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71.
Majumdar A Behnke JF Hippler R Matyash K Schneider R 《The journal of physical chemistry. A》2005,109(41):9371-9377
Chemical reactions in a dielectric barrier discharge at medium pressure of 250-300 mbar have been studied in CH(4)/Ar and CH(4)/N(2) gas mixtures by means of mass spectrometry. The main reaction scheme is production of H(2) by fragmentation of CH(4), but also production of higher order hydrocarbon molecules such as C(n)H(m) with n up to 9 including formation of different functional CN groups is observed. Formation of C(2)H(2), C(2)H(4), and C(2)H(6) molecules has been investigated in some detail. Significant differences are noted in comparison to a theoretical estimate. 相似文献
72.
A few 2-substituted 1-(1-ethoxyethyl)benzimidazoles have been prepared and the rate constants for their hydrolysis measured at various temperatures and oxonium ion concentrations. The formal kinetics followed and the effect of varying the 2-substitution on the hydrolysis rate suggest that the acid-catalyzed cleavage of these compounds involves a rapid initial protonation of the benzimidazole ring and a subsequent rate-limiting heterolysis of the protonated substrate to form a free nitrogen base and an ocarbenium ion derived from the ethoxyethyl group. The values obtained for the entropy of activation are consistent with the assumed unimolecular nature of the rate-limiting step. The effects of 2-substituents on the acidities of the protonated substrates and their heterolysis rates have been compared. The latter partial reaction has been suggested to be the subject of steric acceleration. 相似文献
73.
Günter Ehrlich Thomas Nestler Rainer Voigtmann Willi Moldenhauer 《Mikrochimica acta》1989,98(4-6):249-258
To compare concentration profiles in solids in an objective manner, a multi-dimensional generalization of the comparison of two means by Student'st-test is proposed. The approach is based on piecewise modelling the profiles using rougha priori information, estimating the model parameters and their covariance matrix and comparing the estimated parameters by use of multidimensional test variables. The piecewise modelling is treated in the most important cases in such a way that the partial functions are straight lines or cubic polynoms (splines) with continuity at all knots in each case. It enables us to compare whole profiles as well as the most relevant parts of them. Two ways of estimating the covariance matrix as a generalization of the variance estimation are discussed. The approach is useful for any kind of line profiles if rough information on the profile type is available. As an example SIMS depth-profiles of aluminum obtained from thin-layer systems after different technological heat treatments are considered. These profiles are modeled by three straight lines. 相似文献
74.
O. Seidelmann L. Beyer Grit Zdobinsky R. Kirmse F. Dietze R. Richter 《无机化学与普通化学杂志》1996,622(4):692-700
N,N-Dialkyl-N′-ferrocenoylthioureas and Ferrocene-1,1′ -dicarbonic-acid-di-N,N-dialkylthioureides as Ligands for Transition Metals: Synthesis, Acid-Dissociation Constants, X-Ray Structure Determination, and EPR-Single Crystal Investigation Reaction of ferrocenoylisothiocyanate or ferrocene-1,1′ -dicarbonic acid -diisothiocyanate with secondary amines gives N,N-dialkyl-N′ -ferrocenoylthioureas or the respective ferrocene-1,1′-dicarbonic acid-di-N,N-dialkyl-thioureides. The former yield neutral complexes with transition metal ions (Ni2+, Cu2+, Co3+, Pt2+, Fe3+). The acid dissociation constants of the ligands were determined. The EPR spectra of a bis-(N,N-dinbutyl-N′-ferrocenoylthioureato)copper(II) single crystal are discussed. The X-ray structure determination of ferrocene-1,1′-dicarbonic acid-di-N,N-diethyl-thioureide and its different behaviour against Ni2+ and Cu2+ is presented. 相似文献
75.
