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81.
A. F. Bykov P. P. Semyannikov I. K. Igumenov 《Journal of Thermal Analysis and Calorimetry》1992,38(6):1463-1475
The processes of thermal destruction of copper(II) bis(dipivaloylmethanate) (Cu(dpm)2) in the temperature range 150°–550°C were studied by using a two-temperature variant of a double chamber Knudsen cell, with mass spectrometric recording of the gas-phase composition. The temperature range of stability of the vapour of the complex in vacuum was determined, as were those of its mixtures with oxygen in different proportions. The temperature dependence of the rate constant of the thermolysis of (Cu(dpm)2) vapour was obtained. The thermal stability of Hdpm vapour and the influence of oxygen on the thermolysis of the ligand were studied.
Zusammenfassung Unter Verwendung einer Zweitemperaturenvariante der Knudsenschen Doppelkammerzelle wurde mittels MS-Untersuchung der Gasphasenzusammensetzung im Temperaturbereich 150°–550°C der thermische Abbau von Kupfer(II)-bis(dipivaloylmethanat) (Cu(dpm)2) untersucht. Es wurde der Temperaturbereich für die Stabilität der gasförmigen Komplexe in Vakuum sowie in Gemischen mit Sauerstoff in verschiedenen Verhältnissen bestimmt. Dabei wurde die Temperaturabhängigkeit der Geschwindigkeitskonstante für die Thermolyse von Cu(dpm)2 ermittelt. Weiterhin wurde die thermische Stabilität von Hdpm-Dampf sowie der Einfluß von Sauerstoff auf die Thermolyse der Liganden bestimmt.相似文献
82.
I. Brandariz F. Arce X. L. Armesto F. Penedo M. Sastre de Vicente 《Monatshefte für Chemie / Chemical Monthly》1993,124(3):249-257
Summary A systematic study of the dependence of acid-base stoichiometric constants on the ionic strength has been carried out for the aminoacidL-valine in ClK and BrK solutions. The observed dependence has been interpreted by using Guggenheim, Scatchard and Pitzer models for the activity coefficients of the species involved in the equilibria.
Die Abhängigkeit von Gleichgewichtskonstanten desL-Valin von der Ionenstärke entsprechend den Modellen von Guggenheim, Scatchard und Pitzer
Zusammenfassung Es wurde anL-Valin in KCl- und KBr-Lösungen eine systematische Studie der Abhängigkeit der Säure-Base-Stöchiometrie von der Ionenstärke durchgeführt. Die beobachteten Abhängigkeiten wurden aufgrund der nach den Modellen von Guggenheim, Scatchard und Pitzer erhaltenen Aktivitätskoeffizienten der an den Gleichgewichten beteiligten Spezies interpretiert.相似文献
83.
A. A. El-Asmy 《中国化学会会志》1988,35(1):29-34
The preparation and characterization of a series of new coordination compounds of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) containing o-methyl- or o-chlorobenzoyl-4-phenyl-3-thiosemicarbazide (HMBPT, HCBPT=HL) are reported. The reaction products were investigated by analyses, electrolytic conductance, magnetic susceptibility, reflectance and IR spectral studies. The IR spectra show that HMBPT and HCBPT coordinate with the metal ions via different coordination sites (NS and/or NO). The spectral data support the suggestion that the ligands form his-chelates with Ni(II) and Cu(II) of square planar stereochemistry and of general formulae ML2·H2O, where L is the uninegatively charged bidentate ligand. The Co(II) ion forms octahedral and tetrahedral structures with HMBPT and HCBPT, respectively. The ligand field parameters (D4, B and β) for the Co(II) chelates were calculated using the averaged-ligand-field approximation. The influence of the benzene ring substituents (o-chloro or o-methyl) on the stereochemistry are discussed. Also, the formation of the complexes in solution was tested by the pH-metric method. 相似文献
84.
S. V. Galushko 《Chromatographia》1993,36(1):39-42
Summary To calculate retention in reversed-phase, high-performance liquid chromatography a method based on the molecular structure of the analyte and the characteristics of sorbents and mobile phases has been employed. Characteristics of different ODS-columns in water-methanol eluents have been determined. 相似文献
85.
86.
