A comparative study of CH4 and CF4 rf discharges using a consistent plasma physics and chemistry simulator

A self-consistent, one-dimensional simulator for the physics and chemistry of radio frequency (rf) plasmas was developed and applied for CH₄ and CF₄. The simulator consists of a fluid model for the discharge physics, a commercial Boltzmann equation solver for calculations of electron energy distribution fuction (EEDF), a generalized plasma chemistry code, and an interface module among the three models. The CH₄ and CF₄ discharges are compared and contrasted: CH₄ plasmas are electropositive, with negative ion densities one order of magnitude less than those of electrons, whereas CF₄ plasmas are electronegative, with ten times more negative ions than electrons. The high-energy tail of tire EEDF in CH₄, lies below both the Druyvensteyn and Maxwell distributions, whereas tire EEDF high-energy tail in CF₄ lies between the two. For CH₄, the chemistry model was applied for four species, namely, CH₄ CH₃ CH₂, and H, whereas for CF₄, five species were examined namely CF₄, CF₃, CF₂, CF, and F The predicted densities and profiles compare favorably with experimental data. Finally, the chemistry results were fedback into the physics model until convergence was obtained.     

Enthalpies of crystallization of equilibrium solid phases occurring in the system KNO3−NH4NO3−H2O at 298.15 K

The concentration dependencies of the differential enthalpies of solution along several crystallization paths in the above mentioned system were measured. On this basis enthalpies of crystallization of equilibrium solid phases occurring there were calculated.     

A theory of molecules in molecules IV. Application to the Hydrogen Bonding Interaction in NH3 · H2O

The theory of molecules in molecules introduced in previous articles is applied to study the hydrogen bonding interaction between an ammonia molecule as proton acceptor and a water molecule as proton donor. The localized orbitals which are assumed to be least affected by the formation of the hydrogen bond are transferred unaltered from calculations on the fragments NH₃ and H₂O, the remaining orbitals are recalculated. A projection operator is used to obtain orthogonality to the transferred orbitals. Additional approximations have been introduced in order to be able to save computational time. These approximations can be justified and are seen to lead to binding energies and bond lengths which are in satisfactory agreement with the SCF values. The point charge approximation for the calculation of the interaction energy between the two sets of transferred localized orbitals is, however, not applicable in this case. An energy analysis of the effect of the hydrogen bond on the localized orbitals of the two fragments is given.     

Enthalpy of solution and effect of temperature on activity coefficients in MSO4−H2SO4−H2O system

Results of calorimetric determination of integral enthalpies of solution of some hydrates (monohydrates and heptahydrates) of 3d transition metal sulphates such as FeSO₄, NiSO₄ and MnSO₄ in three-component systems at sulphuric acid concentrations up to 2M are reported. Measured values of integral enthalpies of solution are the basis for calculation of activity coefficient temperature dependences according to Pitzer's model.     

The influence of electron correlation on reaction energies. The dimerization energies of BH3 and LiH

Results of rigorous computations employing extended Gaussian-type basis sets are reported for BH₃, B₂H₆, LiH, and Li₂H₂ in their respective equilibrium geometries. The dimerization energy of BH₃ is calculated as −20.7 kcal/mol within the Hartree-Fock approximation and as −36.6 kcal/mol if electron correlation is included. The corresponding results for the dimerization of LiH are −47.3 kcal/mol and −48.3 kcal/mol. Partitioning of the correlation energy contributions allows to attribute the effect of electron correlation to the increase of next neighbour bond interactions on the dimerization of BH₃ and LiH. The difficulties of accurate computations of reaction energies are discussed in detail.     

On the reduction of Cr3+ during the thermal decomposition of fluorochromates(III) with nitrogen containing cations

The thermal decomposition of [CO(NH₂)₂H]CrF₆·H₂O, (C₃N₆H₈)CrF₅·H₂O and the solid state reaction of CrF₃ and melamine are investigated under non-reciprocal quasi-static conditions and compared with the thermal behaviour of other fluorochromates(III) ([Cr(NH₃)₆]CrF₆, (NH₄)₃CrF and [C(NH₂)₃]₃CrF₆). The comparison of the results shows that the amount of chromium(II) in the final product is determined by the thermal stability and consequently by the decomposition temperature of the intermediates. Neither bonding properties in the starting materials nor the absolute amount of generated NH₃ influence the composition of the final product.     

Potential energy surfaces for BeH2 and BH2

The diatomics-in-molecules method has been used to obtain potential energy surfaces (PES) for the molecules BeH₂ and BH₂. The method is used in a way proposed by Tully [1]. The present paper contains an analysis of some features of PES in the vicinity of their crossing near linear configurations of the molecules.     

