Theoretical Studies on Formation Mechanism of Resonance States for Na＋I2→Na^＋ ＋I2^－ System

An extended linear combination of arrangement channels-scattering wave-function(LCAC-SW) quantum scattering dynamic method combined with ab initio quantum chemical calculation was used to study the forma-tion mechanism of the resonance states for the collinear Na I2→Na^ I2^- I^2- ion-pair formation process on At-en-Lanting-Los potential energy surface. The resonance energy and the resonance width or the lifetime for the first resonance peak were calculated. The resonance can be identified as the Feshbach type and the physi-cal interpretation is given. The geometric structure of the resonance state for the title system has been opti-mized.     

LCAC-SW quantum scattering dynamic study on the ion-pair formation process

LCAC-SW method has been extended to study the reaction dynamics for ion-pair formation processes. M X2→-M X2- reaction system involves two potential energy surfaces, i.e., the covalence state (M X2) and the ionic state (M X2-) and their crossing effect. The working equations for calculating state-to-state probability have been derived based on the above two-state model. Satisfied results of collinear state-to-state probabilities for K I2→K I2- ion-pair formation system have been obtained.     

Theoretical Study on the Long-lived Complexes for the Na＋I2 Collision System

For the Na I2 collision system, theoretical study is performed on the QCISD(T) level by using ab initio method. The ab initio potential energy surfaces are got and on them the long-lived complexes are found and optimized. These results verify the crossed molecule beam experimental phenomenon and the detailed geometry structures are given for the first time. The role of the complexes in the reaction path is also described in detail.     

Effect of La_2O_3/γAl_2O_3 Catalyst on the Activation of CH_4 and CO_2 to C_02 Hydrocarbons under Non-equilibrium Plasma

The oxidative coupling of methane (OCM) to C2 hydrocarbons using carbon dioxide as oxidant is an attractive process from environmental point of view. Only a few research papers reported for it1-3. In general, the yield of C2 hydrocarbons was about 6%. This indicated that the method of catalytic activation was unfavorable to the reaction. It is necessary for us to find a new method in order to activate reaction and improve C2 hydrocarbon yield. Non-equilibrium plasma is a cold plasma in…     

Investigation on the gelation behavior of biodegradable poly(butylene succinate) during isothermal crystallization process

The early stage of polymer crystallization may be viewed as physical gelation process,i.e.,the phase transition of polymer from liquid to solid.Determination of the gel point is of significance in polymer processing.In this work,the gelation behavior of poly(butylene succinate)(PBS) at different temperatures has been investigated by rheological method.It was found that during the isothermal crystallization process of PBS,both the storage modulus(G′) and the loss modulus(G″) increase with time,and the rheological response of the system varies from viscous-dominated(G′G″),meaning the phase transition from liquid to solid.The physical gel point was determined by the intersection point of loss tangent curves measured under different frequencies.The gel time(t_c) for PBS was found to increase with increasing crystallization temperature.The relative crystallinity of PBS at the gel point is very low(2.5%-8.5%) and increases with increasing the crystallization temperature.The low crystallinity of PBS at the gel point suggests that only a few junctions are necessary to form a spanning network,indicating that the network is"loosely"connected,in another word,the critical gel is soft.Due to the elevated crystallinity at gel point under higher crystallization temperature,the gel strength S_g increases, while the relaxation exponent n decreases with increasing the crystallization temperature.These experimental results suggest that rheological method is an effective tool for verifying the gel point of biodegradable semi-crystalline polymers.     

三元体系KCl-SrCl_2-H_2O 25℃相平衡研究

Phase equilibria in the ternary system KCl-SrCl2-H2O at 25 ℃ was studied by using the isothermal method. Density and refractive index of the solution were also determined. The phase diagram was plotted according to the experimental data. In the equilibrium phase diagram of KCl-SrCl2-H2O, there is one invariant point, two univariant curves and two regions of crystallization: KCl and SrCl2·6H2O. In the invariant point, the composition of the liquid phase (mass fraction, wB) was wKCl 7.22%, wSrCl232.31%, the solid phase was KCl and SrCl2·6H2O. Neither double salts nor solid solutions between KCl and SrCl2·6H2O were found, and dehydration of SrCl2·6H2O didn′t occur in the system. The system is a simple eutectic type.     

