分解水制氢的KNO3—I2循环之研究：Ⅲ.代替电解反应的一个子循环

本文提出了一个硫酸中间盐子循环用以代替分解水制氢的KNO_3-I_2混合循环中的电解反应,从而使原混合循环变为一个纯热化学循环。     

Influence of pH on electrophoretic behavior of phenothiazines and determination of pKa values by capillary zone electrophoresis

The influence of buffer pH on the electrophoretic behavior of 13 structurally related phenothiazines and determination of pK(a) values by capillary zone electrophoresis (CZE) were investigated. The results indicate that phenothiazines with a piperazine substituent behave quite differently from those with substituents having an aliphatic side chain or a piperidine moiety over the pH range studied. To separate these phenothiazines, it is preferable to select buffer pH in the range of 2.5-3.5. The pK(a) values of phenothiazines with three different types of substituents attached at the 10-position of the phenothiazine ring were determined. The determination of pK(a) values of phenothiazines allows us to rationalize the influence of buffer pH on the migration behavior of these compounds in CZE.     

碳酸氢铵制纯碱的研究

本文对“中间盐”复分解制碱法进行了研究。“中间盐”的加入不能使两个三盐共饱和点在干盐图上发生明显的移动,但能使三盐介稳平衡点的介稳期延长,从而使得用碳酸氢铵和食盐通过复分解制碱成为可能。     

Studies of the Factors Controlling Regioselective Nucleophilic Addition to Dienylium-Iron Complexes

Tricarbonyl(4-alkoxyl-1-alkylcyclohexadienylium)iron complexes (I) react with metal-cation enolate nucleophiles to give in most cases a mixture of products (II) and (III), resulting from attack at the C-1 and C-5 termini of the dienylium ring. Factors that control the regioselectivity of nucleophilic addition, including the steric and electronic effects of the 4-alkoxyl and 1-alkyl substituents, the degree of association between the enolate nucleophiles and their counterions, and the polarity of the solvents, were investigated.     

Adsorption recovery of thorium(IV) by Myrica rubra tannin and larch tannin immobilized onto collagen fibres

Novel adsorbents which can concentrate Th(IV) in aqueous solution were prepared by immobilizingMyrica rubra tannin and larch tannin onto collagen fibre matrices. The adsorption capacities of the immobilized tannins to Th(IV) are related to temperature and pH value of the adsorption process. For example, when the initial concentration of Th(IV) was 116.0 mg·l^-1 and the immobilized tannin was 100 mg, the adsorption capacities of immobilized Myrica rubra tannin and larch tannin were 55.98 mg Th(IV)·g^-1 and 13.19 mg Th(IV)·g^-1, respectively at 303 K, and 73.67 mg Th(IV)·g^-1 and 18.19 mg Th(IV)·g^-1 at 323 K. It was also found that the higher adsorption capacity was obtained at higher pH value. The adsorption equilibrium data of the immobilized tannins for Th(IV) can be well fitted by the Langmuir model and the mechanism of the adsorption was found to be a chemical adsorption. In general, the adsorption capacity of immobilized Myrica rubra tannin to Th(IV) is significantly higher than that of immobilized larch tannin, probably due to the fact that the B ring of Myrica rubra tannin has a pyrogallol structure which has higher reaction activity with metal ions. The breakthrough point of the adsorption column of immobilized Myrica rubra tannin was at 33 bed volumes for the experimental system. The mass transfer coefficient of adsorption column determined by Adams-Bohart equation was 1.61·10^-4 l·mg^-1.min^-1. The adsorption column can be easily regenerated by 0.1 mol·l^-1 HNO₃ solution, showing outstanding ability of concentrating Th(IV). This revised version was published online in July 2006 with corrections to the Cover Date.     

An efficient and general method for resolving cyclopropene carboxylic acids

A general method is described for the resolution of cycloprop-2-ene carboxylic acids via diastereomeric N-acyloxazolidines prepared from enantiomerically pure oxazolidinones. Although a number of oxazolidinones were shown to resolve cyclopropene carboxylic acids, the oxazolidinones of S-phenylalaninol, S-phenylglycine and (1S,2R)-cis-1-amino-2-indanol are optimal in terms of resolving power and cost effectiveness. Separations were performed using simple flash chromatography, and because there is typically a large difference in R_f values it is possible to separate gram quantities of pure diastereomers in a single chromatogram. The cycloprop-2-ene carboxylic acids that can be resolved include those that are substituted at the 1-position by H, Ph, α-naphthyl, CO₂Me, CH₂OMOM, and trans-styryl; alkene substituents include Me, n-alkyl, Ph and tethered alkynes. Remarkably, 2-methyl-3-propylcycloprop-2-ene carboxylic acid can also be resolved with ease. The relative configurations of four diastereomerically pure oxazolidines were determined by X-ray crystallography. Reduction of the N-acyloxazolidinones with LiBH₄ give enantiomerically pure derivatives of 3-hydroxymethylcyclopropene that react with either MeMgCl or vinylMgCl and catalytic CuI to give enantiomerically pure products of syn-addition.     

Synthesis and magnetic properties of trinuclear copper(II) complexes bridged by dimethylglyoximate groups

Summary New three Cu^II-Cu^II-Cu^II homotrinuclear complexes have been synthesized, namely [Cu(dmg)₂{CuL}₂](ClO₄)₂ [L = 5-nitro-1,10-phenanthroline (5-NO₂-phen), 4,4-dimethyl-2,2-bipyridiine (DMbpy), tetramethylenediamine (TMDA) and dimethylglyoximate ion (dmg)^2-]. The magnetic susceptibilities of complexes (1) (L = 5-NO₂-phen) and (2) (L = DMbpy) were measured in the 4.2–300 K range, giving the parameters,J = -335cm^-1 (1) andJ= -327.5cm^-1 (2). The results demonstrate a very strong antiferromagnetic exchange interaction between the adjacent copper(II) ions.     

