Models of H3+ in warm, diffuse, molecular gas in the Galactic centre

Oka et al. (Oka et al. 2005 Astrophys. J. 632, 882-893) have recently observed a large column density of H3+ in the Galactic centre. In one of the gaseous components, a column density of H3+ in its metastable level (3,3) of approximately 4 x 10(14) cm(-2) is measured. From the excitation of H3+, they deduce a density below 50 cm(-3) and a temperature approximately 270 K. In this paper, we report results for this region from a new version of our PDR code which includes the H3+ excitation. Models show it is unlikely that the mean temperature of the gas could be above 100 K. We also show that there is a possibility to produce hot H3+ in C-shocks.     

H3+ cooling in primordial gas

Simulations of the thermal and dynamical evolution of primordial gas typically focus on the role played by H2 cooling. H2 is the dominant coolant in low-density primordial gas and it is usually assumed that it remains dominant at high densities. However, H2 is not an effective coolant at high densities, owing to the low critical density at which it reaches local thermodynamic equilibrium and to the large opacities that develop in its emission lines. It is therefore important to quantify the contribution made to the cooling rate by emission from the other molecules and ions present in the gas. A particularly interesting candidate is the H3+ ion, which is known to be an effective coolant at high densities in planetary atmospheres. In this paper, we present results from simulations of the thermal and chemical evolution of gravitationally collapsing primordial gas, which include a detailed treatment of H3+ chemistry and an approximate treatment of H3+ cooling. We show that in most cases, the contribution from H3+ is too small to be important, but if a sufficiently strong ionizing background is present, then H3+ cooling may become significant.     

Characteristics of Hydrogen Storage Alloy Mg2Ni Produced by Hydriding Combustion Synthesis

A high activity and large capacity of hydrogen storage alloy Mg2Ni by hydriding combustion synthesis was investigatedby means of pressure composition isotherms, X-ray diffraction and scanning electron microscopy. The results showedthat the maximum hydrogen absorption capacity of Mg2Ni is 3.25 mass fraction at 523 K, just after synthesis withoutany activation. The relationships between the equilibrium plateau pressure and the temperature for Mg2Ni were lgp(0.1 Mpa)=3026/T 5.814 (523 K≤ T ≤623 K) for hydriding and Igp (0.1 Mpa)=-3613/T 6.715 (523 K≤T ≤623 K) for dehydriding. The kinetic equation is [-ln(1 - α)]3/2 = kt and the apparent activation energy for thenucleation and growth-controlled hydrogen absorption and desorption were determined to be 64.3±2.31 kJ/(mol.H2)and 59.9±2.99 kJ/(moI.H2) respectively.     

Experimental determination of equilibrium constant for the complexing reaction of nitric oxide with hexamminecobalt(II) in aqueous solution

Ammonia solution can be used to scrub NO from the flue gases by adding soluble cobalt(II) salts into the aqueous ammonia solutions. The hexamminecobalt(II), Co(NH3)6(2+), formed by ammonia binding with Co2+ is the active constituent of eliminating NO from the flue gas streams. The hexamminecobalt(II) can combine with NO to form a complex. For the development of this process, the data of the equilibrium constants for the coordination between NO and Co(NH3)6(2+)over a range of temperature is very important. Therefore, a series of experiments were performed in a bubble column to investigate the chemical equilibrium. The equilibrium constant was determined in the temperature range of 30.0-80.0 degrees C under atmospheric pressure at pH 9.14. All experimental data fit the following equation well: [formula: see text] where the enthalpy and entropy are DeltaH degrees = - (44.559 +/- 2.329)kJ mol(-1) and DeltaS degrees = - (109.50 +/- 7.126) J K(-1)mol(-1), respectively.     

