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51.
The formation of negative hydrogen ions in a conventional hollow cathode discharge has been investigated. A mixture of Ne and H2 proved to be more advantageous compared to pure hydrogen. The study has been performed by solving the electron Boltzmann equation, coupled with a system of balance equations for neon and hydrogen neutral and charged particles. The vibrational distribution function of hydrogen has been calculated. Our calculations show unusually high population of vibrationally excited hydrogen molecules in a Ne–H2 mixture, which explains the high density of negative hydrogen ions under optimal conditions (total gas pressure of few Torr, hydrogen number mole fraction of 1–10% and discharge current of 10–100 mA). Line intensities originating from highly excited neon states vs. hydrogen pressure have been calculated and a comparison with existing experimental results has been made. 相似文献
52.
Eugenio?Garcia-Pa?eda Pilar?Guardado Alfredo?MaestreEmail author 《Journal of solution chemistry》2004,33(10):1277-1293
Partial molar volumes at infinite dilution, V02, of alkali–metal halides (LiCl, NaCl KCl RbCl CsCl, NaBr, KBr, KI), tetra-n-alkylammonium bromides, R4NBr (R=Me, Et, n-Pr, n-Bu, n-Pen), NaBPh4, and Ph4PCl have been determined in binary solvent mixtures of water with 2-methyl-2-butanol covering the water-rich region and the alcohol-rich region at 298.15 K. V02 for alkali–metal halides show relatively little dependence on the solvent composition. However, in the case of hydrophobic electrolytes the observed effects are more pronounced. A good linear dependence between V02(R4NBr) and the molecular weight of the tetra-n-alkylammonium cation is found. Limiting single-ion volumes have been obtained using the assumption that V0(Ph4P+)–V0(BPh–4)=2.0 cm3-mol–1. The trends in the single-ion volumes are discussed in both solvent regions. 相似文献
53.
Radiation-chemical transformations of chloride solutions in the presence of iodide additives were studied by pulse radiolysis.
Radical anion Cl2
⋅− oxidize I− ion, while in the secondary reactions Cl2 reacts with I− to form a mixed trihalide ion ICl2
−. A reaction model that satisfactorily describes the experimental data was proposed.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1336–1340, June, 2005. 相似文献
54.
《Electroanalysis》2004,16(8):633-639
A potentiometric sensor constructed from a mixture of 25% (m/m) spinel‐type manganese oxide (lambda‐MnO2), 50% (m/m) graphite powder and 25% (m/m) mineral oil is used for the determination of lithium ions in a flow injection analysis system. Experimental parameters, such as pH of the carrier solution, flow rate, injection sample volume, and selectivity for Li+ against other alkali and alkaline‐earth ions and the response time of this sensor were investigated. The sensor response to lithium ions was linear in the concentration range 8.6×10?5–1.0×10?2 mol L?1 with a slope 78.9±0.3 mV dec?1 over a wide pH range 7–10 (Tris buffer), without interference of other alkali and alkaline‐earth metals. For a flow rate of 5.0 mL min?1 and a injection sample volume of 408.6 μL, the relative standard deviation for repeated injections of a 5.0×10?4 mol L?1 lithium ions was 0.3%. 相似文献
55.
The separation procedure for Ag, B, Cd, Dy, Eu and Sm as impurities in Gd matrix using ICP-AES technique with an extraction chromatographic column has been developed. The spectral interference of the Gd matrix on the elements was eliminated using a chromatography technique with 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (PC-88A) as the mobile phase and XAD-16 resin as the stationary phase. Ag+, B4O72−, and Cd2+ were eluted with 0.1 M HNO3, while rare earth ions were not. The best eluent for separating Eu and Sm in the Gd matrix was 0.3 M HNO3. The limit of quantitation for these elements was 0.6-3.0 ng mL−1. The recovery of Ag, B, and Cd was 90-104% using 0.1 M HNO3 as the eluent, while that of Eu, Gd, and Sm ranged from 100 to 102% with 0.3 M HNO3. Dy was recovered quantitatively with 4 M HNO3. The relative standard deviation of the methods for a set of three replicates was between 1.0 and 15.4% for the synthetic and standard Gd solutions. The proposed separation procedure was used to measure Ag, B, Cd, Dy, Eu, and Sm in a standard Gd solution. 相似文献
56.
Chronoamperograms for gold in solutions containing 0.1 M thiourea, 0.5 M H2SO4, and catalytically active sulfide ions at the concentration c 1 from 1 × 10?5 to 4 × 10?5 M are obtained at different potentials with the aid of an automated setup intended for renewing the electrode surface directly in the solution by cutting off a thin surface layer of the metal. It is shown that the results of measurements of the current practically coincide at a constant value of the product c 1 t, where t is the time period elapsed after the renewal of the electrode surface. Such a coincidence testifies to a diffusion nature of processes that hamper accumulation of sulfide ions at the gold surface. This fact permitted the use of a procedure developed previously for the calculation of polarization curves at constant values of surface coverage θ by catalytically active ions. At θ = const, the voltammetric curves for gold in sulfide-containing thiourea solutions are shown to correspond to the Tafel equation. With the surface coverage increasing, the effective values of the exchange current i 0, transfer coefficient α, and anodic reaction order with respect to thiourea P a increase from the values i }~ 10?5 A cm?2, α }~ 0.12, and P a = 0.2, which are characteristic of pure solutions, to 2 × 10?4 A cm?2, α }~ 0.5, and P a = 1.1 (at θ }~ 0.5). An interpretation to the established regularities is given. 相似文献
57.
H
0 and S
0 values of the complex formation in water of benzo-18-crown-6 (B18C6) with K+, Tl+, and Pb2+ were determined and compared with those of 18-crown-6. The H0 values of B18C6 are negative. The stability in water of the B18C6-metal ion complex at 25°C is governed largely by the magnitude of the H
0 value. The B18C6-metal ion complex is less stable in water than the corresponding 18C6-metal ion complex. This is due largely to a less favorable enthalpic contribution of the B18C6-metal ion complex compared with the corresponding 18C6-metal ion complex. The two aromatic ether oxygen atoms of B18C6 are responsible for the larger H
0 value of the B18C6-metal ion complex compared with the corresponding 18C6-metal ion complex. 相似文献
58.
《Mendeleev Communications》2020,30(5):679-682
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59.
Mark Salomon 《Journal of solution chemistry》1990,19(12):1225-1236
Conductivity data are used to determine thermodynamic complex formation constants for cases in which both the initial electrolyte and the complexed electrolyte form ion pairs. Using the method described in the text, the complex formation constants of Li+, Na+ and K+ with the crown ether 18-crown-6 and of Li+ with the ligand triphenylphosphine oxide in propylene carbonate have been evaluated from conductance data. The complexation of AgBr in propylene carbonate solutions of n-etrabutylammonium bromide has also been studied by the measurement of molar conductivities. The results of these studies indicate that ion pairing should not be neglected, even in high permittivity solvents such as propylene carbonate, and that the ion pair association constants correlate well with structural studies on cation-crown ether molecular conformations. 相似文献
60.
Yu. L. Frolov I. V. Guchik V. A. Shagun A. V. Vashchenko 《Journal of Structural Chemistry》2005,46(6):979-984
Models of alkali metal hydroxide-water-dimethylsulfoxide superbasic media have been constructed using Hartree Fock and DFT (B3LYP) quantum chemical methods; the structure and energies of anion complexes are considered. The hydroxide anion in the models is stabilized as complexes of OH?·H2O and OH?· 2H2O types. 相似文献