Theoretical Study on the Mechanism of VO2^＋ ＋ H2 Reaction in the Gas Phase

The mechanism of VO2+ + H2 reaction in the gas phase was investigated by using density functional theory (DFT) at the CCSD//B3LYP/6-311G(2d, p) level. According to our calculation results, the different reaction mechanisms were found for the singlet and triplet potential energy surfaces (PESs). Especially, the crossing points (CPs) among different PESs were located by means of the intrinsic reaction coordinate (IRC) approach presented by Yoshizawa et al., and the structures and energies of the corresponding minimum energy crossing points (MECPs) were obtained by the mathematical algorithm proposed by Harvey et al. Finally, the frontier molecular orbital (FMO) interaction analyses about MECP1 and MECP2 were used to prove our calculation results.     

Application of Fe2O3/Al2O3 Composite Particles as Oxygen Carrier of Chemical Looping Combustion

Chemical looping combustion (CLC) of carbonaceous compounds has been proposed, in the past decade, as an efficient method for CO2 capture without cost of extra energy penalties. The technique involves the use of a metal oxide as an oxygen carrier that transfers oxygen from combustion air to fuels. The combustion is carried out in a two-step process: in the fuel reactor, the fuel is oxidized by a metal oxide, and in the air reactor, the reduced metal is oxidized back to the original phase. The use of iron oxide as an oxygen carrier has been investigated in this article. Particles composed of 80 wt% Fe2O3, together with Al2O3 as binder, have been prepared by impregnation methods. X-ray diffraction (XRD) analysis reveals that Fe2O3 does not interact with the Al2O3 binder after multi-cycles. The reactivity of the oxygen carrier particles has been studied in twenty-cycle reduction-oxidation tests in a thermal gravimetrical analysis (TGA) reactor. The components in the outlet gas have been analyzed. It has been observed that about 85% of CH4 converted to CO2 and H2O during most of the reduction periods. The oxygen carrier has kept quite a high reactivity in the twenty-cycle reactions. In the first twenty reaction cycles, the reaction rates became slightly higher with the number of cyclic reactions increasing, which was confirmed by the scanning electron microscopy (SEM) test results. The SEM analysis revealed that the pore size inside the particle had been enlarged by the thermal stress during the reaction, which was favorable for diffusion of the gaseous reactants into the particles. The experimental results suggested that the Fe2O3/Al2O3 oxygen carrier was a promising candidate for a CLC system.     

Studies on Phase Behavior of Alkyl Polyglucoside Based on Microemulsions with Modified Fishlike Phase Diagram

The three-phase behavior in the quaternary system of an alkyl (C8/10^- or C12/14^-)polyglucoside / 1-butanol / n-octane / water has been studied at 40℃ with the modified fishlike phase diagram, which is presented by us for the first time. The mass fraction of 1-butanol in the hydrophile-lipophile balanced interfacial layer, A^S, the coordinates of the start point B and the end point E of the phase diagram, and the solubilities of alkyl polyglucoside and 1-butanol in n-octane phase were calculated. The solubilization of the microemulsion was also discussed.     

Growth,Structure,and Spectroscopic Characteristics of the Nd^3＋：LiGd（WO4）2 Crystal

The Nd3+:LiGd(WO4) 2 crystal with dimensions of 25mm×28mm×16mm was grown by the top-seeded solution growth method from the 60 mol% Li2W2O7 flux. LiGd(WO4) 2 crystallizes in the tetragonal system with space group I41/a(C4h6) and cell parameters: a = 5.1986 and c = 11.2652 . The hardness is about 5.0 Mohs' scale. The specific heat is 0.40 J·g-1·K-1 at 50 oC. The thermal expansion coefficients for a-and c-axes are 1.314×10-5 and 2.052×10-5 K-1,respectively. The room-temperature polarized absorption and emission spectra and the fluorescence decay curve was measured. The parameters of oscillator strengths,the spontaneous transition probabilities,the fluorescence branching ratios,the radiative lifetimes,and the emission cross sections have been investigated based on Judd-Ofelt theory and Füchtbauer-Ladenburg method. The absorption cross-section is 5.19×10-20 cm2 at 805 nm for π-polarization and its line width is 15 nm;the emission cross section is 1.726×10-19 cm2 at 1060.5 nm for π-polarization. The fluorescence and radiative lifetimes are 86 and 158 μs,respectively. The fluorescence quantum efficiency is 54.43%.     