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     

Untersuchungen der Hydroxylammonium-Aluminate

Summary Two microcristalline phases have been isolated from aqueous solutions: (NH₃OH)₂AlF₅(A) and (NH₃OH)AlF₄·H₂O(B). They crystallize in the orthorhombic system with cell parameters for A:a=6.475 (3) Å,b=7.295 (3) Å,c=10.827 (5) Å, and for B:a=7.003 (3) Å,b=8.489 (4) Å,c=10.745 (5) Å. The Hydroxylammonium-aluminates were characterized by vibrational spectroscopy and their thermal decomposition studied by DSC and TG analysis.

     

On the bond order of C2 and N2

The commonly adopted bond order values of C₂ and N₂ are critically investigated with a new bond order concept. Ab initio calculations with extended basis sets suggest that C₂ can be described by a double to triple bond closer to acetylene than to ethylene and N₂ by a triple bond. The basis set dependence is discussed. Also a relation between the number of basis functions, MO's and non-vanishing eigenvalues of the bond order parts of the density matrix is presented.     

The deviation of the true heating rate with respect to the programmed one

The paper deals with the influence of the deviation of the true heating rate with respect to the programmed one on the values of non-isothermal kinetic parameters for the solid-gas thermal decompositions of CaC₂O₄.H₂O and [Ni(NH₃)₆]Br₂. An original method, based on integration over small ranges of the variables and making use of local heating rates, was applied in order to determine the non-isothermal kinetic parameter values. The results show significant differences between values of non-isothermal kinetic parameters obtained by using true local heating rates and those obtained by using the programmed heating rate.     

Outer shell ionization potentials for ethane by a many-body Green's function method

A calculation based upon the many-body Green's function method is employed to obtain the outer shell vertical ionization potentials of the ethane molecule. An extended basis set is employed to represent the approximate optical potential, derived by the functional derivative approach, as well as the one-electron Green's function. The results obtained confirm a²E_g state for the ion arising from the first ionization process. Supported by a fellowship of the Scuola Normale Superiore.     

Evaluation of 4-amino-2-hydroxybenzoic acid as an eluent for indirect photometric determination of uncommon anions

Summary The efficacity of 4-amino-2-hydroxybenzoic acids as an eluent for the separation and determination of uncommon anions has been evaluated. The intensely absorbing eluent (λ_max 320 nm) offers a convenient indirect photometric approach to quantitate the species of interest in ppm and sub-ppm range. In the singlecolumn ion chromatography mode at 2 mM/2 mL/min and pH=6.0, clean separations of common and uncommon anions can be realized.     

V(HSO_4)_3 promoted oxidation of alcohols and trimethylsilyl,tetrahyropyranyl and methoxymethyl ethers with Cu(NO_3)_2·3H_2O in the absence of solvent

V(HSO_4)_3 has been found to be an efficient reagent for the promotion of the oxidation of alcohols and trimethylsilyl, tetrahydropyranyl and methoxymethyl ethers to their corresponding carbonyl compounds with Cu(NO_3)_2·3H_2O in the absence of solvent.     

Theoretical study on the reaction mechanism of CH4 with CaO

The reaction pathways and energetics for the reaction of methane with CaO are discussed on the singlet spin state potential energy surface at the B3LYP/6-311+G(2df,2p) and QCISD/6-311++G(3df,3pd)//B3LYP/6-311+G(2df,2p) levels of theory. The reaction of methane with CaO is proposed to proceed in the following reaction pathways: CaO + CH₄ → CaOCH₄ → [TS] → CaOH + CH₃, CaO + CH₄ → OCaCH₄ → [TS] → HOCaCH₃ → CaOH + CH₃ or [TS] → CaCH₃OH → Ca + CH₃OH, and OCaCH₄ → [TS] → HCaOCH₃ → CaOCH₃ + H or [TS] → CaCH₃OH → Ca + CH₃OH. The gas-phase methane–methanol conversion by CaO is suggested to proceed via two kinds of important reaction intermediates, HOCaCH₃ and HCaOCH₃, and the reaction pathway via the hydroxy intermediate (HOCaCH₃) is energetically more favorable than the other one via the methoxy intermediate (HCaOCH₃). The hydroxy intermediate HOCaCH₃ is predicted to be the energetically most preferred configuration in the reaction of CaO + CH₄. Meanwhile, these three product channels (CaOH + CH₃, CaOCH₃ + H and Ca + CH₃OH) are expected to compete with each other, and the formation of methyl radical is the most preferable pathway energetically. On the other hand, the intermediates HCaOCH₃ and HOCaCH₃ are predicted to be the energetically preferred configuration in the reaction of Ca + CH₃OH, which is precisely the reverse reaction of methane hydroxylation.     

