New calculations on the ion-molecule processes C2H2(+) + H2 --> C2H3(+) + H and C2H2(+) + H2 --> C2H4+

New high-level quantum chemical calculations have been undertaken to understand the rates and mechanisms of the reactive and associative channels for the reactants C2H2(+) + H2. The reactive channel, which produces C2H3(+) + H, has been shown to be slightly endothermic, confirming earlier calculations at a somewhat lower level and in agreement with some recent experimental work. The associative channel, leading to C2H4+, has been shown to proceed via a transition state with negative energy relative to the reactants, so that association is predicted to be efficient. This result is in conflict with an earlier theoretical study but in agreement with low-temperature experimental measurements.     

A pseudopotential study of the hydrogen bond in H2O·H2S,H2S·H2S and H2O·H2Se systems

Intermolecular potential energy curves for the hydrogen bonded systems H₂O·H₂S, H₂O·H₂Se and H₂S·H₂S were calculated with nonempirical pseudopotentials using optimized-in-molecules basis sets augmented by polarization functions. The H₂O·H₂O interaction energy curve has been also considered as a test case. The present results for H₂O·H₂S and H₂S·H₂S indicate much weaker intermolecular interactions than those found in previous ab initio calculations. The H₂O·H₂Se interaction was found to be quite similar to H₂O·H₂S.This work was partly supported by the Polish Academy of Sciences within the Project PAN-09, 7.1.1.1On leave from Quantum Chemistry Laboratory, Dept. of Chemistry, University of Warsaw, Pasteura 1, 02-093. Warsaw, Poland     

An Ab Initio Study of C2H2.H2, C2H2.N2, and C2H2.Ar Complexes

Ab initio calculations at the post Hartree–Fock level were performed on complexes of acetylene with hydrogen, nitrogen, and argon. Total energies, optimum geometries, and binding energies were calculated, using the 6-311G** and the 6-31+G(2df,2pd) basis sets. Calculations showed the complexes to be more stable than the separate entities, with the exception of the acetylene–hydrogen complex.     

Vibrational polarizabilities for H2+, H2 and N2

General formulae for the purely vibrational contributions to the static polarizabilities A_α,βγ, B_α,β,γδ,and C_αβ,γδ are presented. As specific examples, the vibrational contributions to the γ, B, and C tensors for H₂⁺, H₂ and N₂ are calculated. In addition values of the hexadecapole moment for H₂⁺ at a series of internuclear distances are given.     

Electron energy loss spectroscopy (EELS) of H2O,H2S,H2Se and H2Te

Electronic excitation in H₂O, H₂S, H₂Se and H₂Te molecules has been studied by the EELS technique. Spectra of H₂S and H₂Se are remarkably similar with the 1b₁-nd transition most intense. The intensity of the first transition 1b₁-nsa₁ decreases through H₂O to H₂Se and this transition is absent in H₂Te. Transitions observed by EELS have been compared with optical absorption studies. A correlation diagram of the occupied and the excited states has been provided for these four molecules by making use of UVPES and EELS.     

Rates of reaction of atomic oxygen with C2H3F,C2H3Cl,C2H3Br, 1,1-C2H2F2, and 1,2-C2H2F2

Rate constants for the reactions of atomic oxygen (O³P) with C₂H₃F, C₂H₃Cl, C₂H₃Br, 1,1-C₂H₂F₂, and 1,2-C₂H₂F₂ have been measured at 307°K using a discharge-flow system coupled to a mass spectrometer. The rate constants for these reactions are (in units of 10¹¹ cm³ mole^?1 s^?1) 2.63 ± 0.38, 5.22 ± 0.24, 4.90 ± 0.34, 2.19 ± 0.18, and 2.70 ± 0.34, respectively. For some of these reactions, the product carbonyl halides were identified.     

