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21.
Cathodic stripping methods are described for the determination of traces of thiocyanate ions down to 2 × 10-8 mol l-1 and Cu(II) ions down to 1 × 10-8 mol l-1. The method involves electrolytic accumulation of copper(I) thiocyanate on the surface of a hanging mercury drop electrode followed by stripping of the deposit during the cathodic scan. For the determination of thiocyanate, a copper amalgam electrode can be used. Examples of application of the method for the determination of traces of thiocyanate in common salts, in saliva and urine as well as for the determination of copper(II) ions in tap water are described. 相似文献
22.
Marek Trojanowicz Joanna Szpunar-Łobińska Zdzislaw Michalski 《Mikrochimica acta》1991,103(3-4):159-169
An original computer-controlled solid-state photometer has been developed and its potential for simultaneous multicomponent flow-injection analysis of binary and ternary mixtures is demonstrated. The device is simple in construction. Its principle of operation is based on rapid sequential measurements of the absorbance of the complexes formed by the analytes with chromogenic reagents at the wavelengths corresponding to the emission maxima of three light emitting diodes (563, 580 and 638 nm). 相似文献
23.
The voltammetric behaviour of the In(III)-In(Hg) system was studied at the silver-, graphite-, and glassy carbon-based mercury film electrodes under cyclic and stripping conditions in thiocyanate media. The reversible curves obtained at high thiocyanate ion concentration showed a good agreement with theoretical predictions, particularly for the cathodic process. The anodic curves obtained at thin silver-based mercury film electrodes deviated from theoretical predictions due to the interactions between indium, dissolved in mercury, and the silver substrate of the film electrode. At low thiocyanate ion concentrations, where the current was controlled partly by the rate of the preceding chemical step and partly by diffusion, the variations in the film thickness affected the position of the curve as predicted theoretically for the reversible diffusion controlled case. 相似文献
24.
S. I. Kozlov G. Łapienis G. V. Rakova K. S. Kazanskii 《Polymer Science Series A》2006,48(10):1022-1034
Soluble comb-shaped and swelling network polymers based on monomethacrylate (M = 2080) and bismethacrylate (M = 4000) poly(ethylene oxide) macromonomers, have been synthesized by the controlled atom-transfer radical polymerization in aqueous media. PEG 2000 methyl ether ethyl-2-bromoisobutyrate and 2-bromoisobutyrate, in combination with CuBr, CuBr2, and 2,2′-bipyridyl, have been used as initiators. The length of the main chain of comb-shaped polymers, as estimated with multidetector chromatography, is in good agreement with the calculated values in the 15–20 range at M w /M n = 1.42–1.89. The polymerization of the methacrylate macromonomer proceeds at a high rate and with a nearly quantitative conversion. The replacement of 10–80 mol % CuBr with CuBr2 appreciably decelerates polymerization and decreases polydispersity to 1.14–1.21, while the experimental and calculated values of chain lengths remain equal. This finding indicates a higher level of process control. The polymer networks thus prepared manifest Gaussian elastic behavior, as is evident from the relationship between the elastic modulus G and the swelling degree Q that is consistent with the classical prediction G ~ Q m , where m = ?1/3. Within the framework of the accepted model of networks of this type, this fact suggests the short length of polymethacrylate chains. In addition, the relationship between the time of attainment of the gelation point and the composition of the initiation system agrees with the atomtransfer controlled polymerization mechanism. The efficiencies of various radical polymerization methods for controlling the network structure are compared. 相似文献
25.
Using voltammetric, galvanostatic and potentiostatic techniques, the electrodeposition of cuprous thiocyanate on a copper amalgam electrode has been studied in acidic solutions containing various thiocyanate ion concentrations. Under the conditions used, the formation of two successive monolayers of CuSCN could be studied before the onset of bulk deposition. It was found that the formation of the first monolayer proceeds according to a complex adsorption-nucleation and growth mechanism. In the first stage, cuprous thiocyanate is adsorbed on the amalgam electrode; in the second, the disordered layer of adsorbate rearranges to form two-dimensional crystalline centres; and in the third stage, these centres grow, completing the formation of the entire monolayer. The second monolayer is formed in a much simpler way, according to a mechanism of two-dimensional, instantaneous nucleation and growth. At high thiocyanate ion concentration, the formation of the CuSCN layer is obscurred by the extensive formation of solution soluble species. 相似文献
26.
