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1.
CO/N2, CO/Ar/O2, and CO/N2/O2 gas mixtures are optically pumped using a continuous wave CO laser. Carbon monoxide molecules absorb the laser radiation and transfer energy to nitrogen and oxygen by vibration–vibration energy exchange. Infrared emission and spontaneous Raman spectroscopy are used for diagnostics of optically pumped gases. The experiments demonstrate that strong vibrational disequilibrium can be sustained in diatomic gas mixtures at pressures up to 1 atm, with only a few Watts laser power available. At these conditions, measured first level vibrational temperatures of diatomic species are in the range TV=1900–2300 K for N2, TV=2600–3800 K for CO, and TV=2200–2800 K for O2. The translational–rotational temperature of the gases does not exceed T=700 K. Line-of-sight averaged CO vibrational level populations up to v=40 are inferred from infrared emission spectra. Vibrational level populations of CO (v=0–8), N2 (v=0–4), and O2 (v=0–8) near the axis of the focused CO laser beam are inferred from the Raman spectra of these species. The results demonstrate a possibility of sustaining stable nonequilibrium plasmas in atmospheric pressure air seeded with a few percent of carbon monoxide. The obtained experimental data are compared with modeling calculations that incorporate both major processes of molecular energy transfer and diffusion of vibrationally excited species across the spatially nonuniform excitation region, showing reasonably good agreement.  相似文献   

2.
New cluster compounds — rhenium and potassium thiohalides K3Re6S7Br7 (I) and K4Re6S8Cl6 (II) — have been synthesized. Their crystal structures have been determined by single crystal X-ray diffraction. The compounds are monoclinic; (I): space group P21/c, a = 9.32(1) Å, b = 13.528 Å, c = 12.413 Å, β = 110.21°, Z = 2, R = 0.038; (II): space group C2/m, a = 10.614 Å, b = 17.268 Å, c = 10.448 Å, β = 110.755°, Z = 2, R = 0.042. In both structures, the potassium ions are considerably distorted. The occupancies of the potassium sites are 0.17-0.34 (I) and 0. 01-0.26 (II), correlating well with the coordination numbers (c.n. 7-10 and 2-7 for I and II, respectively). In I, adjacent positions of potassium atoms are aggregated into discrete tetrahedral and angular clusters; in II, the individual (four-and six-membered) cyclic clusters of potassium sites are present along with bent chains of vertex-and edge-sharing tetrahedral “potassium clusters.” The shortest K-K distances in these “clusters” vary from 1.31 Å to 1.54 Å (I) and from 0.66 Å to 1.65 Å (II). The “instability” of the potassium site suggests that I and II are ion conductors.Original Russian Text Copyright © 2004 by S. F. Solodovnikov, S. S. Yarovoi, Yu. V. Mironov, A. V. Virovets, and V. E. Fedorov__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 5, pp. 909–917, September–October, 2004.  相似文献   