Deuterium exchange in the systems of H2O+/H2O and H3O+/H2O

The reactions of H₂O⁺, H₃O⁺, D₂O⁺, and D₃O⁺ with neutral H₂O and D₂O were studied by tandem mass spectrometry. The H₂O⁺ and D₂O⁺ ion reactions exhibited multiple channels, including charge transfer, proton transfer (or hydrogen atom abstraction), and isotopic exchange. The H₃O⁺ and D₃O⁺ ion reactions exhibited only isotope exchange. The variation in the abundances of all ions involved in the reactions was measured over a neutral pressure range from 0 to 2 × 10⁻⁵ Torr. A reaction scheme was chosen, which consisted of a sequence of charge transfer, proton transfer, and isotopic exchange reactions. Exact solutions to two groups of simultaneous differential equations were determined; one group started with the reaction of ionized water, and the other group started with the reactions of protonated water. A nonlinear least-squares regression technique was used to determine the rate coefficients of the individual reactions in the schemes from the ion abundance data. Branching ratios and relative rate coefficients were also determined in this manner.A delta chi-squared analysis of the results of the model fitted to the experimental data indicated that the kinetic information about the primary isotopic exchange processes is statistically the most significant. The errors in the derived values of the kinetic information of subsequent channels increased rapidly. Data from previously published selected ion flow tube (SIFT) study were analyzed in the same manner. Rigorous statistical analysis showed that the statistical isotope scrambling model was unable to explain either the SIFT or the tandem mass spectrometry data. This study shows that statistical analysis can be utilized to assess the validity of possible models in explaining experimentally observed kinetic behaviors.     

Gasphasenreaktionen von H3PF2: Darstellung der Monohalogenphosphane H2PF und H2PCl

Gas Phase Reactions of H₃PF₂: Synthesis of the Monohalogenophosphanes H₂PF and H₂PCl Gas phase reactions of H₃PF₂ at ≤ 10 mbar with hydrides (B₂H₆, HSi(CH₃)₃, HSn(CH₃)₃), amines (H₃N, N(CH₃)₃) and electrophilic halides of B, Si and Ti in the beam of an IR interferometer have been investigated with a time delay of 15 sec. between successive measurements. Gas/solid phase reactions of H₃PF₂ with KF and AlCl₃ and reactions of H₃PF₃ and HPF₄ have been studied similarly. With H₃N, N(CH₃)₃ and electrophilic halides, H₃PF₂ was converted into its dehydrofluorination product H₂PF. This eliminates further HF in the presence of H₃N or N(CH₃)₃, while BCl₃ or TiCl₄ yield the hitherto unknown H₂PCl. The IR spectra of the short-lived species H₂PF and H₂PCl as well as their deuterated isotopomers, which reveal at room temperature and ≤ 10 mbar a halflife time of ≤ 12 min. and ≤ 50 sec. respectively, were recorded and analysed in order to characterize the novel species.     

Rotational inelasticity in high-energy H2H2 collisions

Rotational cross sections for transitions in the H₂H₂ system have been calculated for energies up to ≈ 2.0 eV and for rotor levels up to j = 11 in the effective potential approximation. The cases of para H₂-para H₂, ortho H₂-ortho H₂ and ortho H₂-para H₂ are considered. Correlations and trends in the cross sections have been examined, and it is shown that the high-energy collisions are dominated by coupling effects. The results of this analysis also suggest that the collision process may be profitably viewed as a diffusion of probability among the levels.     

FeCl2-K2MoS4体系电催化还原乙炔为乙烯

采用控电位电解、循环伏安法和交流阻抗法研究了FeCl₂-K₂MoS₄体系对乙炔在石墨电极上还原为乙烯的电催化活性及反应机理。实验结果表明,当石墨阴极的电位控制在-1.50V(vs.SCE)时,FeCl₂+K₂MoS₄的DMF溶液对C₂H₂还原为C₂H₄表现出明显的电催化活性和高的选择性。在-0.5～-1.0V时Mo(Ⅵ)还原为Mo(Ⅴ);在按连串的电子传递机理进行的Mo(Ⅴ)→Mo(Ⅲ)反应的电位区间(-1.0～-1.50V)溶液中所形成的络合品种传递电子的能力更强。Mo(Ⅲ)可能是络合物的电活性成分。     

可见光光解H2S产H2的研究——Rh2O3/CdS悬浮体系中硫化物水溶液的光解

在半导体粉末悬浮体系光解水研究中,最常用的半导体粉末是CdS和TiO₂。前者光谱响应好,可见光即可激发,但易于光腐蚀;后者稳定性好,但禁带宽,仅紫外光可激发。从不同角度改善这二者的性能,一直为人们所关注。在CdS上沉积RuO₂,并选择适宜的反应以抑制CdS的光腐蚀^[1];应用掺杂的方法,使TiO₂的光谱响应扩展至可见区,已取得进展。     

