experiments with refrigerant two-phase flow in a horizontal pipe have been performed and data on flow pattern, void fraction and pressure drop have been obtained. Refrigerants used were R12 and R22, and the range of saturation pressure was from 5.7 to 19.6 bar.In this paper, the experimental equipment and procedure are described in detail, and the data are both tabulated and presented graphically.