An Ab initio Theoretical Study on the Nonadiabatic Coupling for Na＋I2 Collision System

The ionic and neutral state potential energy surfaces (PESs) of Na I2 collision system have been calculated on QCISD(T) level by using ab initio method.The location and depth of the potential well,the collision radius and their fine structures have been analyzed at the equilibrium geometry of I2 molecule.The electronic transfer probabilities are also calculated in terms of Landau-Zener model.The lifetime of scattering resonance state is evaluated by the uncertainty principle.All the results have been compared with those obtained according to the Aten-Lanting-Los PES and Feng‘s PES.     

Fuzzy model prediction of Co (III)Al2O3 catalytic behavior in Fischer-Tropsch synthesis

The application of Co(Ⅲ)/Al2O3 catalyst in Fischer-Tropsch synthesis(FTS)was studied in a wide range of synthesis gas conversions and compared with Fuzzy Simulation results.Present study applies fuzzy model to predicting the product composition of CH4,CO2 and CO in Fischer-Tropsch process for natural gas synthesis,in which the input vector was 4-dimension including four variables(operating pressure, operating temperature,time and CO/H2 ratio)of 70 different experiments and the output product is a composition of CO2,CO and CH4. The Mamdani algorithm has been applied to the training of the fuzzy system and the test set was used to evaluate the performance of the system including R2,ARE,AARE and SD.The results demonstrated that the predicted values from the model were in good consistency with the experimental data.The work indicates how fuzzy inference system(FIS),as a promising predicting technique,would be effectively used in FTS.     

Theoretical Study on the Mechanism of the Gas-phase Reaction of Sc＋ with Propargyl Alcohol

In order to elucidate the reaction mechanisms of reaction Sc^＋ with propargyl alcohol (PPA), the triplet potential energy surface for the reactions has been theoretically investigated using a DFT method. The geometries for the reactants, intermediates, transition states and products were completely optimized at B3LYP/DZVP level. The single point energy of each stationary point was calculated at MP4/(6-311＋G** for C, H, O and Lanl2dz for Sc^＋) level. All the transition states were verified by the vibrational analysis and the internal reaction coordinate (IRC) calculations. The present results show that the reaction takes an insertion-elimination mechanism both along the O—H and C—O bond activation branches, but the C—O bond activation is much more favorable in energy than the O—H bond activation. All theoretical results not only support the existing conclusions inferred from early experiment, but also complement the pathway and mechanism for this reaction.     

Catalytic Systems Containing p-Toluenesulfonic Acid for the Coupling Reaction of Formaldehyde and Methyl Formate

The coupling reaction of formaldehyde(FA)and methyl formate(MF)to form methyl glycolate(MG)and methyl methoxy acetate(MMAc),catalyzed by p-toluenesulfonic acid(p-TsOH)as well as assisted by different kinds of solvents or Ni-containing compounds,had been investigated.The results showed that when the reaction was carried out at 140℃,with a molar ratio of FA to MF of 0.65:1, molar fraction of p-TsOH to total feedstock of 11.0%,and reaction time of 3 h,the yield of MG and MMAc was 31.1% and 17.1%,respectively,p-TsOH catalyzed the coupling reaction by means of the synergistic catalysis of protonic acidity and soft basicity.Adding extra solvents to the reaction system was unfavorable for the reaction.The composite catalytic system consisting of p-TsOH and NiX_2(X=Cl,Br,I)exhibited a high catalytic performance for the coupling reaction,and NiX_2 acted as a promoter in the reaction,whose promotion for the catalysis increased in the following order:NiCl_2相似文献   

阿莫西林与维多利亚蓝B的显色反应及应用

The color reaction of amoxicillin with victoria blue B was studied.A novel visible spectrophotometric method for the determination of amoxicillin has been established.Under pH 8.50～10.5 condition,victoria blue B reacteds with amoxicillin to form red ion association complex.The maximum absorption wavelength was at 630nm and the apparent molar absorptivity(ε) was 2.67×10~4 L·mol~(-1)·cm~(-1) and the linear ranges was 0～5.5 mg·L~(-1).Amoxicillin obey Beer's law in definite concentration range.The optimum reaction conditions and the methodological precision were studied simultaneity.The method was simple and rapid and sensitive for the determination of amoxicillin.This method has been applied to the determination of amoxicillin is in the city sell amoxicillin medicament is in point and average recovery at 98.2%～101.0%.     