The effect of the torsional and stretching vibrations of C2H6 on the H + C2H6 --> H2 + C2H5 reaction

We present a three-dimensional quantum scattering model to treat reactions of the type H + C2H6 --> H2 + C2H5. The model allows the torsional and the stretching degrees of freedom to be treated explicitly. Zero-point energies of the remaining modes are taken into account in electronic structure calculations. An analytical potential-energy surface was developed from a minimal number of ab initio geometry evaluations using the CCSD(T,full)/cc-pVTZ//MP2(full)/cc-pVTZ level of theory. The reaction is endothermic by 1.5 kcal mol(-1) and exhibits a vibrationally adiabatic barrier of 12.0 kcal mol(-1). The results show that the torsional mode influences reactivity when coupled with the vibrational C-H stretching mode. We also found that ethyl radical products are formed internally excited in the torsional mode.     

Speciation in the aqueous H+/H2VO4-/H2O2/phosphate system

The speciation in the aqueous H(+)/H(2)VO(4)(-)/phosphate (dihydrogen phosphate, P(-)) and H(+)/H(2)VO(4)(-)/H(2)O(2)/P(-) systems has been determined in the physiological medium of 0.150 M Na(Cl) at 25 degrees C. A combination of multinuclear NMR integral and chemical shift (Bruker AMX500) as well as potentiometric data (glass electrode) have been collected and treated simultaneously by the computer program LAKE. The pK(a)-values for phosphoric acid have been determined by potentiometric and (31)P NMR chemical shift data, and have been found to be 1.85 +/- 0.02, 6.69 +/- 0.02 and 11.58 +/- 0.07. The errors given are 3sigma. Altogether nine vanadate-phosphate species have been found in the ternary H(+)/H(2)VO(4)(-)/P(-) system in the pH region 1-11, with the following compositions: VP, VP(2) and V(14)P. Equilibrium is very slow in acidic solutions, requiring more than 3 months for the formation of V(14)P species. On the other hand, less than 15 min are needed for equilibration at neutral and alkaline pH. In the quaternary H(+)/H(2)VO(4)(-)/H(2)O(2)/P(-) system, four new species have been found in addition to all binary and ternary complexes. They are of VXP and VX(2)P compositions, where X denotes the peroxo ligand. (51)V and (31)P NMR chemical shifts, compositions and formation constants are given, and equilibrium conditions are illustrated in distribution diagrams as well as the fit of the model to the experimental data. Biological and medical relevance of the species is also discussed and physiological conditions are modelled.     

H2O2—H2SO4体系电化学振荡行为的研究

Ｈ２Ｏ２参与的电化学振荡反应长期以来倍受人们的关注［１,２,３］,文献［１］报道了Ａｇ电极在Ｈ２Ｏ２－ＨＣｌＯ４水溶液中的电势振荡现象;文献［２］报道了Ｐｔ电极Ｈ２Ｏ２－Ｈ２ＳＯ４体系在控电流条件下的电势振荡,其实验的Ｈ２Ｏ２浓度范围为０．０２～０．...     

Direct Synthesis of H2O2 by a H2/O2 Fuel Cell

Direct synthesis of H₂O₂ solutions by a fuel cell method was reviewed. The fuel cell reactor of [O₂, gas-diffusion cathode electrolyte solutions Nafion membrane electrolyte solutions gas-diffusion anode, H₂] is very effective for formation of H₂O₂. The three-phase boundary (O₂(g)–electrode(s)–electrolyte(l)) in the gas-diffusion cathode is essential for efficient formation of H₂O₂. Fast diffusion processes of O₂ to the active surface and of H₂O₂ to the bulk electrolyte solutions are essential for H₂O₂ accumulation. The maxima H₂O₂ concentrations of 1.2 M (3.5 wt%) and 2.4 M (7.0 wt%) were accomplished by the heat-treated Mn-OEP/AC electrocatalyst with H₂SO₄ electrolyte and by the VGCF electrocatalyst with NaOH electrolyte, respectively, under short circuit conditions.