Information content of data and variables and types of weighting in least-squares regression methods
Algorithms are given for evaluating the relative amount of useful information related to a particular parameter which is carried by individual data points and intervals of the variables. The algorithms provide an efficient means of using the information contained in a set of data. Applications to the optimization of weighting in regression methods are described. Several informational and combined informational-statistical types of weighting are studied as a means of improving the accuracy and precision of the parameters obtained by non-linear regression. 相似文献
87.
E. L. Anderson M. M. Thomason H. T. Mayfield W. Bertsch 《Journal of separation science》1979,2(6):335-342
A versatile two-dimensional gas chromatograph is described, consisting of 2 separate ovens, one intermediate trap, an auxiliary inlet, and the necessary hardware to effect off-line switching according to the principle of Deans. The unit has been designed for use with high resolution glass capillary columns. The performance of individual instrumental components was critically evaluated. Results showed that low dead volume glass to metal connections were required in the manifold and detector lines to minimize extra-column effects. The mass of the intermediate trap must be low to allow rapid heating. Operational parameters are discussed and examples of some applications are shown. 相似文献
88.
D. J. Burlett 《Journal of Thermal Analysis and Calorimetry》2004,75(2):531-544
The transfer of heat through an elastomeric matrix is important for both the processing of the material and its subsequent
lifetime. Thermal conductivity can be used to evaluate the influence of different polymers and fillers on heat transfer. Additionally,
the dispersion of the filler has an effect on heat transfer and thermal conductivity measurements can be used to provide semi-quantitative
estimations of filler dispersion. The degradation of sulfur-crosslinked elastomer systems has been studied for many years.
The degradation of the crosslinks (changes in sulfur rank) and degradation of the polymer backbone by thermal and/or oxidative
processes have been studied extensively using many techniques including thermal analysis (references). However, the degradation
of the crosslinked-polymer 'network' is less well understood. The relationship of the crosslink network to this degradation
process is a key to both the long term and higher temperature performance of the sulfur-crosslinked elastomer. The changes
in physical properties observed upon exposure of sulfur-crosslinked elastomers can be monitored using dynamic mechanical analysis.
Subsequently, other thermal techniques can be used to monitor the chemistry that is occurring during these degradations. Thermal
desorption/mass spectroscopy and dynamic scanning calorimetry are used to complete the picture of the degradation processes
taking place. Examples of these techniques will be provided to illustrate the utility of the analytical approach, the chemistry
involved in these degradation processes and the effect of changes in the polymer, cure package and other ingredients.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
89.
Moon Hwan Cho Seung Chang Yang Nam Keun Yang Yongjin Kang Jaejung Ko 《Journal of inclusion phenomena and macrocyclic chemistry》1998,30(4):279-287
The thermodynamic parameters for the interaction of Cu2+, Ni2+, Co2+, Cd2+, andAg+ with the new title ligand have been determined by titration calorimetry in 50% THF–methanol (V/V) at 25 °C.Ag+ exhibited remarkably higher complexation selectivity.Ag+ and several transition metal ions have been transportedusing this ligand as carrier in a bulk liquid membrane. CompetitiveAg+–M2+ transport studies have also beencarried out for the same system. In this membrane transport study, high transport of Ag+ was observed in both single and competitiveAg+–M2+ transport studies. The complexformation of N,N-bis[o-(diphenylphosphino)benzylidene]ethylenediamine (P2N2) with silver,[Ag(P2N2)] (NO3), (1) is reported. Complex 1 has been characterized by X-ray crystallography. 1 ismonoclinic, space group P21/n (No. 14), with cell dimensionsa = 13.398(4) , b=12.577(5) , c = 21.521(4) , =100.14(2) , V = 3570(2) 3 and Z = 4. 相似文献
90.
Simple methods of analysis of first-order kinetic processes controlled by distributions of parameters (activation energies and/or frequency factors) are presented. Both the isothermal and nonisothermal regimes are considered. The procedures make use of numerically calculated time derivatives of the concentrations of decaying species (reactants in the case of chemical reactions). They do not require any adjustable initial or boundary values of parameters (like concentration at the infinite time) being thus more accurate and reliable than earlier methods in which kinetic parameters were determined from the concentration, and not from its time derivative. The methods were successfully employed in analysis of the thermally driven cis–trans isomerization of a photochromic crown ether containing the azobenzene moiety incorporated in the crown. 相似文献