3.
Molar excess enthalpiesH E of 1-hexyne + carbon tetrachloride, + dipropyl ether, + triethylamine, and of 3-hexyne + carbon tetrachloride, + dipropyl ether, + triethylamine at 298.15 K and atmospheric pressure were measured with aPicker-type flow microcalorimeter over the whole concentration range. At equimolar concentration,H E of 3-hexyne + carbon tetrachloride is stronglyexothermic (–499 J mol–1), in contrast toH E =+14 J mol–1 for the 1-hexyne system. As expected, for the ether and amine systems inverse behavior is observed: because of the active hydrogen of terminal alkynes the enthalpy of mixing at equimolar concentration is more exothermic with 1-hexyne (–185 J mol–1, dipropyl ether; –300 J mol–1, triethylamine) than with 3-hexyne (–25 J mol–1, dipropyl ether; –92 J mol–1, triethylamine). The curveH E vs. mole fraction is considerably skewed for 3-hexyne (x 1) + triethylamine, the minimum being ca. –197 J mol–1 atx 10.9.
Thermodynamik binärer Mischungen mit Alkinen als eine Komponente. II. Zusatzenthalpien binärer Mischungen von 1-Hexin und 3-Hexin mit Tetrachlorkohlenstoff, Dipropyläther und Triäthylamin bei 298,15 K
Zusammenfassung Die molaren ZusatzenthalpienH E der sechs binären Systeme 1-Hexin + CCl4, + Dipropyläther, + Triäthylamin, und 3-Hexin + CCl4, + Dipropyläther, + Triäthylamin wurden bei 298,15 K und Atmosphärendruck über den gesamten Konzentrationsbereich mit einem dynamischen Strömungsmikrokalorimeter nachPicker gemessen.H E des Systems 3-Hexin + CCl4 ist starkexotherm (–499 J mol–1 fürx=0,5),H E des Systems 1-Hexin + CCl4 endotherm (+14 J mol–1,x=0,5). Hingegen verhalten sich die Mischungen Hexin + Dipropyläther bzw. + Triäthylamin den Erwartungen entsprechend. Wegen des aktiven Wasserstoffs endständiger Alkine ist die Zusatzenthalpie mit 1-Hexin stärker exotherm (–185 J mol–1 mit Dipropyläther und –300 J mol–1 mit Triäthylamin,x=0,5) als mit 3-Hexin (–25 J mol–1 bzw. –92 J mol–1). Die molare Zusatzenthalpie des Systems 3-Hexin (x 1) + Triäthylamin ist ausgeprägt asymmetrisch mit einem Minimum von etwa –197 J mol–1 beix 10,9.


Communicated in part at the 2. Ulmer Kalorimetrietage, March 24–25, 1977, Ulm, Federal Republic of Germany.  相似文献   

4.
The effects of incorporation of heterocyclic moieties into fluorinated poly(ether imide) membranes on their gas transport properties were investigated. Four novel fluorinated poly(ether imide) (PEI) membranes were prepared from four different bis(ether amine)s namely, 4,4-bis[3′-trifluromethyl-4′(4′′-aminobenzoxy)bezyl]biphenyl (BAQP); 1,4-bis[3′-trifluromethyl-4′(4′′-aminobenzoxy)bezyl] benzene (BATP); 2,6-bis[3′-trifluromethyl-4′(4′′-aminobenzoxy)bezyl]pyridine (BAPy) and 2,5-bis[3′-trifluromethyl-4′(4′′-aminobenzoxy)bezyl]thiophene (BATh), and a fluorinated dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane (6FDA) as a common dianhydride. Gas transport properties of these membranes were measured to investigate the effect of chemical structure on gas permeation and diffusion processes over four different gases (e.g., CH4, N2, O2 and CO2) at different temperatures (e.g., 35, 45 and 55 °C) at an applied pressure of 3.5 bar. It has been found that at 35 °C the permselectivities of BAPy and BATh based polymeric membranes (6.4 and 6.6, respectively) toward O2 relative to N2 are higher in comparison to BAQP and BATP (5.5 and 5.3, respectively) containing PEI membranes. The permeability coefficient of CO2 for BAPy and BATh (51.92 and 45.31, respectively at 35 °C) based PEI membranes were observed to be much higher than BAQP and BATP based membranes (36.61 and 33.51, respectively at 35 °C) with comparable selectivity values of CO2 relative to CH4. All these membranes exhibit higher CO2/CH4 selectivity than those of common glassy polymers e.g., cellulose acetate, polysulfone and polycarbonate. The order of permeability of these gases was found as CO2 > O2 > N2 > CH4. The temperature dependency of permeation and diffusion processes enables to calculate the activation energies of the permeation and diffusion processes for these four different gases through four PEI membranes.  相似文献   