Intensity ratios of H lines: departures from the ideal conditions in the range of laser-induced breakdown spectroscopy experiments

In the present paper we analyze the behavior of H line intensity ratios with electron density and electron temperature in intermediate-density plasmas. We analyze the influence on the line intensity ratios of (1) the departures from local thermodynamic equilibrium (LTE) of the level population ratios, (2) the plasma opacity, and (3) the lowering of the ionization potential. We look, particularly, at the lines H(alpha), H(beta), H(gamma), and H(delta) and the energy levels involved in the corresponding atomic transitions for their use as diagnostics in laser-induced breakdown spectroscopy (LIBS) experiments. One important conclusion is that, for typical values of the plasma dimension and the electron temperature taking place in LIBS, i.e., L = 1 mm and T(e) = 10 000 K, respectively, the intensity ratios H(beta)/H(alpha), H(gamma)/H(alpha), and H(delta)/H(alpha) depart from the ideal values by less than 10% in the interval 0.65 x 10(14) part/cm(3) 相似文献   

Giant and uniform fluorescence enhancement over large areas using plasmonic nanodots in 3D resonant cavity nanoantenna by nanoimprinting

Using a new nanoplasmonic architecture and an optimized spacer, we observed the following: (a) the average fluorescence of an infrared dye (indocyanine green) is enhanced by?2970 fold uniformly (variation < 11%) over a large sample area and over a wide range of dye concentrations (380 to 380?000?molecule?μm(-2)), laser excitation powers and laser beam sizes; and (b) for a single molecule placed at a 'hot spot', the fluorescence enhancement is 4.5?×?10(6) fold. The giant and uniform enhancements (orders of magnitude higher than before), plus easy and inexpensive large area fabrication (?>?4″ wafers), should open up wide applications.     

Electrochemiluminescent detection of metal cations using a ruthenium(II) bipyridyl complex containing a crown ether moiety

The effects of metal ions on the electrochemiluminescence (ECL) properties of (bpy)2Ru(AZA-bpy) (bpy = 2,2'-bipyridine; AZA-bpy = 4-(N-aza-18-crown-6-methyl-2,2'-bipyridine) have been investigated. The electrochemistry, photophysics and ECL of Ru(bpy)3(2+) in the presence of Pb2+, Hg2+, Cu2+, and K+ are reported. The anodic oxidation of Ru(bpy)3(2+) produces ECL in the presence of tri-n-propylamine (TPrA) in 50:50 (v/v) CH3CN:H2O solution. Increases in ECL efficiency (photons generated per redox event) up to 20-fold that depend on both the concentration and nature of the metal ion have been observed, making this an interesting system for electrochemiluminescence metal ion sensing.     

H3+ in the diffuse interstellar medium

Three forms of solely hydrogen-bearing molecules--H2, HD and H3+--are observed in diffuse or optically transparent interstellar clouds. Although no comprehensive theory exists for the diffuse interstellar medium or its chemistry, the abundances of these species can generally be accommodated locally within the existing static equilibrium frameworks for heating/cooling, H2-formation on large grains, etc. with one modification demanded equally by observations of HD and H3+, i.e. a pervasive low-level source of H and H2 ionization ca 10 times faster than the usual cosmic ray ionization rate zetaH = 10(-17) s(-1) per free H-atom. We discuss this situation with reference to observation and time-dependent modelling of H2 and H3+ formation. While not wishing to appear ungrateful for the success of what are very simplistic notions of the interstellar medium, we point out several reasons not to feel smug. The equilibrium conditions which foster high H2 and H3+ abundances are very slow to appear and these same simple ideas of static equilibrium cannot explain any, but a few, of the simplest of the trace species, which are ubiquitously embedded in H2-bearing diffuse gases.     

H2O absorption spectroscopy for determination of temperature and H2O mole fraction in high-temperature particle synthesis systems

Water absorption spectroscopy has been successfully demonstrated as a sensitive and accurate means for in situ determination of temperature and H2O mole fraction in silica (SiO2) particle-forming flames. Frequency modulation of near-infrared emission from a semiconductor diode laser was used to obtain multiple line-shape profiles of H2O rovibrational (v1 + v3) transitions in the 7170-7185-cm(-1) region. Temperature was determined by the relative peak height ratios, and XH2O was determined by use of the line-shape profiles. Measurements were made in the multiphase regions of silane/hydrogen/oxygen/ argon flames to verify the applicability of the diagnostic approach to combustion synthesis systems with high particle loadings. A range of equivalence ratios was studied (phi = 0.47 - 2.15). The results were compared with flames where no silane was present and with adiabatic equilibrium calculations. The spectroscopic results for temperature were in good agreement with thermocouple measurements, and the qualitative trends as a function of the equivalence ratio were in good agreement with the equilibrium predictions. The determinations for water mole fraction were in good agreement with theoretical predictions but were sensitive to the spectroscopic model parameters used to describe collisional broadening. Water absorption spectroscopy has substantial potential as a valuable and practical technology for both research and production combustion synthesis facilities.     

