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61.
This paper describes the use of a thin-layered dual-band electrochemical cell operating at flow conditions to determine dipyrone (sodium salt of 1-phenil-2,3-dimethyl-4-methylaminomethanesulfonate-5-pyrazolone) by reaction with electrogenerated iodine. The electrolytic cell consisted of two closely spaced gold electrodes, the upper stream electrode serving as the generator electrode and the downstream electrode working as the collector electrode. A linear dynamic range from 2 to 15 μmol l−1 dipyrone was obtained by using a sample volume of 100 μl, with a detection limit of 1.1 μmol l−1. Standard deviation (S.D.) of 3.4% for 20 repetitive injections of a 40 μmol l−1 dipyrone solution and sampling frequency of 90 h−1 were achieved. The results obtained with the thin-layered dual-band electrochemical cell for dipyrone determination in three different pharmaceutical samples compared well with those found by iodimetry with coulometrically generated iodine. 相似文献
62.
Nikos G. Tsierkezos 《Journal of solution chemistry》2007,36(10):1301-1310
The reduction of benzophenone (Bzph) in 3-pentanone (PEN), acetone (ACE), N,N-dimethylacetamide (DMA), N,N-dimethylformamide (DMF), tetrahydrofuran (THF), acetonitrile (ACN) and dimethyl sulfoxide (DMSO) with n-tetrabutylammonium hexafluorophosphate (TBAPF6) as background electrolyte was studied using the technique of cyclic voltammetry at the temperature of 263.15 K. The half-wave
potentials (E
1/2) were extracted. The reduction of Bzph occurs in two successive one-electron steps to produce first the free radical anion
Bzph− and then the dianion Bzph2−. The results indicated that the radical anion Bzph− is reoxidized to Bzph in all investigated solvent media whereas the dianion Bzph2− is reoxidized to Bzph− only in THF. The heterogeneous electron-transfer rate constants (k
s
) were evaluated by employing the electrochemical rate equation proposed by Nicholson. The rate of electron transfer for the
Bzph/Bzph− couple was found to be relatively slow in all investigated solvent media. Consequently, the electron-transfer processes can
be recognized as quasi-reversible. The diffusion coefficients (D) of Bzph in the investigated solvent media have been calculated using the modified Randles-Sevcik equation. The effect of
the physical and chemical properties of the solvent medium on the electrochemical behavior of Bzph has been examined. 相似文献
63.
Mauro A. La-Scalea Carla M. Souza Menezes Elizabeth I. Ferreira 《Journal of Molecular Structure》2005,730(1-3):111-120
Diffusion coefficients and electrophoretic mobility are two important physicochemical parameters used in mass transport phenomenon studies. The volume of the solute is required to determine or estimate these parameters. Classical methods, such as the LeBas method are commonly used. However, although valid, this method may represent a boring and time-consuming task, depending on the nature and number of compounds to be calculated. In this study, the volumes of a series of neutral and charged substances of the main functional groups present in organic molecules, amino acids, drugs and diverse compounds, such as cytosine and glucose, were calculated according to the LeBas method (VM) and the AM1 semi-empirical method, VW(AM1). The latter showed to be statistically coincident with the former. Employed as a pure value or corrected by the LeBas molar volume, the AM1 molecular volume was also demonstrated to estimate the diffusion coefficients in infinite aqueous dilution within an acceptable average error, according to the Othmer–Thakar, Wilke–Chang and Hayduk–Laudie methods, as well as the electrophoretic mobility of charged substances, such as carboxylates and protonated amines. According to these results, the AM1 method was seen to be statistically valid to calculate molecular volume. Many advantages in the construction of most diverse structures were noted, as well as a reduction in time and an increase in the quality of the information, when run on molecular modeling software. 相似文献
64.
Differencies between the mechanism ofn-hexane and benzene adsorption on active carbon were investigated on the ground of kinetic measurements. As it has been stated, the kinetic measurements show fundamental differencies between the mechanism of adsorption in spite of analogy existing in the state of adsorption equilibrium. Within the range investigated, only the adsorption ofn-hexane follows the model of volume filling of micropores. Existence of those differencies is also confirmed by measurements of effective diffusion coefficient values as well as changes of activation energy of the diffusion—adsorption process.
Anwendung kinetischer Untersuchungen zur Interpretation des Adsorptionsverhaltens vonn-Hexan und Benzol an Aktivkohle
Zusammenfassung Mittels kinetischer Messungen untersuchte man die Unterschiede im Mechanismus des Adsorptionsverlaufes vonn-Hexan und Benzol an Aktivkohle. Man stellte fest, daß trotz der Analogie im Adsorptionsgleichgewichtszustand die kinetischen Messungen auf prinzipielle Unterschiede im Adsorptionsmechanismus hinweisen. Im untersuchten Bereich verläuft nur die Adsorption vonn-Hexane nach dem Modell der Mikroporenvolumenausfüllung. Die auftretenden Unterschiede wurden auch durch die Berechnungen der Werte der effektiven Diffusionskoeffizienten sowie Änderungen der Aktivierungsenergie des Diffusions-Adsorptionsprozesses bestätigt.相似文献
65.