5.
Zusammenfassung Die Darstellung von Si2H5J sowie von Si2H4J2 (SiH3–SiHJ2+SiH2J–SiH2J), Si3H7J (SiH3–SiH2–SiH2J+SiH3–SiHJ–SiH3) und Si3H6J2 (Isomerengemisch) durch Umsetzung der entsprechenden Silane mit elementarem Jod (ohne Verwendung eines Lösungsmittels) wird mitgeteilt. Durch katalytische Mengen Alkohol wird die Reaktion von Jod mit Silanen beschleunigt, gleichzeitig jedoch die Spaltung der Si–Si-Bindung gefördert.
Preparation of disilanyl iodide and trisilanyl iodide
The preparation of Si2H5J as well as Si2H4J2 (SiH3–SiHJ2+SiH2J–SiH2J), Si3H7J (SiH3–SiH2–SiH2J+SiH3–SiHJ–SiH3) and Si3H6J2 (isomeric mixture) by reaction of the corresponding silanes with elementary iodine without using a solvent is communicated. The reaction of iodine with silanes is accelerated by catalysings amounts of alcohol. At the same time, however, the cleavage of the Si–Si-bond is stimulated.


Mit 3 Abbildungen

19. Mitt.:F. Fehér, D. Schinkitz undH. Strack, Z. anorg. allgem. Chem.385, 202 (1971).

B. Mostert, Dissertation Univ. Köln 1961.

A. G. Wronka, Dissertation Univ. Köln 1961.

G. Betzen, Dissertation Univ. Köln 1967,G. Betzen, Diplomarbeit Univ. Köln 1963.  相似文献   

6.
The eluent strengths of para, ortho and meta substituted hydroxy-, nitro-, amino- and sulfobenzoic acids in single column ion chromatographic separations of inorganic and organic anions have been evaluated and compared with benzoic acid.o-Sulfobenzoic acid turns out to be a stronger and efficient eluent compared to others for the separation and determination of monovalent (Cl, NO 2 , Br, NO 3 ) and divalent (SO 4 2– , SeO 4 2– , S2O 3 2– , S2O 6 2– ) inorganic anions. In addition it also functions as an appropriate mobile phase for the detection and quantification of some substituted benzoate ions in an aqueous medium.  相似文献   

7.
A process for the intensification of silver images on AgHal photographic materials designed for detection of high-energy (X- and γ-ray) radiation was proposed, which is based on the “reprecipitation” of elemental silver and a decrease in its dispersion and comprises the treatment of silver with an aqueous solution containing potassium hexacyanoferrate(III) and potassium chloride or bromide at the first step and with a solution containing tin(II) chloride, potassium thiocyanate, sodium N,N′-ethylenediamine tetraacetate, and potassium hydroxide at the second step. By this process, the optical densities of image over a wide (0.5–2.0) range was increased by a factor of 3–5; as a result, the photographic sensitivity S 0.85 and S 2.00 was enhanced by almost an order of magnitude with the retained or slightly increased gradient g, fog density D 0, and resolving power of the material.__________Translated from Khimiya Vysokikh Energii, Vol. 39, No. 5, 2005, pp. 373–378.Original Russian Text Copyright © 2005 by Mikhailov, Kondakov, Krikunenko.  相似文献   

8.
This work reports on the preparation and properties of polydimethylsiloxane (PDMS)/low‐density polyethylene (LDPE) multilayer composite polymer membranes (MCPM) for gas separation applications. The membranes were produced by combining sequential coating with melt‐extrusion/salt leaching techniques. In particular, the gas sorption and permeation properties at different pressure (40–90 psig) and temperature (27–55 °C) are reported with morphology and thermogravimetric properties. The results show that a 20 μm PDMS layer was able to penetrate the microporous LDPE surface layer substrate leading to improved interfacial adhesion. Based on the different gases (CO2, CH4, and C3H8) solubility, permeability, and diffusivity obtained, these membranes are seen as good candidates for industrial gas separations. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1045–1052  相似文献   

9.
Procedures were proposed for the determination of impurities of permanent gases (H2, O2, Ar, N2, and CO), carbon dioxide, and hydrocarbons in high-purity monosilane by gas chromatography with detection limits of 1–3 ppm, 2 ppm, and 0.02–0.04 ppm, respectively, which are lower by 1–2 orders of magnitude than those published in the literature. The procedures make it possible to check the compliance of the purity of monosilane with present standards of microelectronics (TU 48-0513-057.0-91).  相似文献   

