Dipole moment derivatives of H2O and H2S

The dipole and quadrupole derivatives of H₂O and H₂S are calculated analytically, using the coupled Hartree—Fock method first proposed by Gerratt and Mills. The greater efficiency, of this method allows SCF wave functions very, close to the Hartree—Fock limit to be used. Agreement, with experimental data is good.     

Collisional ionization of fast K atoms by H2S and D2S

The process K + H₂S/D₂S → HS^?/DS^? + K⁺+ H/D has been investigated for K impact energies from near threshold to ≈100 eV. Positive and negative ion energy spectra have been obtained in the forward direction. The threshold for HS^? or DS^?production corresponds to the HS^?/DS^?+ H/D limit of the ²A₁ H₂S^?/D₂S^? state at 1.55 eV.     

Catalytic reaction of tetrahydrofuran with H2S

The reaction of tetrahydrofuran with H₂S catalyzed by acid-base catalysts has been studied. Catalysts containing an acid-base pair, i.e. a Lewis acid center and a base center, are the most active and selective towards thiolane. Proton donor catalysts and those containing only basic centers are of low activity and selectivity.

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H₂S - . , - : - , . , , .

     

A quantum-mechanical study of the lone-pairs in H2O and H2S

It is shown from SCF-MO studies using localised orbitals that the angles between the lone-pairs in H₂O and H₂S are 115° and 127°, in agreement with the qualitative predictions of the Sidgwick-Powell theory.     

金属修饰Ti_2N MXene吸附分解H_2S的第一性原理计算

通过第一性原理计算研究了Ti_2NO_2 MXene对H_2S的吸附、分解行为. Ti_2NO_2对H_2S气体分子的吸附结果表明,两者之间为弱的物理吸附, Ti_2NO_2无法有效吸附H_2S气体.采用过渡金属(Sc、 V)修饰Ti_2NO_2的研究结果表明,Sc和V可以在Ti_2NO_2表面上稳定存在,不易发生团聚,其最稳定吸附位为N原子上方.进一步研究了Sc、 V修饰的Ti_2NO_2对H_2S气体分子的吸附行为,结果表明金属修饰后其吸附H_2S的能力明显提高.此外还发现, H_2S分子可以在Sc/Ti_2NO_2和V/Ti_2NO_2表面直接解离为HS*和H*,而后HS*中的H原子再与H*进一步结合形成H_2, S原子则与过渡金属成键. HS*在V/Ti_2NO_2表面解离的势垒为1.69 eV,低于在Sc/Ti_2NO_2表面的2.08 eV,表明V/Ti_2NO_2有望成为吸附、分解H_2S气体的理想候选材料.     

The solubility of H2S in liquid sulfur

The need for fundamental data describing the dissolution of hydrogen sulfide, H₂S, in Claus recovered liquid sulfur prompted an examination of equilibrium H₂S solubility at typical industrial condensation temperatures and partial pressures. An FT/IR absorption technique has been described and new H₂S solubility measurements have been reported for partial H₂S pressures from 0.4 to 56 kPa and temperatures from 120 to 155 °C. The measurements were combined with previously reported values for atmospheric pressures of H₂S and used to calibrate a semi-empirical equation for the Henry's law solubility in liquid sulfur as a function of temperature. Estimations were compared to Claus plant field data and appear to underestimate the H₂S solubility for the first and second catalyst condenser stages. This underestimation was attributed to rapid condensation resulting in super-saturation of the recovered sulfur liquid, or an inaccurate measurement of the condensation temperatures.     

