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81.
Analysis of changes in 35Cl NQR frequency of complexes MCl4.L and MCl4.2L for M = Si, Ge, Sn and Ti was performed. The population of the atomic orbitals was calculated by the quantum chemistry methods PM3 and INDO. The results provided an explanation of the changes in 35Cl NQR frequency and the asymmetry parameter upon complex formation. In the complexes of non-transition elements, a decrease in 35Cl NQR frequency is first of all related to increasing population of pz orbitals on Cl atoms. In the complexes of Ti, the increase in 35Cl NQR frequency depends on a decrease in the pπ to dπ electron density transfer. 相似文献
82.
P. Niedzielski M. Siepak B. Dudzińska-Huczuk 《Central European Journal of Chemistry》2003,1(3):314-324
This paper reports the results of an optimisation study for a procedure to determine the total selenium and its inorganic
species, Se(IV) and Se(VI) using atomic absorption spectrometry combined with hydride generation and in-situ trapping of the
analyte on the inner walls of the graphite tube. With the use of the proposed modification, a detection limit (3σ) of 0.018
ng/ml is achieved. This paper presents exemplary results, according to the proposed procedure, for selenium determination
in samples of marine water. The concentrations of selenium in the samples ranged from <0.02 ng/ml to 0.16ng/ml of Se(IV) and
from <0.02 ng/ml to 0.10 ng/ml of Se(VI). 相似文献
83.
Mariusz Mamiński 《Analytica chimica acta》2005,540(1):153-157
In this paper we report two simple and sensitive spectrophotometric procedures for the determination of dopamine in microfluidic system based on poly(dimethylsiloxane) (PDMS) technology and comparison of their interference-susceptibility. The analytical reactions and measurements were carried out at ambient temperature in a microreactor of total volume 6 μl coupled with a spectrophotometric flow-through cuvette. 相似文献
84.
The role of the electrostatic double-layer interactions in adsorption of colloid particles at solid/liquid interface was reviewed. The phenomenological formulation of the governing PB equation was presented with the expressions for the pressure tensor enabling one to calculate forces, torques and interaction energies between particles in electrolyte solutions. Then, the limiting analytical results for an isolated double-layer (both spherical and planar) were discussed in relation to the effective surface potential concept. The range of validity of the approximate expression connecting the surface potential and the effective surface potential with surface charge for various electrolytes was estimated. The results for double-layer systems were next presented including the case of two planar double-layers and two dissimilar spherical particles. Limiting solutions for short and long distances as well as for low potentials (linear HHF model) were discussed. The approximate models for calculating interactions of spheres, i.e., the extended Derjaguin summation method and the linear superposition approach (LSA) were also introduced. The results stemming from these models were compared with the exact numerical solution obtained in bispherical coordinate system. Possibilities of describing interactions of nonspherical particles (e.g., spheroids) in terms of the Derjaguin and the equivalent sphere methods were pointed out. In further part of the review the role of these electrostatic interactions in adsorption of colloid particles was discussed. Theoretical predictions were presented enabling a quantitative determination of both the initial adsorption flux for low surface coverages and the surface blocking effects for larger surface coverages. Possibility of bilayer adsorption for dilute electrolytes was mentioned. The theoretical results concerning both the adsorption kinetics and structure formation were then confronted with experimental evidences obtained in the well-defined systems, e.g., the impinging-jet cells and the packed-bed columns of monodisperse spherical particles. The experiments proved that the initial adsorption flux was considerably increased in dilute electrolytes whereas the monolayer coverages were considerably decreased due to lateral interactions among particles. It was then concluded that the good agreement between experimental and theoretical data confirmed the thesis of an essential role of the electrostatic interactions in adsorption phenomena of colloid particles. 相似文献
85.
Copolymerization of acrylonitrile with methacrylates on a matrix has been examined (using methacrylate of p-cresol-formaldehyde resin). It has been found that the copolymerization proceeds at 70° without an initiator. The reactivity ratios depend on the length of the matrix used. The method of calculating Q and e according to the Alfrey-Price scheme has been discussed for the system under investigation. 相似文献
86.