10.
Polydimethylsiloxane (PDMS) is the most commonly used membrane material for the separation of condensable vapors from lighter gases. In this study, a composite PDMS membrane was prepared and its gas permeation properties were investigated at various upstream pressures. A microporous cellulose acetate (CA) support was initially prepared and characterized. Then, PDMS solution, containing crosslinker and catalyst, was cast over the support. Sorption and permeation of C3H8, CO2, CH4, and H2 in the prepared composite membrane were measured. Using sorption and permeation data of gases, diffusion coefficients were calculated based on solution‐diffusion mechanism. Similar to other rubbery membranes, the prepared PDMS membrane advantageously exhibited less resistance to permeation of heavier gases, such as C3H8, compared to the lighter ones, such as CO2, CH4, and H2. This result was attributed to the very high solubility of larger gas molecules in the hydrocarbon‐based PDMS membrane in spite of their lower diffusion coefficients relative to smaller molecules. Increasing feed pressure increased permeability, solubility, and diffusion coefficients of the heavier gases while decreased those of the lighter ones. At constant temperature (25°C), empirical linear relations were proposed for permeability, solubility, and diffusion coefficients as a function of transmembrane pressure. C3H8/gas solubility, diffusivity, and overall selectivities were found to increase with increasing feed pressure. Ideal selectivity values of 9, 30, and 82 for C3H8 over CO2, CH4, and H2, respectively, at an upstream pressure of 8 atm, confirmed the outstanding separation performance of the prepared membrane. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

11.
The interaction of iron carbonyls Fe n (CO) m (wheren = 1,m = 5;n = 2,m = 9;n = 3,m = 12) with anionic Lewis bases (H, F, Cl, Br , I, CN, SCN, N3 , MeSO3 , MeCO2 , CF3CO2 , S2 , CO3 2–, and SO4 2–) passes through two-stage redox-disproportionation. The first stage is the formation of an iron carbonyl-base complex, [Fe n (CO) m–1C(O)L], and the second is a single-electron reduction of this complex by another molecule of the initial iron carbonyl, giving rise to Fe(l) and Fe(–l) derivatives.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 248–249, January, 1996.  相似文献   

12.
In recent work (Int. J. Mass Spec., vol. 282, pp. 112–122) we have considered the effect of apertures on the fields inside rf traps at points on the trap axis. We now complement and complete that work by considering off-axis fields in axially symmetric (referred to as “3D”) and in two dimensional (“2D”) ion traps whose electrodes have apertures, i.e., holes in 3D and slits in 2D. Our approximation has two parts. The first, EnoAperture, is the field obtained numerically for the trap under study with apertures artificially closed. We have used the boundary element method (BEM) for obtaining this field. The second part, EdueToAperture, is an analytical expression for the field contribution of the aperture.In EdueToAperture, aperture size is a free parameter. A key element in our approximation is the electrostatic field near an infinite thin plate with an aperture, and with different constant-valued far field intensities on either side. Compact expressions for this field can be found using separation of variables, wherein the choice of coordinate system is crucial. This field is, in turn, used four times within our trap-specific approximation.The off-axis field expressions for the 3D geometries were tested on the quadrupole ion trap (QIT) and the cylindrical ion trap (CIT), and the corresponding expressions for the 2D geometries were tested on the linear ion trap (LIT) and the rectilinear ion trap (RIT). For each geometry, we have considered apertures which are 10%, 30%, and 50% of the trap dimension. We have found that our analytical correction term EdueToAperture, though based on a classical small-aperture approximation, gives good results even for relatively large apertures.  相似文献   

13.
This paper presents the results of the re-investigation of polarized IR spectra of adipic acid and of its d2, d8 and d10 deuterium derivative crystals. The spectra were measured at 77 K by a transmission method using polarized light for two different crystalline faces. Theoretical analysis concerned linear dichroic effects and H/D isotopic effects observed in the spectra of the hydrogen and deuterium bonds in adipic acid crystals at the frequency ranges of the νO–H and the νO–D bands. The two-branch fine structure pattern of the νO–H and νO–D bands and the basic linear dichroic effects characterizing them were ascribed to the vibronic mechanism of vibrational dipole selection rule breaking for IR transitions in centrosymmetric hydrogen bond dimers. It was proved that for isotopically diluted crystalline samples of adipic acid, a non-random distribution of protons and deuterons occurs in the dimers (H/D isotopic “self-organization” effect). This effect results from the dynamical co-operative interactions involving the dimeric hydrogen bonds.  相似文献   

