Comparison of the Kinetics of the Exchange Mechanism of the Thallium Ion with 18C6 and with Pentaglyme in Acetonitrile Solutions

Abstract

In acetonitrile solutions, the exchange reaction is bimolecular in the Tl⁺ + 18C6 system, while in the Tl⁺ + pentaglyme system the associative-dissociative and the bimolecular mechanisms coexist at room temperature and the bimolecular exchange reaction dominates at 263° K. For the bimolecular mechanism in the case of Tl⁺ + 18C6 and the associative-dissociative mechanism in the case of Tl⁺ + pentaglyme, the activation energies of the exchange reactions change with temperature. At 298° K, in the Tl⁺ + 18C6 system the activation energy for the bimolecular exchange reaction is ≈ 2 kcal.mol^?1 and exchange rate constant (k₁) is (4.1 ± 0.1) × 10⁷ s^?1mol^?1; in the Tl⁺ + pentaglyme system, the activation energy for the associative-dissociative exchange reaction is ≈ 5 kcal mol^?1 and the decomplexation rate constant (k_?2) is (2.2 ± 0.4) X 10⁵ s^?1. The activation energy for the bimolecular exchange in the Tl⁺ + pentaglyme system was determined to be 3.00 ± 0.05 kcal.mol_?1 and the exchange rate constant (3.0 ± 0.1) X 10⁸ s^?1 mol^?1.     

Theoretical investigation of the spin-Hamiltonian parameters and optical spectra for the doped Cu2+ in ZnCdO nanopowder

The spin-Hamiltonian (SH) parameters (g factors g_||, g_⊥ and hyperfine structure constants A_||, A_⊥) and d–d transitions for ZnCdO:Cu²⁺ are calculated based on the perturbation formulas for a 3d⁹ ion in tetragonally elongated octahedra. Good agreement between the calculated results (four SH parameters and three optical absorption bands) and the experimental results can be obtained. Since the SH parameters are sensitive to the local structure of a paramagnetic impurity center, the tetragonal distortion (characterized by the relative elongation ratio ρ ≈ 3.5% along the C₄ axis) of the impurity center due to the Jahn–Teller effect is also acquired from the calculations. The negative and positive signs of hyperfine structure constants A_|| and A_⊥ for ZnCdO:Cu²⁺, respectively, are also suggested in the discussions.     

气力提升系统气液两相流数值模拟分析

污水处理、油田采油、液态金属冷却反应堆和磁流体动力转换器等领域采用气力提升系统有其显著优势.由于不同液体介质与气体介质密度对气力提升系统性能影响较大,因此本文基于Fluent仿真软件,采用欧拉模型、k-ω剪切应力输运湍流模型数值模拟了氮气-水、氮气-煤油、氮气-水银及空气-水、氩气-水、氮气-水下气力提升系统内气液两相流动行为,分析了系统稳定时提升立管内气相体积分数、提升液体流量、提升效率、提升管出口处液体径向速度的变化规律.研究结果表明:1)氮气-水、氮气-煤油、氮气-水银系统中,提升管内液体介质密度越大,提升管内气相体积分数越小、提升液体流量越大、提升效率越高;2)空气-水、氩气-水、氮气-水系统中,提升管内气体介质密度越大,提升管内气相体积分数越小、提升液体流量越大、提升效率峰值越小;3)提升管出口处提升液体径向速度随气体充入量的不断增加而整体波动升高,最终管轴中心附近液体速度较大,管壁附近液体速度较小.本文研究成果为污水处理、气举采油、液态重金属冷却核反应堆和磁流体动力转换器等应用领域的气力提升技术的优化提供科学的理论基础.     

Microstructure evolution and passivation quality of hydrogenated amorphous silicon oxide(a-SiOx:H) on〈100〉- and 〈111〉-orientated c-Si wafers

Hydrogenated amorphous silicon oxide(a-SiOx:H) is an attractive passivation material to suppress epitaxial growth and reduce the parasitic absorption loss in silicon heterojunction(SHJ) solar cells. In this paper, a-SiOx:H layers on different orientated c-Si substrates are fabricated. An optimal effective lifetime(τ(eff)) of 4743 μs and corresponding implied opencircuit voltage(iV(oc)) of 724 mV are obtained on〈100〉-orientated c-Si wafers. While τ(eff) of 2429 μs and iV_oc of 699 mV are achieved on 111-orientated substrate. The FTIR and XPS results indicate that the a-SiOx:H network consists of SiOx(Si-rich), Si–OH, Si–O–SiHx, SiO2 ≡ Si–Si, and O3 ≡ Si–Si. A passivation evolution mechanism is proposed to explain the different passivation results on different c-Si wafers. By modulating the a-SiOx:H layer, the planar silicon heterojunction solar cell can achieve an efficiency of 18.15%.     