Direct drag measurements in a turbulent flat-plate boundary layer with turbulence manipulators

The effect of turbulence manipulators on the turbulent boundary layer above a flat plate has been investigated. These turbulence manipulators are often referred to as Large Eddy Break Up (LEBU) devices. The basic idea is that thin blades or airfoils are inserted into the turbulent flow in order to reduce the fluctuating vertical velocity component v above the flat plate. In this way, the turbulent momentum transfer and with it the wall shear stress downstream of the manipulator should be decreased. In our experiments, for comparison, a merely drag-producing wire also was inserted into the boundary layer.In particular, the trade-off between the drag of the turbulence manipulator and the drag reduction due to the shear-stress reduction on the flat plate downstream of the manipulator has been considered. The measurements were carried out with very accurate force balances for both the manipulator drag and the shear stress on the flat plate. As it turns out, no net drag reduction is found for a fairly large set of configurations. A single thin blade as a manipulator performed best, i.e., it was closest to break-even. However, a further improvement is unlikely, because the device drag of the thin blade elements used here has already been reduced to only that due to laminar skin friction, and is thus the minimum possible drag. Airfoils performed slightly worse, because their device drag was higher. A purely drag-producing wire device performed disastrously. The wire device, which consisted of a wire with another thin wire wound around it to suppress coherent vortex shedding and vibration, was designed to have (and did have) the same drag as the airfoil manipulator with which it was compared. The comparison showed that airfoil and blade manipulators recovered 75–90% of their device drag through a shear-stress reduction downstream, whereas the wire device recovered only about 25–30% of its device drag.Conventional LEBU manipulators with airfoils or thin blades produce between 0.25% and 1% net drag increase, whereas the wire device (with equal device drag) produces as much as 4% net drag increase. These data are valid for the specific plate length of our experiments, which was long enough in downstream extent to realize the full effect of the LEBU manipulators. Turbulence manipulators do indeed decrease the turbulent momentum exchange in the boundary layer by rectifying the turbulent fluctuations. This generates a significant shear-stress reduction downstream, which is much more than just the effect of the wake of the manipulator. However, the device drag of the manipulator cannot be reduced without simultaneously reducing the skin friction reduction. Thus, the manipulator's device drag exceeds, or at best cancels, the drag reduction achieved by the shear-stress reduction downstream. A critical survey of previous investigations shows that the suggestion that turbulence manipulators may produce net drag reduction is also not supported by the available previous drag force measurements. The issue had been stirred up by less conclusive measurements based on local velocity data, i.e., data collected using the so-called momentum balance technique.List of symbols b lateral breadth of test plate - c chord length of turbulence manipulator - d diameter of wire manipulator - e distance of the elastic center from the leading edge of the manipulator airfoil - h height of manipulator above test plate - q dynamic pressure of the potential flow above the test plate - s spacing of turbulence manipulator elements - t thickness of turbulence manipulator elements - u,v,w fluctuating velocities in downstream, platenormal, and lateral directions - x distance from the leading edge of the test plate in the downstream direction - x ₀ location of the trailing edge of the first manipulator - z distance from test plate center in the lateral direction - C _D drag coefficient - C _L lift coefficient - D _m drag of manipulated plate including device drag and shear stress, calculated from manipulator location to downstream location - D ₀ drag of unmanipulated plate boundary layer, consisting of the shear stress calculated from manipulator location to downstream location - F drag force - F ₀ total skin friction force, measured over a distance from 0.4 m upstream of manipulator to 6.35 m downstream of manipulator, measured without turbulence manipulator - F _LEBU device drag force of the LEBU, i.e., the turbulence manipulator - F _m total drag force of manipulated plate, consisting of - F _LEBU and skin friction force, measured over a distance from 0.4 m upstream of manipulator to 6.35 m downstream - F _cf skin friction force as measured by the floating element balance, manipulated case - F _cfo skin friction force, as measured by the floating element balance, unmanipulated case - F _cf skin friction saving, defined as F _cf = F _cf – F _cfo - F _cf cumulative skin friction savings, i.e., the sum of the skin friction savings F _cf , added up from the location of the manipulator to the downstream location , as shown in Fig. 11. In Fig. 13 the cumulative skin friction savings are summarized up to their asymptotic value, reached at 200 - Re _c Reynolds number of the manipulator elements, calculated with the chord length c and the local velocity in the boundary layer - Re ₀ Reynolds number at the location x ₀ of the manipulator, calculated with the momentum thickness of the boundary layer and the mean flow velocity U - U mean flow velocity in the potential regime of the wind tunnel test section - angle of attack of the manipulator airfoils - ₀ boundary layer thickness at the location x ₀ of the manipulator - dimensionless distance from the manipulator in the downstream direction, defined as - density of the air - ₀ local skin friction shear stress, unmanipulated case - _{0 Average} skin friction shear stress, average value over the lateral span (b = 2 m) of the test plate, unmanipulated case - _m local skin friction shear stress, manipulated case - momentum thickness of the undisturbed turbulent boundary layer at the location x ₀ The authors would like to thank Prof. H. H. Fernholz for his scientific and administrative support. The hardware for the experiments was designed and built by C. Daase, W. Hage and R. Makris. Funding for the project was provided by the Deutsche Forschungsgemeinschaft and is gratefully acknowledged.