14.
Interaction of R n M-derivatives of 4-nitrophenol and thiophenol (R n M= PhHG, PPh3Au, Ph3Sn, Ph4Sb) with a set of inorganic and organic anions (Cl, Br, I, CN, [PhOCO], [4-NO2C6H4OCO]) was studied by IR and electronic spectroscopy in solvents with different polarities and coordinating properties (C6H6, CH2Cl2, DMSO). The dependence of the character of the interaction with the anions on the nature of the metal atom and heteroatom, the type of anions and the nature of the media was analyzed. Such interaction leads to ion-molecular complexes, and also to dissociation of the X-M bond (X = O, S, M = Au, Hg. Sb) with formation of the (4-NO2C6H4X) anion even in weakly polar media. Only in the case of 4-NO2C6H4OSnPh3 does the reaction stop at the stage of complex formation. In other cases the role of complex formation with anions is less than with neutral coordinating reagents.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 7, pp. 1838–1841, July, 1996.  相似文献   

15.
BaVSe3 has been synthesized and its crystal structure determined at 293(2)°K. The structure was solved in the hexagonal space group P63/mmc (D46h), with a = 6.9990(11) and c = 5.8621(13) Å. Scans (2 Θ) of a polycrystalline sample revealed that BaVSe3 undergoes a transition to an orthorhombic unit cell (b′ 31/2 a, aa, cc) at 303(5)°K. Magnetic susceptibility measurements between 4 and 300°K indicate that BaVSe3 is paramagnetic down to 41(1)°K, where magnetic ordering occurs, with a magnetic moment in the ordered phase of 0.2 μB per vanadium atom. The orthorhombic lattice distortion may be caused by the “freezing in” of “soft” vibrational modes.  相似文献   

16.
We apply multiple-scattering calculations to the analyses of Sn L3-edge X-ray absorption near-edge structure (XANES) spectra for environmental organotin compounds such as SnCl4−nMen, SnCl4−nBtn, and SnCl4−nPhn (n = 0–4) where Me = CH3, Bt = C4H9, and Ph = C6H5. The XANES peak at 3960 eV has rich information on the local structure. Referring to the optimized structures by density functional theory (DFT) calculations, multiple-scattering calculations well explain the observed spectral changes for different “organic extents”. The present study also supports the widely-used semiempirical rule called ‘Natoli’s rule’ for these environmental compounds, which will be useful to use XANES spectra for the practical analytical tools.  相似文献   

17.
This paper discusses the gas permeation properties of poly(ethylene oxide) (PEO)-based segmented block copolymers containing monodisperse amide segments. These monodisperse segments give rise to a well phase-separated morphology, comprising a continuous PEO phase with dispersed crystallised amide segments. The influence of the polyether phase composition and of the temperature on the permeation properties of various gases (i.e., CO2, N2, He, CH4, O2 and H2) as well as on the pure gas selectivities were studied in the temperature range of −5 °C to 75 °C. The CO2 permeability increased strongly with PEO concentration, and this effect could partly be explained by the dispersed hard segment concentration and partly by the changing chain flexibility. By decreasing the PEO melting temperature the low temperature permeabilities were improved. The gas transport values were dependant on both the dispersed hard segment concentration and the polyether segment length (length between crosslinks). The gas selectivities were dependant on the polyether segment length and thus the chain flexibility.  相似文献   

18.
An idea was presented of treating the chromatographed substance as a “solute,” and the chromatographic system, composed of the stationary and the mobile phase as a “solvent.” Moreover the concept of “local equilibrium” was introduced, allowing to regard a given chromatographic spot as a “binary solution.” Thus a possibility arose to apply the classical thermodynamic approach, normally used for binary solutions, and namely: μi = μi + RT ln xiƒi, where μi—chemical potential of the “i”-th compound in the solution, μi—chemical potential of the pure “i”-th compound, xi-molar fraction of the “i”-th compound, ƒi—its activity coefficient, in a modified form, suitable for the chromatographic purpose.  相似文献   