In-situ SiN combined with etch-stop barrier structure for high-frequency AlGaN/GaN HEMT

The etch-stop structure including the in-situ SiN and AlGaN/GaN barrier is proposed for high frequency applications.The etch-stop process is realized by placing an in-situ SiN layer on the top of the thin AlGaN barrier.F-based etching can be self-terminated after removing SiN,leaving the AlGaN barrier in the gate region.With this in-situ SiN and thin barrier etch-stop structure,the short channel effect can be suppressed,meanwhile achieving highly precisely controlled and low damage etching process.The device shows a maximum drain current of 1022 mA/mm,a peak transconductance of 459 mS/mm,and a maximum oscillation frequency(fmax)of 248 GHz.     

大规模合成具有氧空位的多孔Bi2O3用于有效降解亚甲基蓝

光催化降解有机污染物由于其具有低能耗和绿色环保的特点,已经成为研究的热点. 氧化铋纳米晶体的带隙在2.0∽2.8 eV之间,利用它催化可见光降解有机污染物具有较高的活性,从而引起了越来越多的关注. 尽管近年来已经开发了几种制备Bi₂O₃基半导体材料的方法,但是仍然难以用简单的方法大规模地制备高活性的Bi₂O₃催化剂. 因此,开发简单可行的大规模制备Bi₂O₃纳米晶体的方法对于工业废水处理的潜在应用具有重要意义. 本文通过蚀刻商用BiSn粉末,然后进行热处理,成功地大规模制备了多孔Bi₂O₃. 获得的多孔Bi₂O₃在亚甲基蓝(MB)的光催化降解中表现出优异的活性和稳定性. 对该机理的进一步研究表明,多孔Bi₂O₃合适的能带结构允许生成活性氧物种,例如O₂^-·和·OH,可有效降解MB.     

Halogen bond between hypervalent halogens YF3/YF5 (Y=Cl,Br, I) and H2X (X= O,S, Se)

ABSTRACT

The complexes of H₂X (X?=?O, S, Se) with hypervalent halogens YF₃ and YF₅ (Y?=?Cl, Br, I) have been studied. The σ-hole on the Y atom participates in a halogen bond with the lone pair on the chalcogen atom. In addition, some secondary interactions coexist with the halogen bond in most complexes. The interaction energy correlates with the nature of both X and Y atoms. In most cases, the complex is more stable for the heavier Y atom and the lighter X atom. Of course, there are some exceptions in H₂X···YF₃. YF₃ forms a more stable complex with H₂X than does YF₅. These complexes are dominated by electrostatic interaction and the halogen bond involving H₂S and H₂Se exhibits some covalent character.

Halogen bond plays an important role in chemical reactions and multivalent halogens can regulate chemical reactions by participating in a halogen bond. Thus we compare the effect of the chalcogen electron donor on the strength and nature of halogen bonding involving multivalent halogens.     

Applications of Markov spectra for the weighted partition network by the substitution rule

The weighted self-similar network is introduced in an iterative way. In order to understand the topological properties of the self-similar network, we have done a lot of research in this field.Firstly, according to the symmetry feature of the self-similar network, we deduce the recursive relationship of its eigenvalues at two successive generations of the transition-weighted matrix.Then, we obtain eigenvalues of the Laplacian matrix from these two successive generations.Finally, we calculate an accurate expression for the eigentime identity and Kirchhoff index from the spectrum of the Laplacian matrix.     

On the measurement of normal stress differences in steady shear flow

Summary Compared to the similar pressure-distribution cone-and-plate apparatus of Adams and Lodge (4), the new apparatus' improvements include: temperature control of the cone (as well as the plate); increased stiffening of the frame; four (not three) pressuremeasuring holes in the cone/plate region; inclusion of a pressure-measuring hole on the axis under the cone truncation; exclusive use of a vertical free liquid boundary at the cone rim (without a sea of liquid). Temperature control of the rotating cone and of the fixed plate leads to acceptable temperature uniformity in the test liquid for working temperatures within 10°C or 20°C of ambient; the corresponding interval is about 1°C if the cone temperature control is abandoned. Pressure gradients measured using a Newtonian liquid agree with those calculated using Walters' eq. (3). For a viscoelastic liquid, after subtracting inertial contributions, pressure distributions measured at a given shear rate in the cone/plate region do not change when the gap angle is changed from 2° to 3°, showing that the effects of secondary flow are negligible. Values ofN ₃ =N ₁ + 2N ₂ obtained from the gradients of these distributions are believed to be in error by not more than ±1 Pa, in favorable cases. The present most useful ranges are: 10 to 5000 Pa forN ₃; 0.1 to 200 sec^–1 for shear rate; up to 5 Pa s for viscosity; and 5 to 40°C for temperature. As an application, it is shown that adding 0.1% of a high molecular weight polyisobutylene to a 2% polyisobutylene solution doublesN ₃ and has no detectable effect on the viscosity measured at low shear rates with a Ferranti-Shirley viscometer.

