铵盐水溶液与金属镁的反应

本文通过实验,讨论了铵盐水溶液和金属镁反应的化学反应实质,并从热力学——化学反应的自发性、动力学——化学反应速度两个方面探讨了铵盐对镁与水反应的影响。

Fluidized-bed chlorination thermodynamics and kinetics of Kenya natural rutile ore

Natural rutile and gaseous chlorine with carbon as reductant were used to prepare titanium tetrachloride. Thermodynamics and kinetics of chlorination of Kenya natural rutile particles in a batch-type fluidized bed were studied at 1173-1273 K. Thermodynamic analysis of this system revealed that the equation of producing CO was dominant at high temperatures. Based on the gas-solid multi-phase reaction theory and a two-phase model for the fluidized bed, the mathematical description for the chlorination reaction of rutile was proposed. The reaction parameters and the average concentration of gaseous chlorine in the emulsion phase were estimated. The average concentration of emulsion phase in the range of fluidized bed was calculated as 0.3 mol/m^3. The results showed that the chlorination of natural rutile proceeded principally in the emulsion phase, and the reaction rate was mainly controlled by the surface reaction.

基于聚合反应机理的膨胀型高聚物浆液平面裂隙注浆仿真方法研究

现行高聚物浆液裂隙注浆扩散模拟方法多采用浆液密度变化经验表达式进行计算,这种简化处理方法没有考虑浆液内在的化学反应驱动机制,其求解结果与实际情况存在较大偏差。为解决这一问题,基于计算流体动力学理论,考虑浆液聚合反应机理,建立了描述高聚物浆液在平面裂隙中流动扩散过程的“化学反应-流体动力学”模型,用龙格库塔方法求解化学反应动力学方程,用平面裂隙注浆准三维模型离散流动控制方程,用SIMPLE算法实施迭代控制,实现了对浆液化学反应、温度场、流场的耦合求解。在此基础上,对绝热条件下高聚物浆液在平面裂隙中的扩散过程进行了数值模拟,分析了浆液组分反应转化率、温度、扩散范围、密度、压力等随时间变化规律,结果表明:伴随浆液化学反应进程,其组分转化率、温度逐渐增大,浆液扩散范围、密度变化表现出明显的阶段性特征;浆液密度随时间经历缓慢减小、急剧下降、逐渐趋缓三个阶段,与此相对应,其扩散范围最初平稳增加,随后快速扩大,最终趋于稳定,其压力则呈现缓慢增大、急剧上升、逐渐下降的三阶段变化特征。所开展工作为深入研究温度、压力等因素对浆液扩散行为的影响奠定了基础。

Hydrodynamic Instabilities Driven by Acid-base Neutralization Reaction in Immiscible System

The hydrodynamic instabilities driven by an acid-base neutralization reaction, in contact along a plane interface, placed in a Hele-Shaw cell under the gravitational field are reported. The system consists of the heavier aqueous tetramethyle-ammonium hydroxide below the lighter layer of organic phase with propionic acid as reacting specie. The effect of chemical composition on hydrodynamic instabilities during interfacial mass transfer accompanied by a neutralization reaction is investigated. Depending on the initial concentration of the reacting species, Marangoni convection in the form of roll ceils or trains of waves is observed. Mach- Zehnder interferometer is used to measure the change in base concentration at the time of instability formation. The results show that the instabilities resulted from the convection flow are more efficient to the mechanism of mass transfer and can drastically alter pattern formation in the system.

Complexation extraction of scheelite and transformation behaviour of tungsten-containing phase using H_(2)SO_(4) solution with H_(2)C_(2)O_(4) as complexing agent

The extraction of tungsten from scheelite was carried out using a sulfuric acid solution with oxalic acid as the chelating agent.Tungsten was obtained in the form of highly soluble hydrogen aqua oxalato tungstate H_(2)[WO_(3)(C_(2)O_(4))·H_(2)O] during the leaching process,while calcium remained in the residue as calcium sulfate dihydrate(CaSO4·2H2O).About 99.2%of the tungsten was leached at 70℃,1.5 mol/L sulfuric acid,1 mol/L oxalic acid,a liquid/solid ratio of 25:1(mL/g),an oxalic acid to sulfuric acid molar ratio of 1:1,a stirring speed of 300 r/min and a leaching time of 2 h.H_(2)[WO_(3)(C_(2)O_(4))·H_(2)O]was thermally decomposed into tungstic acid(H_(2)WO_(4)),and tungsten trioxide(WO_(3))was directly produced by calcining H_(2)WO_(4) at 700℃ for 2 h.The surface chemical reaction was determined to be the controlling step during tungsten leaching,and the apparent activation energy was calculated to be 51.43 kJ/mol.

