Simple, expedient methods for the determination of water and electrolyte contents of cellulose solvent systems

The concentrations of water, W, and electrolytes present in solutions of LiCl in N,N-dimethylacetamide, LiCl/DMAc, and of tetrabutylammonium fluoride. x-hydrate in DMSO, TBAF.xW/DMSO can be accurately and expediently determined by three independent methods, UV–vis, FTIR and EMF measurement. The first relies on the use of solvatochromic probes whose spectra are sensitive to solution composition. It is applicable to W/LiCl/DMAc solutions but not to TBAF.xW/DMSO, because the charge-transfer complex bands of the probes are suppressed by strong interactions with the latter electrolyte. Integration of ν_OH band of water may be employed in order to determine [W], hence [electrolyte] by weight difference. EMF measurement uses ion-selective electrodes in order to determine [electrolyte], hence [W] by weight difference. Results of the latter method were in excellent agreement with those of FTIR. The reason for the failure of Karl Fischer titration is addressed, and the relevance of the results obtained to functionalization of cellulose under homogenous solution conditions is briefly commented on.     

Mathematics achievement and interest in mathematics from a differential perspective

In this article, we present results of an empirical study with 500 German students of grades 7 and 8. The study focussed on students' mathematics achievement and their interest in mathematics as well as on the relation between these two constructs. In particular, the results show that the development of an individual student's achievement between grade 7 and grade 8 depends on the achievement level of the specific classroom and therefore on the specific mathematics instruction Interest in mathematics could be regarded a predictor for mathematics achievement Moreover, our findings suggest that the students show hardly any fear of mathematics independent of their achievement level.     

Complex magnetism in ultra-thin films: atomic-scale spin structures and resolution by the spin-polarized scanning tunneling microscope

In this paper we present a density functional theory investigation of complex magnetic structures in ultra-thin films. The focus is on magnetically frustrated antiferromagnetic Cr and Mn monolayers deposited on a triangular lattice provided by a Ag (111) substrate. This involves non-collinear magnetic structures, which we treat by first-principles calculations on the basis of the vector spin-density formulation of the density functional theory. We find for Cr/Ag (111) a coplanar non-collinear periodic 120° Néel structure, for Mn/Ag (111) a row-wise antiferromagnetic structure, and for Fe/Ag (111) a ferromagnetic structure as magnetic ground states. The spin-polarized scanning tunneling microscope (SP–STM) operated in the constant-current mode is proposed as a powerful tool to investigate complex atomic-scale magnetic structures of otherwise chemically equivalent atoms. We discuss a recent application of this operation mode of the SP–STM on Mn/W (110), which led to the first observation of a two-dimensional antiferromagnet on a non-magnetic metal. The future potential of this approach is demonstrated by calculating SP–STM images for different magnetic structures of Cr/Ag (111). The results show that the predicted non-collinear magnetic ground state structure can clearly be discriminated from competing magnetic structures. A general discussion of the application of different operation modes of the SP–STM is presented on the basis of the model of Tersoff and Hamann. Received: 07 May 2001 / Accepted: 23 July 2001 / Published online: 3 April 2002     

Korrosionsuntersuchung

Ohne Zusammenfassung     

Pattern formation in diffusion-limited reactions

The conditions for macroscopic segregation ofA andB in a steady-stateA+B 0 reaction are studied in infinite systems. Segregation occurs in one and two dimensions and is marginal ford=3. We note the dependence of these results on the precise experimental conditions assumed in the theory. We also note the difference between these results and our earlier ones for finite systems where the critical dimension isd=2.     

Analogy between the Lorenz strange attractor and a bistable stochastic oscillator

The relation between the aperiodic solution of the Lorenz model and that of a stochastic anharmonic oscillator is explored. The stochastic oscillator is constructed by replacing (t) in the Lorenz model by a stochastic variable(t) of specified statistics. The resulting system is of course not isomorphic to the Lorenz model, but does share with it a number of statistical properties. Thus, within the confines of these measures the two systems are physically very similar.     

Statistical replacement for systems with delta-correlated fluctuations

Nonlinear systems with stochastic parameters are approximated by simpler systems using a method that we call statistical replacement. This method is an extension of the previously developed AGREE which was restricted to systems with additive fluctuations. Statistical replacement incorporates the distinctions between globally stable thermodynamically closed systems and thermodynamically open systems that can be unstable.     

HPLC isolation and NMR structure elucidation of the most prominent octabromo isomer in technical octabromo diphenyl ether

The major octabromo isomer of technical octabromo diphenyl ether mixture (technical octaBDE) DE-79 was isolated by RP-HPLC. Three serially coupled columns (each 250 mm long) enabled a good separation of the target compound from other congeners using 100% ACN as eluent. Approximately 100 microg of the target compound was isolated with a purity of >90% and investigated by MS for confirmation of the degree of bromination. 1H-NMR and 2-D 1H-13C correlation NMR spectra unequivocally clarified that the octaBDE in question is 2,2',3,3',4,4',6,6'-octabromodiphenyl ether (BDE 197). Based on annual production rates of technical BDE products (1999/2001), approximately 380 tons of BDE 197 were annually produced which, on the long term, may enter the environment. Compared with other individual BDE congeners, BDE 197 has the seventh highest application rate. Reductive debromination of BDE 197 can lead to four hepta-, 15 hexa-, 23 penta-, and 28 tetra-BDE isomers, respectively. This variety includes all known major BDEs of environmental concern (BDE 47, 85, 99, 100, 153, 154, and 183). The identification of BDE 197 in technical octaBDE DE-79 strongly suggests that research on the environmental fate of BDEs should include this key-BDE congener.