Phase Equilibrium for Structure-H Hydrates Formed with Methane and Methyl-Substituted Cyclic Ether

Clathrate hydrate formation in a (methane + either 3-methyltetrahydropyran or 2-methyltetrahydrofuran + water) system is demonstrated. The first data of the quadruple (water + structure-H hydrate + either 3-methyltetrahydropyran or 2-methyltetrahydrofuran + methane) equilibrium pressure–temperature conditions are measured over temperatures from 273 to 286 K. In the 3-methyltetrahydropyran system, the equilibrium pressures are lower by 1.6–2 MPa than those of the structure-I methane hydrate formed in the methane + water system at given temperatures. In the 2-methyltetrahydrofuran system, equilibrium pressures at temperatures below 278 K are lower than those for the structure-I methane hydrate, and at temperatures above 278 K, they are higher. These phase equilibria suggest the formation of hydrates other than structure-I methane hydrates in the two systems. The crystallographic structures of the hydrates are determined to be structure H by means of X-ray diffraction as expected from considerations of sizes and shapes of the 3-methyltetrahydropyran and 2-methyltetrahydrofuran molecules     

Electrochemical studies of the interaction of metal chelates with DNA. 4. Voltammetric and electrogenerated chemiluminescent studies of the interaction of tris(2,2'-bipyridine)osmium(II) with DNA

Cyclic voltammetric and electrogenerated chemiluminescent data were used to study the binding of tris(2,2'-bipyridine)-osmium(II), Os(bpy)3(2+), an electrostatic binder, to calf thymus DNA. The oxidized form of the osmium complex, Os(bpy)3(3+), has a stronger association to DNA than the reduced form, Os(bpy)3(2+), as indicated by the negative shift of E0' of the CV waves (K3+/K2+ = 3.35). The calculated binding constant, K2+, and binding site size, s, for the Os(byp)3(2+)-DNA system depended slightly on whether a mobile or a static equilibrium was assumed. In 10 mM NaCl, 10 mM Tris pH 7, K2+ = (7.3 +/- 0.4) x 10(3) M-1 and s = 3 base pairs (mobile) and K2+ = (5.0 +/- 0.2) x 10(3) M-1 and s = 3 base pairs (static). Electrogenerated chemiluminescence (ECL) was produced upon oxidation of Os(bpy)3(2+) at a Pt electrode in a solution containing 10 mM C2O4(2-) and 10 mM phosphate at pH 5. Addition of DNA caused a decrease in the emission intensity (I); a plot of I vs relative DNA concentration yielded K2+ = (6.5 +/- 0.5) x 10(3) M-1 and s = 3 base pairs. The osmium complex produced ECL when bound to the DNA molecule with an efficiency of 30% that of the unbound chelate.     

Ion-Pair Extraction of Metalloporphyrins into Acetonitrile for Determination of Copper(II)