19.
 A gas permeation system using two gaseous streams flowing on both sides of a membrane is developed. This gas permeation device and a coulometric detector are adapted for the continuous measurement of relatively high concentrations of sulphur dioxide. The interferences of other gases (NO2, NO and CO2) can be eliminated by using a scrubber behind the gas permeation device in the acceptor stream. The effects of the donor flow rates and gas pressure as well as the membrane thickness on the signal are discussed. The relative standard deviation is 1.3% (n=7) for 2.002×10-3 mol/mol certified sulphur dioxide. Received: 19 July 1996/Revised: 22 October 1996/Accepted: 29 October 1996  相似文献   

20.
Pulverized coal plasma gasification   总被引:11,自引:0,他引:11  
A number of experiments on the plasma-vapor gasification of brown coals of three types have been carried out using an experimental plant with an electric-arc reactor of the combined type. On the basis of the material and heat balances, process parameters have been obtained: the degree of carbon gasification (c), the level of sulfur conversion into the gas phase (s), the synthesis gas concentration (CO+Hz) in the gaseous products, and the specific power consumption for the gasification process. The degree of gasification was 90.5-95.0%, the concentration of the synthesis gas amounted to 84.7–85.7%, and the level of sulfur conversion into the gas phase was 94.3–96.7%. Numerical study of the process of plasma gasification of coals was carried out using a mathematical model of motion, heating, and gasification of polydisperse coal particles in an electric-arc reactor of the combined type with an internal heat source (arc). The initial conditions for a conjugate system of nonlinear differential equations of the gas dynamics and kinetics of a pulverized coal stream interacting with the electric arc and oxidizer (water vapor) agree with the initial conditions of the experiments. The computation results satisfactorily correlate with the experimental data. The mathematical model can be used for the determination of reagent residence time and geometrical dimensions of the plasma reactor for the gasification of coals.Nomenclature c i volume concentration of components (kmol m–3) - x longitudinal coordinate (m) - f i source members, determined by variation of the ith component due to chemical reactions in unit volume in unit time (kmol m–3s–1) - velocity (m s–1) - M s ash mass in one particle (kg) - C D particle drag coefficient - 3.14 - r s particle radius (m) - d particle diameter (m) - density (kg m–3) - C p heat capacity of components (J molt– K–1) - Q j thermal effect of reaction (J kmol–1) - Ej activation energy of reaction - N l volume concentration of particles of thelth fraction (m–3) - T temperature (K) - emissivity factor of coal particles - 5.67 × 10–8, blackbody emissivity coefficient (W m–2 K–4) - P pressure (Pa) - S reactor cross section (m2) - D reactor diameter (m) - V reactor volume (m3) - L R reactor length (m) - F W friction force on the wall (N) - f g friction coefficient - residence time (s) - Nu Nusselt number - Re Reynolds number - Pr Prandtl number - thermal conductivity of gas (J m s–1 K–1) - R 8.3 × 103, universal gas constant (J kmol K–1) - µ i molecular mass of component (kg kmol–1) - dynamic viscosity coefficient of gas (kg m–1 s–1) - thermal efficiency of plasma reactor - qarc specific heat flow from arc (W m–3) - P 1 heat supplied in vapor at T = 405 K (W) - P 2 heat loss to wall (W) - P 3 heat loss in the gas and slag separator chamber (W) - P 4 heat loss in the synthesis gas oxidation chamber (W) - P 5 heat loss in the slag catcher (W) - P 6 heat carried away in the off-gas (W) - P heat input of arc (W) - P arc electric power of arc (W) - Qsp specific power consumption (kw Hr kg–1) - d w specific heat flow to wall (W m–2) - c degree of carbon gasification (%) - s level of sulfur conversion into gas phase (%)  相似文献   

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