Photofragmentation of H2S in the first continuum

The dynamics of the photofragmentation of H₂S in the first continuum has been investigated at laser wavelengths 193, 222 and 248 nm. The HS fragments are produced mainly in υ = 0, as expected, but a non-negligible part of the HS radicals produced are vibrationally excited. The distribution of the vibrationally excited radicals peaks at υ = 3 or 4 at 193 nm and at υ = 2 at 222 nm. From the angular distribution of the H fragments it can be concluded that the anisotropy parameter β decreases with increasing wavelength. These results can be explained by a predissociation mechanism. Excitation in the first continuum takes place from the ¹A₁ ground state to the bound ¹B₁ state. This state is predissociated by a repulsive ¹A₂ state producing electronically ground-state H and HS fragments, of which the HS fragments can be vibrationally excited, resulting in a bimodal vibrational distribution. The increase of β with increasing wavelength is caused by a non-negligible lifetime in the ¹B₁ state.     

XPS- und AES-Untersuchungen an Eisen-Kupfer-Legierungen nach kathodischer Polarisation in H2SO4/H2S

Ohne Zusammenfassung

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XPS- and AES-studies of iron-copper alloys after cathodic polarization in H₂SO₄/H₂S

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Eine ausführliche Veröffentlichung unter stärkerer Berücksichtigung der elektrochemischen Untersuchungen findet sich in Corrosion Science (1984) 24:591–611: C. Kato, H. J. Grabke, B. Egert und G. Panzner, Electrochemical and Surface Analytical Studies on Hydrogen Permeation with Fe-Cu Alloys in Sulfuric acid with and without H₂S.     

Laser induced chemiluminescence of BCl3/H2S mixtures

Visible chemiluminescence has been observed from mixtures of BCl₃ and H₂S when subjected to intense 10.6 μm radiation from a CO₂ laser. The spectrum of the emission is found to contain a molecular band structure superimposed on an underlying continuum. The visible fluorescence displays a strong dependence on the incident CO₂ laser power and a temporal component that is faster than gas collision times. The implications of this with regard to laser isotope separation are discussed.     

H2S/H2硫化温度对MoP/SiO2催化剂硫醚化性能的影响

以负载磷酸钼为前驱体,采用程序升温还原法制备了MoP/SiO₂催化剂,以体积分数3%H₂S/H₂对其进行了硫化处理,利用XRD、CO化学吸附、NH₃-TPD、HRTEM-EDX、ICP-AES以及XPS等手段对催化剂进行了表征,研究了硫化温度对MoP/SiO₂催化剂结构和异戊二烯与正丁硫醇硫醚化性能的影响。结果表明,即使在400℃硫化处理也未改变MoP/SiO₂催化剂中MoP体相结构;随着硫化温度提高,催化剂表面酸量增加、金属位数量减少,降低了催化剂C-S键氢解及异戊二烯深度加氢活性,但同时也提高了催化剂烯烃聚合活性。经120℃硫化处理的MoP/SiO₂兼具较佳硫醚化及异戊二烯选择加氢性能。     

The diffusion coefficient of H2S in liquid sulfur

The diffusion coefficient of H₂S in liquid sulfur is a key kinetic parameter that has been missing in literature. In this paper, a pressure decay method was applied to measure the diffusion coefficients of H₂S in liquid sulfur at 403 and 423 K. This pressure decay process was then modeled by taking the simultaneous diffusion and reversible chemical reactions between H₂S and liquid sulfur into consideration. The diffusion coefficients and reaction rate constants were numerically determined by fitting theoretical curves to experimental data using Finite Element Method and Genetic Algorithm. The solubility of H₂S in liquid sulfur at 403 and 423 K was also calculated and the results agreed with the semi-empirical correlation lately reported in literature. This study further extended the validity of the correlation to higher partial H₂S pressure conditions.     

H2S在立方ZrO2(110)面的吸附与解离

采用量子化学的密度泛甬理论方法,探讨了H2S、HS和S在立方ZrO2(110)面上不同吸附位的吸附情况.构型优化的结果表明:在bridge位H2S以垂直底物平面H原子向上、垂直底物平面H原子向下、平行底物平面和hollow位H2S平行底物平面模式吸附在ZrO2(110)面发生解离吸附.SH和S的最佳吸附位分别为桥位和顶位.Mulliken布局和态密度分析显示S原子的p轨道与Zr原子的d轨道发生相互作用.通过计算解离反应的能垒,表明H2S分子在立方ZrO2(110)面发生两步解离.     