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Zusammenfassung Im Vergleich zu dem ähnlichen Kegel-Platte-Gerät von Adams und Lodge (4) zur Messung der Druckverteilung wurden an dem neuen Gerät die folgenden Verbesserungen vorgenommen: Temperaturregelung an Kegel und Platte, Versteifung des Rahmens, vier (anstatt drei) Druckmeßlöcher im Kegel-Platte-Bereich, ein zusätzliches Druckmeßloch auf der Achse unter der Kegelstumpf-Deckfläche, ausschließliche Verwendung einer vertikalen freien Grenzfläche der Flüssigkeit am Kegelrand (ohne umgebenden Flüssigkeitssee). Die Temperaturregelung des rotierenden Kegels und der festen Platte führt zu einer ausreichenden Temperaturgleichförmigkeit in der Testflüssigkeit für Betriebstemperaturen, die höchstens um 10–20°C von der Umgebungstemperatur abweichen. Dieses Intervall beträgt dagegen nur etwa 1°C, wenn auf die Temperaturregelung am Kegel verzichtet wird. Für newtonsche Flüssigkeiten entsprechen die gemessenen Druckgradienten den mittels der Gleichung von Walters (3) berechneten. Für viskoelastische Flüssigkeiten zeigen sich bei der Änderung des Spaltwinkels von 2° auf 3° nach Abzug der Trägheitsbeiträge keine Änderungen der bei einer bestimmten Schergeschwindigkeit gemessenen Druckverteilung. Dies zeigt, daß Sekundärströmungseffekte vernachlässigbar sind. Es darf angenommen werden, daß die Werte vonN ₃ =N ₁ + 2N ₂, die man aus den Gradienten dieser Verteilungen erhält, unter günstigen Umständen mit einem Fehler von nicht mehr als ±1 Pa behaftet sind. Gegenwärtig liegen die günstigsten Bereiche bei 10 bis 5000 Pa fürN ₃, 0,1 bis 200 s^–1 für die Schergeschwindigkeit, unterhalb von 5 Pa s für die Viskosität und 5 bis 40°C für die Temperatur. Als Anwendung wird gezeigt, daß ein Zusatz von 0,1% hochmolekularen Polyisobutylens zu einer 2%igen Polyisobutylenlösung den Wert vonN ₃ verdoppelt, aber keinen erkennbaren Einfluß auf die (bei geringen Schergeschwindigkeiten mit einem Ferranti-Shirley-Viskosimeter gemessen) Viskosität hat.

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udsf unidirectional shear flow - TCP truncated-cone and plate - N ₁,N ₂ 1st and 2nd normal stress differences in udsf - N ₃ N ₁ + 2N ₂ - : = A is defined by the equationA := B - P ^* hole pressurePw – Pm; Pw, Pm = pressures measured by flush transducer and by hole-mounted transducer - t time - , strain rate, shear rate - (P,t) covariant body metric tensor at particleP and timet - ⁱ , _i covariant and contravariant udsf body base vectors (i = 1, 2, 3) - ^–1 inverse of - R, plate radius, cone/plate gap angle - r ₀,h ₀ radius and height of cone truncation - r,, spherical polar coordinates; cone axis = 0; plate surface = /2 - physical components of stress; for a tensile component - cone angular velocity - p on the plate = /2 - ,T, density, absolute temperature, viscosity - P 0.15 ²(r ² –R ²) (inertial contribution) [2.7] - P _ve contribution [2.8] from flow perturbations of viscoelastic origin - r _i i = 1,2,3,4; values ofr at centers of holes in cone/plate region - P _i () pressure change recorded by transducerTi when cone angular velocity goes from zero to - 1/2 {P _i ()+ P _i (–)} (average for 2 senses of rotation) - rim pressure, from least-squares line through four points - Re Reynolds' number:R ²/ - (P,t)/t With 11 figures and 2 tables     

噪声对滑动移除近似熵的影响

受外强迫和仪器本身的测量误差等因素的影响, 观测数据中经常包含噪声和扰动等一些虚假的信息. 针对这一问题, 本文研究了各种不同噪声对滑动移除近似熵的影响. 研究结果表明, 滑动移除近似熵的检测结果受尖峰噪声和高斯白噪声的影响较小, 意味着其具有很强的抗噪能力, 这为该方法在实际观测资料中的广泛应用提供了坚实的实验基础.