Kinetic study on reactive extraction of phenylalanine enantiomers with BINAP-copper complexes

Enantioselective liquid–liquid extraction has attracted considerable attention for its potential use in largescale production. Kinetic data are needed for the reliable scale-up of the process. This paper reports the kinetic study of reactive extraction of phenylalanine(Phe) enantiomers with BINAP–copper complex(BINAP–Cu) as a chiral selector. The theory of extraction accompanied by a chemical reaction was applied.The effects of agitation speed, interfacial area, p H value of aqueous phase, initial concentration of Phe enantiomers and initial concentration of BINAP–Cu on the specific rate of extraction were investigated. The forward rate constants of the reactions in the reactive extraction process are 7.93 × 10-5m5/2·mol-1/2·s-1for D-Phe and 1.29 × 10-4m5/2·mol-1/2·s-1for L-Phe.

Diffusion-controlled Adsorption Kinetics at Air/Solution Surface Studied by Maximum Bubble Pressure Method

In studying the diffusion-controlled adsorption kinetics of aqueous surfactant solutions at the air/solution surface by means of the maximal bubble pressure method, Fick's diffusion equation for a sphere should be used. In this paper the equation was solved by means of Laplace transformation under different initial and boundary conditions. The dynamic surface adsorption F(t) for a surfactant solution, which was used to describe the diffusion-controlled adsorption kinetics at the solution surface, was derived. Different from the planar surface adsorption, the dynamic surface adsorption F(t) for the short time consists of two terms: one is the same as Ward-Tordai equation and the other reflects the geometric effect caused by the spherical bubble surface. This effect should not be neglected for the very small radius of the capillary. The equilibrium surface tension γeq and the dynamic surface tension γ(t) of aqueous C10E6 [CH3(CH2)9(OCH2CH2)6OH] solution at temperature 25℃ were measuredby means of Wilhelmy plate method and maximal bubble pressure method respectively. As t→ 0, the theoreticalanalysis is in good agreement with experimental results and the dependence of γ(t) on is linear.

Degradation of microcystin-RR in water by chlorine dioxide

Due to the potent hepatotoxicity and tumor-promoting activity of microcystins, a successful removal of these toxins during drinking water treatment processes is of increasing concem. The oxidation kinetics of MC-RR by chlorine dioxide （ClO2） was studied with HPLC and characterization of the reaction products was performed with UV-spectrometry, TOC and LC-MS. Our experimental results show that the oxidation process is a second order overall and a first order with respect to ClO2 and MC-RR. The activation energy of MC-RR degradation by ClO2 is 53.07 kJ/mol. The rate constant k of the action can be increased by increasing temperature and decreasing pH value and ranged from 6.11 × 10^2 L/（mol.min） to 5.29× 10^2 L/（mol-min） at pH from 3.44 to 10.41 at 10℃. Reaction products were determined to be organic and volatile, because they could be almost removed from aqueous solution by heating for 15 min at 60 ~C. In addition, the main oxidation products have m/z values of 1072 and are identified as dihydroxy isomers of MC-RR.

Magneto-hydrodynamic flow of squeezed fluid with binary chemical reaction and activation energy