Equilibrium study of ion-pair extraction of a cationic water-soluble porphyrin [5,10,15,20-tetrakis(1-methylpyridinium-4-yl)porphyrin, H(2)tmpyp(4+)] and its metalloporphyrins (MP) into the acetonitrile layer, separated by addition of sodium chloride (4.00 mol dm(-)(3)) to a 1:1 (v/v) acetonitrile-water mixed solvent, was carried out to develop a new and useful method for the determination of a subnanogram amount of copper(II). M denotes Zn(2+), Cu(2+), Co(3+), Fe(3+), and Mn(3+), and P(2)(-) is porphyrinate ion. The extraction and dissociation constants of the ion-pair complexes, defined by K(ex) = [MP(ClO(4))(4)](org)[MP(4+)](aq)(-)(1)[ClO(4)(-)](aq)(-)(4), K(dis,1) = [MP(ClO(4))(3)(+)](org)[ClO(4)(-)](org)[MP(ClO(4))(4)](org)(-)(1), and K(dis,2) = [MP(ClO(4))(2)(2+)](org)[ClO(4)(-)](org)[MP(ClO(4))(3)(+)](org)(-)(1), were determined by taking into account the partition constant of sodium perchlorate (K(D) = 1.82 ± 0.01). The equilibrium constants were found to be K(ex)K(dis,1) = (7.2 ± 1.3) × 10(4), (6.4 ± 0.9) × 10(4), (1.35 ± 0.13) × 10(5), (4.8 ± 0.6) × 10(3), (1.23 ± 0.05) × 10(4), and (1.42 ± 0.07) × 10(3) at 25 °C for the free base porphyrin (H(2)tmpyp(4+)) and the metalloporphyrins of zinc(II), copper(II), cobalt(III), iron(III), and manganese(III), respectively. The K(dis,2) values were (2.9 ± 1.4) × 10(-)(2), (3.1 ± 1.1) × 10(-)(2), (8.0 ± 4.9) × 10(-)(3), and (5.1 ± 2.2) × 10(-)(2) for the free base porphyrins and the metalloporphyrins of zinc(II), copper(II), and cobalt(III), respectively. The results were developed for determination of a trace amount of copper(II) (3 × 10(-)(8)-4 × 10(-)(6) mol dm(-)(3)) in natural water samples using H(2)tmpyp(4+) with a molar absorptivity of 3.1 × 10(5) mol(-)(1) dm(3) cm(-)(1) at a precision of 1.3% (RSD). The determination of copper(II) was not interfered by the presence of 10(-)(4) mol dm(-)(3) of Mn(2+), Co(2+), Ni(2+), Hg(2+), Cd(2+), Ag(+), Cr(3+), V(5+), Al(3+), Mg(2+), Ca(2+), Br(-), I(-), SCN(-), and S(2)O(3)(2)(-) and 10(-)(5) mol dm(-)(3) of Fe(3+), Zn(2+), and Pd(2+).     

Equilibrium modeling of mixtures of methanol and water

An understanding of the species that form in mixtures of alcohol and water is important for their use in liquid chromatography applications. In reverse-phase liquid chromatography the retention of solutes on a chromatography column is influenced by the composition of the mobile phase, and in the case of alcohol and water mobile phases, the amount of free alcohol and water present. Previous and similar modeling studies of methanol (MeOH) and water mixtures by near-infrared (NIR) spectroscopy have found up to four species present including free MeOH and water and MeOH and water complexes formed by hydrogen bonding associations. In this work an equilibrium model has been applied to NIR measurements of MeOH and water mixtures. A high-performance liquid chromatography (HPLC) pump was coupled to an NIR flow cell to produce a gradual change in mixture composition. This resulted in a greater mixture resolution than has been achieved previously by manual mixture preparation. It was determined that five species contributed to the data. An equilibria model consisting of MeOH, H2O, MeOH(H2O) (log K(MeOH)H2O = 0.10+/-0.03), MeOH(H2O)4 (log K(MeOH)4H2O = -2.14+/-0.08), and MeOH(H2O)9 (log K(MeOH)9H2O = -8.6+/-0.1) was successfully fitted to the data. The model supports the results of previous work and highlights the progressive formation of MeOH and water complexes that occur with changing mixture composition. The model also supports that mixtures of MeOH and water are not simple binary mixtures and that this is responsible for observed deviations from expected elution behavior.     

Electrochemically mediated reduction of horseradish peroxidase by 1,1'-ferrocenedimethanol in organic solvents