Dagmara Jacewicz Agnieszka Łapińska Aleksandra Dąbrowska Lech Chmurzyński 《Transition Metal Chemistry》2006,31(1):111-117
The kinetics of the reaction between gaseous CO2 and the cis-[Cr(phen)2(OH2)2]3+ ion leading to the formation of the carbonato complex ion, have been studied over the pH and temperature ranges: 3 < pH <
6 and 5 < T < 25 °C, respectively, at a constant ionic strength of 1 m (NaClO4). Investigations were carried out using the stopped-flow spectrophotometry technique in the UV–Vis range: 340–700 nm. The
major reactant species in the pH range studied was cis-[Cr(phen)2(OH)(OH2)]2+ ion, which underwent reaction with CO2 to form cis-[Cr(phen)2(OH2)(HCO3)]2+ ion. Subsequently, slower ring closure of the latter species to form the bidentate carbonato chelate was observed. The possible
mechanism has been discussed and the activation parameters ΔH† and ΔS† were also determined for the reaction studied. 相似文献
27.
Electrosorption of hydrogen into palladium-gold alloys 总被引:1,自引:0,他引:1
M. Łukaszewski K. Kuśmierczyk J. Kotowski H. Siwek A. Czerwiński 《Journal of Solid State Electrochemistry》2003,7(2):69-76
Hydrogen electrosorption into Pd-Au alloys has been studied in acidic solutions (1 M H2SO4) using cyclic voltammetry. Pd-Au electrodes with limited volume were prepared by electrochemical co-deposition. It was found
that the maximum H/(Pd+Au) ratios decrease monotonically with increasing gold content and reach zero at ca. 70 at% Au. Similarly
to the case of Pd limited volume electrodes, two peaks in the hydrogen region, corresponding to two types of sorbed hydrogen,
are observed on voltammograms for Pd-rich alloys. The hydrogen capacity, H/(Pd+Au), measured electrochemically, depends on
the sweep rate in the cyclic voltammetry experiments, which suggests that two different mechanisms for hydrogen desorption
from the Pd-Au alloy are possible. After a strong decrease of Pd concentration at the electrode surface, caused by long cyclic
polarization to sufficiently anodic potentials, the amount of absorbed hydrogen is still significant for alloys initially
rich in Pd. The results obtained from CO adsorption experiments suggest that only Pd atoms are active in the hydrogen absorption/desorption
process.
Electronic Publication 相似文献
28.
Joanna Szpunar-Łobińska Michiel Ceulemans Wilfried Dirkx Claudia Witte Ryszard Łobiński Freddy C. Adams 《Mikrochimica acta》1994,113(3-6):287-298
Interferences in trace and ultratrace speciation analysis of organotin and organolead compounds in various samples by gas chromatography coupled with atomic absorption spectrometry (AAS) and/or microwave induced plasma atomic emission spectrometry (MIP AES) are investigated. Particular attention is given to the effects of matrix co-extractives and reagents impurities introduced during sample preparation. Their influence on the detection limits is discussed in terms of baseline noise level, blank value, formation of artefacts and signal suppression. Loss of column resolution during the analysis of some matrices is observed. 相似文献
29.
Using the silver based mercury film electrode (SBMFE) and cyclic and stripping voltammetric techniques the behaviour of cadmium has been compared with the behaviour of lead as well as with the predictions of the theory of de Vries and van Dalen. At the SBMFE with film thickness between 0.1 and 2 μm lead behaves with good agreement with theoretical predictions and only at thicknesses higher than 2 μm some deviations occur due to collecting of the excess mercury at the bottom of the wire electrode. On the other hand even at thin film electrodes the behaviour of cadmium deviates significantly from the predictions of the theory. The height of the anodic peak decreases and its width increases; also the displacement of the potentials of both cathodic and anodic peaks is smaller than the values predicted theoretically. The deviations are caused neither by the formation of intermetallic compounds in the bulk of mercury phase nor by the formation of heterogenous cadmium amalgam; they reflect the interaction between cadmium dissolved in mercury and the solid silver amalgam which is the substrate of the mercury film. Owing to the effect discussed the stripping determination of cadmium at SBMFE is characterized by a lower sensitivity and reproducibility. 相似文献
30.
During the reactions of lithium oxide with aluminium nitride, and of lithium nitride with aluminium oxide, the formation has been observed of a previously unknown compound, of composition Li2AlNO. The course of its thermal decomposition has also been determined.
Zusammenfassung Es wurde das Auftreten einer bisher unbekannten Verbindung der Zusammensetzung LiAlNO bei den Reaktionen von Lithiumoxid mit Aluminiumnitrid und Lithiumnitrid mit Aluminiumoxid beobachtet. Der Verlauf der thermischen Zersetzung dieser Verbindung wurde bestimmt.
Li2AlNO. .相似文献