Gert Brandl Fritz Kastner Rainer Fritsch Herbert Zinner Albrecht Mannschreck 《Monatshefte für Chemie / Chemical Monthly》1992,123(11):1059-1069
Summary A procedure is described which serves to measure circular dichrograms () on line during stops of flow in liquid chromatography. Since the concentration of substrate in the spectrometer cell during the stop is not known, the differential absorption coefficients are calculated from the experimental differential absorbances A by means of UV absorption (i. e. photomultiplier voltage) data. Verifications of the procedure are obtained by its application to three substrates (Table 1), the () spectra of which were known. The present on-line technique is compared with a corresponding off-line method.The N,N-dimethylthiobenzamides1 and2 as well as the 9,10-phenanthrenequinone7 consist of interconvertible enantiomers because their planar states are destabilized by steric overcrowding of groups. The unknown dichrograms () of1, 2 and7 are obtained (Figs. 2 and 4) and discussed with reference to the helicities of these molecules.In memory of the late Professor Dr. Dr. h. c. Günther Snatzke. 相似文献
76.
77.
The complex [C5H5RhH(C2H4)PMe3]BF4 (I) reacts with NaF and NaCN by deprotonation to give C5H5Rh(PMe3)C2H4 but with NaCl, NaBr and NaI the ethylrhodium compounds C5H5RhC2H5(PMe3)X (II–IV) are obtained. The reactions of I with CO and PPri3 yield the BF4 salts of the cations [C5H5RhH(CO)PMe3]+ and [C5H5RhH(PPri3)PMe3]+ (V, VI), respectively, from which the uncharged complexes C5H5Rh(CO)PMe3 (VII) and C5H5Rh(PPRi3)PMe3 (VIII) are prepared. The carbonyl compound VII is also accessible either from C5H5Rh(CO)2 and PMe3 or from C5H5Rh(PMe3)2 and CO. The reaction of I with ethylene leads to the BF4 salt of the cation [C5H5RhC2H5(PMe3)C2H4]+ (X) which on treatment with PMe3 forms the complex [C5H5RhC2H5(PMe3)C2H4PMe3]BF4 (XI). The compound [C5H5RhH(C2H4)PPri3]BF4 (XII) reacts with NaI by insertion to yield C5H5RhC2H5(PPri3)I (XIII) whereas with PPri3 the salt [C5H5RhH(PPri3)2]BF4 (XIV) is produced. The bis(triisopropylphosphine) complex C5H5Rh(PPri3)2 (XVI) is obtained from XIV and NaH. 相似文献
78.
Anton Meller Walter Maringgele Rainer Oesterle 《Monatshefte für Chemie / Chemical Monthly》1980,111(5):1087-1096
The reaction of galliumtrichloride and galliumtribomide resp. with 2,6-dimethyl- and 2,4,6-trimethyl-N-trimethylsilyl-trifluoroacetanilide leads to the trifluoracetanilidodihalogenogallanes1–3. The 2,6,9-trioxa-4,8-diaza-1,5-digalla-bicyclo-[3.3.1]-nonadiene derivatives1 a–3 a are formed probably as by products.N-Trimethylsilyltrifluoroacetamide reacts with galliumtrichloride to yield the trifluoroacetamido-dichlorogallane4.N-Trimethylsilyl-N,N,N-triorganyl-thioureas react with galliumtrichloride under elimination of chlorotrimethylsilane to give the thio-ureido-gallanes5 and6. IfN,N-diorganylureas andN,N-diorganyl-thio-ureas resp. are reacted with galliumtrichloride and methyl-gallium-dichloride resp., the thio-ureido- and ureido-gallanes7–9 are obtained by elimination of hydrogenchloride. The compounds are characterized by analysis and spectral data (NMR:1H,19F; MS; IR). The substances are monomeric in the gas phase, obviously due to internal coordination.
30. Mitt.:W. Maringgele undA. Meller, J. Organomet. Chem., im Druck. 相似文献
79.
80.
Zusammenfassung Durch den Einsatz zweiwertiger Ionen in der wäßrigen Subphase kann die Packungsdichte gespreiteter Monoschichten wasserunlöslicher Tenside pH-abhän-gig erhöht werden. Ergebnisse für Octadecylamin auf einer Lösung von Natriumhydrogensphosphat werden angegeben.
Mit 2 Abbildungen 相似文献
Summary The packing density of spread monolayers of waterinsoluble surface-active agents can be increased by use of bivalent ions in the aqueous subphase. Results for octadecyl amine spread on a solution of sodium hydrogen phosphate are given.
Mit 2 Abbildungen 相似文献