Does the molecular structure of CaH2 affect the dihydrogen bonding in CaH2 … HY (Y = CH3, C2H3, C2H, CN, and NC) complexes? A quantum chemistry study using MP2 and B3LYP methods

Second-order M ller-Plesset(MP2) and density functional theory(DFT) calculations have been carried out in order to investigate the structures and properties of dihydrogen-bonded CaH 2 HY(Y = CH 3,C 2 H 3,C 2 H,CN,and NC) complexes.Our calculations revealed two possible structures for CaH 2 in CaH 2 HY complexes:linear(I) and bent(II).The bond lengths,interaction energies,and strengths for H H interactions obtained by both MP2 and B3LYP methods are quite close to each other.It was found that the interaction energy decreases with increasing electron density at the Ca-H bond critical point.Atom-in-molecule(AIM) results show that for all of Ca-H H-Y interactions considered here,the Laplacian of the electron density at the H H bond critical point is positive,indicating the electrostatic nature of these Ca-H H-Y dihydrogen bonded systems.     

A Convenient Method for Chlorination in Allylic Position

A convenient method for the chlorination in allylic position was developed by using the aqueous solution of sodium hypochlorite(2%-5% active chlorine) and an acid as chlorination reagent in a diphase system.The method has the advantage of cheap reagents, mild reaction conditions and good yields. The quantity and the feeding rate of the chlorination reagent can be controlled easily. The method is particularly suitable for the chlorination in laboratories.     

Simulation and energy performance assessment of CO2 removal from crude synthetic natural gas via physical absorption process

The paper presents an energy performance assessment of CO2 removal for crude synthetic natural gas (SNG) upgrade by Selexol absorption process. A simplified process simulation of the Selexol process concerning power requirement and separation performance was developed. The assessment indicates that less pressure difference between crude SNG and absorption pressure favors the energy performance of CO2 removal process. When both crude SNG and absorption pressures are 20 bar, CO2 removal process has the best energy performance. The optimal specific power consumption of the CO2 removal process is 566 kJ/kg CO2 . The sensitivity analysis shows that the CO2 removal efficiency would significantly influence the total power consumption of the removal process, as well as higher heating value (HHV) and CO2 content in SNG. However, the specific power consumption excluding crude SNG and SNG compressions changes little with the variance of CO2 removal efficiency. If by-product CO2 is compressed for CO2 capture, the process would turn into a CO2 -sink for the atmosphere. Correspondingly, an increase of 281 kJ/kg CO2 in specific power consumption is required for compressing the separated CO2 .     

The Standard Association Constant of Ion Pair [GaCl]^2＋ in the Sysem of HCl＋GaCl3＋H2O

The standard association constants of ionic pair [GaCl]^2 ,Kas,were determined by emf (electromotive force) method at 278.15 to 318.15K. The thermodynamic quantities for the ionic association process were calculated and it was pointed that the association entropy is driving force to form the ionic pair.     

四元交互体系Li^＋,K^＋／cL^—,CO^2—3—H2O在298K时相平？…

Zabuye Saline Lake, Tibet, China, is unrivalled in the world for its very high salinity, in particular, for the very high concentration of ions of lithium, potassium, and boron in the brine. It belongs to alkaline and carbonate-borate-type salt lake. As a part of the study on phase equilibrium of the 6component subsystem Li+, Na+, K+/C1-, CO2-3, B4O2-7-H2O of the brine system, a study on the reciprocal quaternary system Li+, K+/C1-, CO32-H2O at 298 K was done with isothermal dissolution equilibrium method in the present work. The phase equilibrium of the reciprocal quaternary system Li+,K+/C1, CO2-3-H2O at 298 K was studied with isothermal dissolution method in this work. The physicochemistry properties of the corresponding equilibrium solutions such as densities, viscosities, refractive index, conductivities and pH value were determined. The dried salt diagram of the system consists of four crystallization fields (KC1, Li2CO3, LiCI·H2O, K2CO3·3/2H2O) and five isothermal solubility curves.There are no double slat or solid solution found. Pitzer′s model of the electrolyte solution theory was used for parameterization from the results of solubility determination for subsystems and the prediction of solubilities for the reciprocal quaternary system was made. The solubility data of the experiment are in agreement with those calculated.