离子液体介质中FeCl3•6H2O催化下芳香醛与5,5-二甲基-1,3-环己二酮的缩合反应

考察了在离子液体1-正丁基-3-甲基咪唑四氟硼酸盐([bmim][BF₄])介质中, 芳香醛与5,5-二甲基-1,3-环己二酮的缩合反应. 实验结果表明, 在催化量的FeCl₃•6H₂O存在下, 该反应可高产率地生成氧杂蒽二酮类化合物3; 而在TMSCl/FeCl₃•6H₂O复合催化体系的催化下, 则得到氧杂蒽二酮类化合物的开环衍生物4, 反应具有非常好的选择性. 该论文提供的方法操作简单、产率高、选择性好而且对环境友好. 在反应结束后, 所用催化剂及离子液体都很容易回收, 并能有效重复使用.     

Kinetics of the thermal decomposition of [Co(NH3)6]2(C2O4)3·4H2O

The thermal decomposition of [Co(NH₃)₆]₂(C₂O₄)₃·4H₂O was studied under isothermal conditions in flowing air and argon. Dissociation of the above complex occurs in three stages. The kinetics of the particular stages thermal decomposition have been evaluated. The R_N and/or A_M models were selected as those best fitting the experimental TG curves. The activation energies,E, and lnA were calculated with a conventional procedure and by a new method suggested by Kogaet al. [10, 11]. Comparison of the results have showed that the Arrhenius parameters values estimated by the use of both methods are very close. The calculated activation energies were in air: 96 kJ mol^–1 (R_1.575, stage I); 101 kJ mol^–1 (Ain1.725 stage II); 185 kJ mol^–1 (A _2.9, stage III) and in argon: 66 kJ mol^–1 (A _1.25, stage I); 87 kJ mol^–1 (A _1.825, stage II); 133 kJ mol^–1 (A _2.525, stage III).     

CuFe-SAPO-34分子筛的结构和催化性能研究

采用一步水热合成法,通过调变初始凝胶中的硅铁比,制备系列铜铁含量不同的CuFe-SAPO-34催化剂用于NH₃选择性催化还原NO_x反应（NH₃-SCR）,并采用ICP、XRD、SEM、BET、H₂-TPR等方法对其结构进行表征.结果表明,CuFe-SAPO-34催化剂具有典型的CHA结构,Cu和Fe均处于分子筛载体的离子交换位.当初始凝胶SiO₂/Fe₂O₃=10时,Cu_2.5Fe_3.1-SAPO-34催化剂具有最大的比表面积和孔容.掺杂适量的Fe,可提高活性物种Cu²⁺的比例及其氧化还原性能,显著降低Cu物种的聚集程度.NH₃-SCR反应结果表明,Cu_2.5Fe_3.1-SAPO-34催化剂具有最宽的反应温度窗口.与Cu-SAPO-34相比,Fe的掺杂显著提高了其高温段的催化活性和低温抗水能力,提高了Cu-CHA催化剂在实际应用中的稳定性.     

Viscosity of aqueous NH4Cl and tracer diffusion coefficients of ions,water and non-electrolytes in aqueous NH4Cl,KI, and MgCl2 at 25°C

Viscosities for aqueous NH₄Cl and tracer diffusion coefficients for²²Na⁺,³⁶Cl^–, HTO, and CH₃OH, acetone and dimethylformamide (all¹⁴C-labelled) in NH₄Cl supporting electrolyte are reported for 25°, together with tracer diffusion coefficients for²²Na⁺,³⁶Cl^–, and¹⁴CH₃OH in 1M KI, and for¹⁴CH₃OH in 1M MgCl₂. The diffusion coefficient of HTO in NH₄Cl solutions is slightly larger, for most of the concentration range investigated (0.05 to 4.5 M), than the value for pure water and is almost unaffected by the supporting electrolyte up to about 4M. Similar behavior is shown by CH₃OH, acetone and dimethylformamide in NH₄Cl solutions. Onsager limiting law behavior is approached by Cl^– at NH₄Cl concentrations in the 0.05–0.1M region but at much lower concentrations by Na⁺.     

On the correct spin lattice for the spin-gapped magnetic solid NH4CuPO4·H2O

NH₄CuPO₄·H₂O is a spin-gapped compound that has been described in terms of an isolated antiferromagnetic spin dimer model. To explore the origin of this spin gap, we examined the spin exchange interactions of NH₄CuPO₄·H₂O by performing qualitative spin dimer analysis based on extended Hückel tight binding calculations and also by carrying out quantitative mapping analysis based on first principles density functional theory electronic band structure calculations. Our study indicates that, to a first approximation, the magnetic properties of NH₄CuPO₄·H₂O should be described by an antiferromagnetic and ferromagnetic alternating chain.