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The convergence of the eigenchannel (EK) and R-matrix (RM) theories - depending on their free parameters - is numerically investigated by comparing with a simple, analytically solvable model. The comparison shows that the results of the EK-theory are in general closer to the exact solution than those of the RM-theory. Especially in regions of sharp resonances the dependence of the expansion of the wave functions on the interaction radius ac and on the boundary condition Bc is very strong in the RM-theory and one needs very many levels to achieve good results.
The association of Schlen k’s hydrocarbon was studied by means of osmometric and magnetic measurements. The mixed chain-ring-association can be explained satisfactorily assuming that two different dimers and four monomer species participate in the equilibria, including a monomeric diamagnetic ring. The equilibria existing between the different species are discussed. For the equilibria between the monomer and dimer species, which can be detected in solutions of normal viscosity by means of ESR-measurements, the unexpected values of ΔH=0 for the enthalpie of association and ΔS= +19.7 e. u. for the entropie of association were found.
Substituted amides react with tridiloromethanesulfenyl chloride in the presence of triethylamine to following compounds: S=PCl2NCH3SCCl3, S=PFCl2NCH3SCCl3, S =PFClNCH3SCCl3, S=PF2NCH3SCCl3, O = PCl2NCH3SCCl3, O= PFClNCH3SCCl3, O = PF2NCH3SCCl3, FSO2NCH3SCCl3 and CF3SO2-NCH3SCCl3. The properties of these substances are described. They were characteriszed by elemental analyses, IR- and mass spectra. 19F-, 1H- and 31P-NMR spectra are reported and discussed.
By reacting S = PX2NHCH3 or O = PX2NHCH3 (X = F and/or Cl) with S = PF2Br in the presence of triethylamine the following compounds are prepared: S = PCl2NCH3F2P = S, S = PFClNCH3F2P = S, O = PCl2NCH3F2P = S and O = PFClNCH3F2P = S. Also, the infrared, proton NMR, fluorine NMR, phosphorus NMR, and mass spectral data of these compounds are presented and discussed.
The preparations of the following compounds are described: O = PF2N = PCl2N = PCl3, O = PF2N = PCl2N = PCl2N (CH3) 2, O = PF2N=PCl2N = PCl2N (C2H5) 2, O = PF2N = PCl2N (CH3) 2, O = PF2N = PCl2N (C2H5)2, O = PF2N = PCl2N (CH3) Si (CH3)3, O = PF2N = PCl2NCS, O = PFClN = PCl2N (CH3)2, O = PFClN = PCl2N (C2H5)2, O = PFClN = PCl [N (C2H5)2]2 and O =P (C6H5) FN = PCl3. They were characterized by 1H-, 19F- and 31P-nmr spectroscopy. Analytical, ir and mass spectral data are reported. The properties of these substances are compared with the corresponding thiophosphorylderivatives.
Gel layers of crosslinked polyacrylamide with different porosities were synthesized and their properties compared. At high concentrations of bifunctional monomers macroporous gels were formed, one of which (total monomer concentration 14%, methylene-bis-acrylamide 40%) permitted even high molecular weight proteins (e. g. γ-globulins) to diffuse more readily than in 2 per cent agar or agarose gels. Different immunological techniques were modified for application with this polymer. It offers advantages especially with respect to porosity, storability and sample application for quantitative diffusion techniques.
The ion-molecule reactions of thiothionylfluoride have been studied by ion cyclotron resonance spectrometry. The major secondary ions are S2F3+ , S3F+ , and S3F2+. In a consecutive reaction of S3F2+ the tertiary ion S4F2+ is formed. The rate constant of the IMR with the greatest yield S2F2+ + SSF2 → S3F2+ + SF was estimated to k = 2 · 10-9 cm 3 molecule -1 sec -1 . The results were compared with the mass spectrum of thiothionylfluoride. They permit conclusions on chemical reactions of lower sulphurfluorides.