A simple isotherm equation is derived for the adsorption of an organic component onto activated carbon in presence of water vapour. The theoretical results are compared with experimental data for toluene-water vapour-activated carbon, which were published byRipperger andGermerdonk [10].
Symbols a i adsorbate concentration in adsorbent, kg/kg of carbon - a 0i monolayer capacity, kg/kg of carbon - b i kinetic parameter of theLangmuir equation - E j adsorption energy in thej-th layer - i i-th component (1 — water vapour, 2 — organic compound) - j j-th layer - m number of layers - n number of adsorbed components - p partial pressure, Pa - p* saturation partial pressure, Pa - p C water vapour partial pressure at begining of capillary condensation, Pa - surface coverage 相似文献
Vorhersage der Adsorption einer organischen Komponente und Wasserdampf an Aktivkohle
Zusammenfassung Es wird eine einfache Adsorptionsisotherme abgeleitet, welche die gleichzeitige Adsorption eines organischen Stoffes und Wasser an Aktivkohle beschreibt. Die theoretischen Ergebnisse werden mit experimentellen Resultaten vonRipperger undGermerdonk [10] für Toluol-Wasser-Aktivkohle verglichen.
Symbols a i adsorbate concentration in adsorbent, kg/kg of carbon - a 0i monolayer capacity, kg/kg of carbon - b i kinetic parameter of theLangmuir equation - E j adsorption energy in thej-th layer - i i-th component (1 — water vapour, 2 — organic compound) - j j-th layer - m number of layers - n number of adsorbed components - p partial pressure, Pa - p* saturation partial pressure, Pa - p C water vapour partial pressure at begining of capillary condensation, Pa - surface coverage 相似文献
87.
Aromatization of the title compound with selected acidic catalysts has been investigated. It has been established that depending upon the reaction conditions trienone 2,1 -methyltrienone3, dienone 4, diacetoxyketone5 or dione 6 are formed as the major products. Dienone 4 and dione 6 are the main compounds of the reactions of tosyloxyketone 10 with KHSO4 and HBraq, respectively. The reaction of acetoxyketone 8 with HBraq furnishes epimeric 3-bromoketones 12 and 13 in the ratio about 1:1. 相似文献
88.
Janusz Slawiski Marian Elbanowski‡ Danuta Slawiska 《Photochemistry and photobiology》1980,32(2):253-260
The spectral distribution of the chemiluminescence, fluorescence and phosphorescence of tryptophan aqueous solutions irradiated with high and low pressure mercury lamps has been measured. The blue emission bands in the region of 380–520 nm observed both in the chemi- and photoluminescence, as well as an absorbance increase at 230 and 330 nm, indicate oxidative degradation of tryptophan leading to the formation of derivatives of N-formylkynurenine, xanthurenic and anthranilic acids. Red emission bands at 630 and 705 nm in the spectrum of the chemiluminescence, an enhancement of light intensity by D2 O and its decrease by NaN3 and DABCO suggest a partial contribution of O2 (1 Δg ) to the photooxidation and chemiluminescence of tryptophan. The enthalpy of the exergonic reactions, leading to the formation of luminescing products, was calculated to average -270 kJ-mol. 相似文献
89.