Cyclic voltammetry is an efficient means of analyzing the catalytic reduction of H2O2 at immobilized horseradish peroxidase (HRP)-Eastman AQ 55 electrodes in the presence of 1,1'-ferrocenedimethanol as a one-electron reversible cosubstrate. This system was employed to study the kinetics of the reduction of compound II of HRP in a number of organic solvents. An electrocatalytic response was detected in methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, acetone, 2-butanone, 1,2-propanediol, acetonitrile, ethyl acetate, and ethylene glycol. Unusual bell-shaped variations of the peak or plateau catalytic current with the substrate concentration were observed in all solvents tested. The results obtained in methanol, acetonitrile, and 1-propanol were analyzed using the model developed by Saveant (Limoges, B.; Saveant, J.-M.; Yazidi, D. J. Am. Chem. Soc. 2003, 125, 9192-9203). The values of k3Gamma0 and K3,M, where k3 = k3,1k3,2/(k3,-1 + k3,2), Gamma0 is the surface concentration of active enzyme, and K3,M = (k3,-1 + k3,2)/k3,1, were determined. The values of k3Gamma0 for the mediated reduction of compound II of HRP in methanol, 1-propanol, and acetonitrile (in the presence of 5% aqueous buffer) were not affected by the solvent dielectric constant but decreased with solvent hydrophobicity. The value of K3,M obtained in methanol was similar to that obtained for [Os(bpy)2pyCl]2+ in aqueous buffer.     

Tweezer-type neutral carrier-based calcium-selective membrane electrode with drastically reduced anionic interference

A new calcium-selective ionophore N,N-dioctyl-3alpha,12alpha-bis(N-heptyl-N-methylcarbamoyl-methoxyacetamidoacetoxy)-5beta-cholan-24-amide (denoted as BACA), was synthesized, and its potentiometric performance has been evaluated in comparison with that of the best known calcium-selective neutral carriers, ETH 129 and ETH 1001. The 1H NMR spectra of BACA titrated with Ca(SCN)2 suggest that BACA forms a 1:1 complex, tweezing a calcium ion between the two parallel diamide groups substituted on a rigid bile acid frame. The calcium-selective membrane based on BACA was less selective to calcium (log K(Ca2+ j)POT = -4.2, -4.2, -4.6, and -4.8, respectively, for j = Mg2+, Li+, Na+, and K+) than those based on ETH 129 (log K(Ca2+ j)POT = -4.4, -4.3, -5.4, and -5.4, respectively, in the same order) and ETH 1001 (log K(Ca2+ j)POT = -4.4, -4.4, -5.4, and -5.4), implying that BACA forms a weaker calcium complex than the other two ETH compounds. In our experimental conditions, potentiometrically determined complex formation constants of calcium-selective neutral carriers (log beta(Ca2+ L)) were 15.2, 14.0, and 8.6 for ETH 129, ETH 1001, and BACA, respectively. A slightly reduced calcium selectivity of BACA, however, affects the anionic interference-free calcium-selective membrane; the BACA-based membrane exhibits a Nernstian response up to 10(-1) M Ca2+ in the presence of lipophilic anions (e.g., SCN-, ClO4-, salicylate, and I-) and anionic surfactant, whereas the ETH 129- and ETH 1001-based ones suffer from serious anionic interference showing a curvature or leveled off response over about 10(-4) M. It was demonstrated that such a trade off does not affect the analytical performance of BACA-based electrode in most applications, including clinical analysis.     

Preparation of a Cation Exchanger from Cork Waste：Thermodynamic Study of the Ion Exchange Processes

An ion exchanger was prepared by sulfonation of cork-waste chars. The exchange properties of the resultant material were characterized using Na+, Ca2+ or Fe3+ aqueous solutions. The content of metal ions in the solutions were determined by atomic absorption spectrometry. On the basis of the results obtained, the chemical equilibrium and its thermodynamic aspects related to the ion exchange process were studied. It was found that equilibrium constant K varies by the order: Na+0 and △5°>0, with -△G° following the sequence: Ca2+>Na+>Fe3+.     