Calculation of recombination rate constants in (H2?O2) system

Rate constants of the three-body recombination for the elementary three-molecule stages in hydrogen oxydation have been calculated.

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, .

     

Reaction kinetics of multiphoton excited BCI3 with H2S

In order to investigate unique behaviors in kinetics of the reaction of multiphoton excited BCl₃ with H₂S, two kinds of experiments were performed. The first, parallel beam experiment, gives the activation energy of the primary reaction pathway considerably smaller than the bond strength. The second, focussed beam experiment, shows that the isotope selectivity increase with incident pulse energy. Both results were found different from typical multiphoton dissociation experiments, showing its own characteristics.     

LaCoO3对H2S选择氧化性能的影响

使用溶胶-凝胶法制备了LaCoO₃催化剂,采用XRD、BET和XPS等方式对催化剂进行了表征,考察了该催化剂制备过程中煅烧温度、表面活性剂PEG-6000和PEG-20000含量对其H₂S选择氧化制硫磺反应催化活性的影响。结果表明,表面活性剂PEG-6000及PEG-20000的添加能明显提高LaCoO₃的催化活性。0.02 mol La（NO₃）₃+0.02mol Co（NO₃）₂溶液中添加0.30 g PEG-20000、煅烧温度为650℃时所制备的LaCoO₃催化活性最好;在最佳反应温度260℃下,H₂S的转化率达到96.10%,硫选择性为93.77%。     

Kinetic studies of thiolane synthesis from tetrahydrofurane and H2S

Kinetic studies of tetrahydrofuran reaction with H₂S were carried out in a flow-circulation reactor. Presumably, the reaction takes place through dissociative chemisorption of reactants and the interaction of surface structures formed to produce thiolane and water. A kinetic equation that agrees with the suggested mechanism has been derived.

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- H₂S. , . , .

     

H2O, H2S与双卤分子间相互作用的电子密度拓扑研究

运用量子化学微扰理论MP2和密度泛函B3LYP方法, 采用6-311＋＋G(d,p)基组, 对H₂O, H₂S与双卤分子XY (XY＝F₂, Cl₂, Br₂, ClF, BrF, BrCl)形成的卤键复合物进行构型全优化, 并计算得到了这些体系的分子间相互作用能. 利用电子密度拓扑分析方法对卤键复合物的拓扑性质进行了分析研究, 探讨了该类分子间卤键的作用本质. 结果表明, 形成卤键后, 作为电子受体的双卤分子X—Y键长增长, 振动频率减小. 复合物体系中的卤键介于共价键与离子键之间, 偏于静电作用成分为主.     

Activity of catalysts in 1-butanol reaction with H2S

Reaction of 1-butanol with H₂S has been studied at 300 °C and 0.1 MPa on catalysts of various composition. The catalysts that contain mainly strong proton sites on their surface accelerate dehydration of alcohol alone. In the presence of catalysts possessing acidic and basic Lewis sites 1-butanethiol is formed. Reaction rate increases as the concentration and strength of Lewis acid sites increase.     

Reaction of dodecanol-1 with H2S on acid catalysts

The reaction of dodecanol-1 with H₂S has been studied at 275°C and 0.1 MPa on acid catalysts. Catalysts having only strong proton sites accelerate alcohol dehydration, whereas catalysts with Lewis acid sites support dodecanethiol-1 formation as well. The catalytic activity per one Lewis acid site rises with the increase of the site strength.     

Infrared spectroscopic studies of H2S adsorption on γ-Al2O3

IR spectra of H₂S adsorbed in various quantities on -Al₂O₃ have been studied. The method of spectral probes has been used to determine the extent of H₂S blocking of Lewis acid and basic centers.

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- , -Al₂O₃. .