Bogusław Bobrański 《Mikrochimica acta》1956,44(12):1735-1746
Zusammenfassung Das vom Verfasser undE. Sucharda schon 1928 angewandte Prinzip, die durch das Verhalten der Substanz beim Erhitzen bewirkten Druckschwankungen im Verbrennungsrohre zum Zwecke der automatischen Regulierung der Vergasungsgeschwindigkeit der Substanz bei der Elementaranalyse auszunutzen, wurde bei der Konstruktion einer neuen, elektrisch betriebenen, automatischen Apparatur angewandt. Hierbei wird das mit der Substanz gefüllte Mikroschiffchen mittels eines elektrischen Hochfrequenzgenerators erhitzt. Der Stromzufluß zu dem Hochfrequenzgenerator wird durch die erwähnten Druckschwankungen einoder ausgeschaltet. Die Verbrennung verläuft dann bei praktisch konstantem Druck im Verbrennungsrohre, also auch bei konstantem Sauerstoffüberschuß. Die neue Apparatur wird an Hand beigefügter Abbildungen beschrieben. Als Absorptionsmittel für Stickstoffoxyde werden 1 bis 2 g Bleidioxyd in einem 12 cm langen Porzellanschiffchen bei 190° angewandt. Die Absorption des Wassers erfolgt durch wasserfreies Kobaltchlorid, die der Kohlensäure ausschließlich durch Ascarit. Die Sauerstoffgeschwindigkeit im Verbrennungsrohre beträgt 8 ml pro Minute. Bei Substanzen, die mehr als 10% N enthalten, wird zwischen den Kohlensäureabsorptionsapparat und den Wasserabsorptionsapparat ein mit Mangandioxyd gefüllter Apparat eingeschaltet.
Summary The principle used by the author andE. Sucharda as early as 1928, which employs the variations in pressure in the combustion tube resulting from the behavior of the substance when heated, for automatically regulating the rate of gasifying the substance was applied in the construction of a new electrically operated automatic apparatus. The micro boat charged with the sample is heated by means of a high frequency generator. The flow of current to the high frequency generator is switched on and off by the variations in pressure mentioned above. The combustion then proceeds at practically constant pressure in the combustion tube, and even when there is a constant excess of oxygen. The new apparatus is described in the accompanying figures. The nitrogen oxides are absorbed in 1 to 2 grams of lead dioxide contained in a porcelain boat (12 cm long) at 190°. The absorption of the water is by means of anhydrous cobalt chloride, while the carbon dioxide is taken up in ascarite. The speed of the oxygen in the combustion tube is 8 ml per minute. In the case of samples that contain more than 10% nitrogen, an apparatus filled with manganese dioxide is placed between the carbon dioxide absorber and the apparatus for taking up the water.
Résumé Le principe de l'utilisation des variations de pression qui se produisent dans un tube à combustion en analyse élémentaire, lors du chauffage de la substance, a été utilisé dès 1928 par l'auteur etE. Sucharda pour la régulation automatique de la gazéification de cette substance. Il a été appliqué à la construction d'un nouvel appareil automatique commandé électriquement. La micronacelle qui contient la substance est chauffée électriquement à l'aide d'un générateur de courant de haute fréquence. Les variations de pression pendant la combustion provoquent l'ouverture ou la fermeture du circuit d'alimentation de ce générateur. Il en résulte que la combustion est effectuée à pression pratiquement constante ainsi qu'à excès d'oxygène constant. Ce nouvel appareil est décrit sur les figures de la publication.On utilise 1 à 2 grammes de bioxyde de plomb disposés dans une nacelle de porcelaine de 12 cm de longueur, portée à 190° pour absorber les oxydes de l'azote. L'eau est absorbée par du chlorure de cobalt anhydre et l'anhydride carbonique exclusivement par de l'ascarite. Le débit du courant d'oxygène dans le tube de combustion est de 8 ml par minute. Pour les substances contenant plus de 10% d'azote, on intercale un absorbeur à bioxyde de manganèse entre l'absorbeur à anhydride carbonique et l'absorbeur à eau.相似文献
90.
Acidolytic cleavage of unsymmetrically substituted dithioacetal monoxides, ArCH(SR)S(O)Me has been used to prepare linear unsymmetrical disulfides RSSMe. Disproportionation was suppressed by the addition of a small amount of benzyl mercaptan. The required starting materials were conveniently obtained from appropriately substituted sulfines ArC(=SO)SR and methyl lithium. The following disulfides were prepared: R =n-C4H9 (73.5%), n-C7H15 (78%), Ph (77.3%), AcO(CH2)10 (81.5%).The unsymmetrical dithioacetal PhCH(SEt)SC7H15-n gave upon oxidation with one equivalent of peracid a mixture of two dithioacetal monoxides which on treatment with HClO4 led to three disulfides. This result is discussed in term of the mechanism of acidolysis. 相似文献