几种CFCs代用工质的PVTx实验研究

在对实验方法进行探讨的基础上,对HFC32、RFC143a、HCFC142b和二元混合物系HCFC22/HFC152a等CFCs替代工质进行了PVTx实验研究。蒸汽压和过热区PVTx实验精度为|△T|<28mK、|△P|<1.4kPa、|△v/v|<0.1％、|△x|<0.01％;采用直接观察泡点法测量纯质饱和液体密度精度为|△T|<38mK、|△ρ/ρ|<0.05％。基于界面消失位置和临界乳光现象测定了HFC32的临界密度为ρ_c=430±4Kg/m~3、临界温度T_c=351.28±0.05K,结合本文所给蒸汽压方程得出临界压力为P_c=5.801±0.008MPa。     

Gravity segregation in a homogeneous waterflooded stratum in a seismoacoustic field

The oil saturation distribution in a homogeneous waterflooded oil stratum in a seismoacoustic field is calculated in a computer experiment based on a theoretical model of capillary-gravity segregation.Notation x length coordinate - t time - k(x) absolute permeability of porous medium - s saturation of nonwetting phase - v_i filtration rate of i-th phase - _i viscosity of i-th phase - k_i(s) relative phase permeability - Y_i bulk density - p_i pressure in the phase - p_c capillary pressure - i=1 nonwetting phase - i=2 wetting phase - x_j coordinate of common boundary of j-th and (j+1)-st seams - H stratum thickness - p_c ^j capillary pressure in j-th seam - a sufficiently small number - k₀ characteristic permeability - interphase tension - f(s) Leverett function - =x/H relative height in stratum Translated from Inzhenerno-Fizicheskii Zhurnal, Vol. 55, No. 4, pp. 589–593, October, 1988.     

Near-infrared spectroscopy of H3+ above the barrier to linearity

Since the Royal Society Discussion Meeting on H3+ in 2000, the laboratory spectroscopy of H3+ has entered a new regime. For the first time, transitions of H3+ above the barrier to linearity have been observed. A highly sensitive near-infrared spectrometer based on a titanium:sapphire laser and incorporating a dual-beam, double-modulation technique with bidirectional optical multi-passing has been developed in order to detect these transitions, which are more than 4600 times weaker than the fundamental band. We discuss our recent work on the 2v1 + 2v2(2) <-- 0, 3v1 + v2(1) <-- 0, v1 + 4v2(2) <-- 0, v1 + 4V2(4) <-- 0 and 2v1 + 3v2(1) <-- 0 combination bands and the 5v2(1) <-- 0, 5v2(3) <-- 0, 52(5) <-- 0 and 6v2(2) <-- 0 overtone bands. Experimentally determined energy levels provide a critical test of ab initio calculations in this challenging energy regime (greater than 10,000 cm(-1)). By comparing the experimental energy levels and theoretical energy levels from ab initio calculations in which the adiabatic and relativistic corrections are incorporated, the extent of higher-order effects such as non-adiabatic and radiative corrections is revealed.     

Selective potassium ion recognition by benzo-15-crown-5 fluoroionophore/gamma-cyclodextrin complex sensors in water

Three fluoroionophores Cn (n = 1, 3, 5), in which the crown ether unit and pyrenyl moiety are connected by a -(CH2)n- spacer, have been used to construct supramolecular Cn/gamma-cyclodextrin (gamma-CyD) complexes for alkali metal ion sensing in water. The Cn (n = 3, 5) are found to selectively form 2:1 complexes with K+ in the presence of gamma-CyD and exhibit the pyrene dimer emission in water. Equilibrium analysis of the C3/gamma-CyD complex reveals that the observed dimer emission arises from a 2:1:1 complex of C3 with K+ and gamma-CyD. In the absence of K+, the fluorescence lifetimes for the dimer species ((C3)2CyD and (C3)2(CyD)2) and the monomer species (C3CyD and C3(CyD)2) are 13-18 and 130-180 ns, respectively. Upon addition of 0.10 M KCI, a rising component corresponding to pyrene excimer formation is observed at the dimer emission region. For the C3/gamma-CyD complex, the apparent association constant for K+ of (3.8 +/- 1.3) x 10(9) M(-2) is only slightly affected by the presence of Na+. Although the C5/gamma-CyD complex shows high sensitivity for K+, the selectivity for K+ over Na+ is lower than that of the C3/gamma-CyD complex. In contrast, fluoroionophore C1 with the shortest methylene spacer exhibits no response for alkali metal cations in the presence of gamma-CyD. These results demonstrate that the response function of supramolecular Cn/gamma-CyD complexes is strongly affected by the methylene spacer length of Cn. The highest K+ selectivity is obtained for the C3/gamma-CyD complexes in water.