The present paper gives an account of different aspects of the tracer diffusion of Cs+ ions in alkali metal bromides. We have measured the diffusion coefficients, D, of cesium ions in 1% agar gel medium at 25 ∘C using a zone-diffusion technique over a concentration range of 5 × 10−5 to 0.1 mol,dm−3. The values of the diffusion coefficients were found to deviate from theory, which are explained on the basis of different
types of interactions occurring in the ion-gel-water system. The study is also focused on the effect of alkali metal bromides
on the obstruction effect and activation energy for the tracer-diffusion of cesium ions in agar gel medium. It is observed
that both parameters, extent of obstruction, ∝, and activation energy, E, decrease with increasing charge density of the cation of the supporting electrolyte. The influence of these trends is explained
on the basis of competitive hydration between the ions and agar molecules, and the relative distortion in the water structure
that is brought about by these different ions and agar molecules. 相似文献
66.
A. M. Stoneham 《Journal of computer-aided molecular design》1989,3(4):355-361
Summary Recent developments in computing and in the theory of simulation have extended greatly the successes of the modelling of ionic crystals pioneered by Mott and Littleton. This has changed the way in which computer experiments are brought to bear on an increasing range of solid-state phenomena. Yet applied science creates new demands, both in the form of new types of system and in terms of the complexity and subtlety of what is studied. The author's brief survey looks at some of the successes and gaps from interfaces and catalysts to neurotransmitters and from superconductors to slags. 相似文献
67.
Octavio Surez-Iglesias Ignacio Medina Consuelo Pizarro Julio L. Bueno 《Fluid Phase Equilibria》2007,260(2):279-286
The Taylor–Aris chromatographic technique was employed for the determination of diffusion coefficients of 2-fluoroanisole, 2-bromoanisole, allylbenzene and 1,3-divinylbenzene at infinite dilution in supercritical carbon dioxide from 313.16 to 333.16 K and pressures between 15 and 35 MPa. As expected, the diffusivities rise when temperature increases and pressure decreases. Numerous predictive equations are compared with experimental data: Lai–Tan, Liu–Ruckenstein cluster formula, Woerlee, Hippler–Schubert–Troe, Catchpole–King, Eaton–Akgerman, He, He–Yu, Liu–Silva–Macedo, Funazukuri and coworkers, Dariva–Coelho–Oliveira, Zhu–Lu–Zhou–Wang–Shi and the Liu–Ruckenstein RHS formula. The equations of He, He–Yu and Catchpole–King are the best of all, but cannot be used in the whole range of temperatures and solvent densities. 相似文献
68.
Abohachem Laguecir Serge Ulrich Jérôme Labille Nicolas Fatin-Rouge Serge Stoll Jacques Buffle 《European Polymer Journal》2006,42(5):1135-1144
Monte Carlo simulations, experimental titrations and fluorescence correlation spectroscopy experiments were used to investigate the conformational and electrical properties of polyacrylic acids (PAA). On the one hand, titration curves were calculated to get an insight into the role of pH on the degree of ionization and conformation of PAA chains. On the other hand, experimental potentiometric titrations of PAA were also achieved for different PAA molecular weights and compared to the calculated titration curves obtained by Monte Carlo coarse grained simulations. It was found that for a large range at intermediate PAA ionizations, a good correlation is obtained between experimental and simulations data thanks to the prominence of electrostatic interactions in this domain. The effect of ionic concentration and PAA molecular weight on the titration curves was also investigated. In order to get a better understanding of PAA conformational behavior, we also investigated PAA diffusion properties in aqueous solutions as a function of pH and ionic strength by fluorescence correlation spectroscopy (FCS), thanks to its high sensitivity to measure diffusion coefficients of tracer solutes. Good qualitative agreements were observed between experimental diffusivities and polymer properties calculated from MC simulations. It was shown that the high molecular weight PAA chains display more significant changes in diffusivity in agreement with the ionization degrees and conformational changes observed in the simulations. 相似文献
69.
Javid T Safarov 《The Journal of chemical thermodynamics》2003,35(12):1929-1937
The (p,ρ,T) and (ps,ρs,Ts) properties of {(1−x)CH3OH + xLiBr} over a wide range of state parameters are reported for the first time. The experiments were carried out in a constant volume piezometer over a temperature range from 298.15 K to 398.15 K, at 0.08421, 0.13617, 0.19692, 0.23133 and 0.26891 mole fractions and from atmospheric pressure up to 60 MPa. The experimental uncertainties are ΔT=±3 mK for temperature, Δp=±5·10−2 MPa for high pressure and Δp=±5·10−4 MPa for atmospheric pressure, Δρ=±3·10−2 kg · m−3 for density. An equation of state was derived for correlation of the experimental data of the solutions. 相似文献
70.
Short-term solid-phase microextraction (SPME) was performed to test a recently proposed semi-empirical model for the prediction of concentrations of analyte in water samples from the fibre-extracted mass without further calibration. The mass uptake rates obtained for benzene, toluene, ethylbenzene and p-xylene (BTEX) differ considerably from the before published, showing that interfibre comparability is a serious issue. The relative prediction errors are between -55% for benzene and +82% for p-dichlorobenzene under optimal conditions, i.e. they are by an order of magnitude higher than originally published. A sensitivity analysis shows the dominant influence of the estimated thickness of the diffusional boundary layer around the fibre on the concentration predicted. Empirical modification of the model equation for this parameter yields satisfactory results under the conditions tested for both BTEX and the selected chlorobenzenes. 相似文献