The present exploration is conducted to describe the motion of viscous fluid embedded in squeezed channel under the applied magnetics effects.The processes of heat and mass transport incorporate the temperature-dependent binary chemical reaction with modified Arrhenius theory of activation energy function which is not yet disclosed for squeezing flow mechanism.The flow,heat and mass regime are exposed to be governed via dimensionless,highly non-linear,ordinary differential equations (ODEs) under no-slip walls boundary conditions.A well-tempered analytical convergent procedure is adopted for the solutions of boundary value problem.A detailed study is accounted through graphs in the form of flow velocity field,temperature and fluid concentration distributions for various emerging parameters of enormous interest.Skin-friction,Nusselt and Sherwood numbers have been acquired and disclosed through plots.The results indicate that fluid temperature follows an increasing trend with dominant dimensionless reaction rate σ and activation energy parameter E.However,an increment in σ and E parameters is found to decline in fluid concentration.The current study arises numerous engineering and industrial processes including polymer industry,compression and injection shaping,lubrication system,formation of paper sheets,thin fiber,molding of plastic sheets.In the area of chemical engineering,geothermal engineering,cooling of nuclear reacting,nuclear or chemical system,bimolecular reactions,biochemical process and electrically conducting polymeric flows can be controlled by utilizing magnetic fields.Motivated by such applications,the proposed study has been developed.

Photochemical reactions of poly(3-butoxythiophene-2,5-diyl) with chloroform

Photochemical reactions of poly(3-butoxythiophene-2,5-diyl) with chloroform under irradiation with light were studied. The reactions were separately carried out under air, oxygen, and nitrogen. The obtained results showed that this reaction belongs to the pseudo-first-order reaction with a rate constant kobs of 1.4×10?5 s?1 at room temperature. The presence or absence of air, oxygen, and nitrogen did not have obvious effects on the reaction rate under irradiation with light.

Prediction of pyrolysis kinetic parameters from biomass constituents based on simplex-lattice mixture design

The aim of this study is to determine the effect of the main chemical components ofbiomass： cellulose, hemicel- lulose and lignin, on chemical kinetics ofbiomass pyrolysis. The experiments were designed based on a simplex- lattice mixture design. The pyrolysis was observed by using a thermogravimetric analyzer. The curves obtained from the employed analytical method fit the experimental data （R2 〉 0.9）. This indicated that this method has the potential to determine the kinetic parameters such as the activation energy （E~）, frequency factor （A） and re- action order （n） for each point of the experimental design. The results obtained from the simplex-lattice mixture design indicated that cellulose had a significant effect on Ea and A, and the interaction between cellulose and lignin had an important effect on the reaction order, n. The proposed models were then proved to be useful for predicting pyrolysis behavior in real biomass and so could be used as a simple approximation for predicting the overall trend of chemical reaction kinetics.

Differential Cross Sections and Collision-Induced Rotational Alignment in Inelastic Scattering of NO(X)by Xe

Fully A-doublet resolved differential cross sections and collision-induced rotational alignment moments have been measured for the NO(X)-Xe collision system at a collision energy of 519 cm^-1.The experiments combine initial quantum state selection,employing a hexapole inhomogeneous electric field,with quantum state resolved detection,using(1+1')resonantly enhanced multiphoton ionization and velocity map ion imaging.The differential cross sections and polarization dependent differential cross sections are shown to agree well with quantum mechanical scattering calculations performed on ab initio potential energy surfaces[J.Klos et al.J.Chem.Phys.137,014312(2012)].By comparison with quasi-classical trajectory calculations,quantum mechanical scattering calculations on a hard-shell potential,and kinematic apse model calculations,the effects of the attractive part of the potential on the measured differential cross sections and collision-induced rotational alignment moments are assessed.

Synthesis of 1-(5-nitro-3-benzopseudothiazolyl)-3-(4-phenylazophenyl)-triazene and Its Color Reaction with Cobalt

A new chromogenic reagent, 1 -（5 - nitro- 3 - benzopsendothiazde）- 3 -（4 - phenylazophenyl） - triazene （NBPTPAPT） has been synthesized and used as a sensitive reagent for the spectrophotometric determination of cobalt. In the presence of Tween - 80, the reagent with Co （ Ⅱ ） forms a yellow complex （1 ： 2） in the buffer solution of Na2B4O7 - NaOH at pH 10.54. The apparent molar absorptivity is 1.220× 10^5 L· mol^- 1· cm^- 1 with the linear range of 0 - 240μg/ L for Co （Ⅱ） by dual-wavelength spectrophotometry. Trace cobalt in vitamin B12 and tea samples has been determined with satisfactory results.

Surface Photocatalysis-TPD Spectrometer for Photochemical Kinetics

A surface photocatalysis-TPD apparatus devoted to studying kinetics and mechanism of pho- tocatalytic processes with various signal crystal surfaces has been constructed. Extremely high vacuum （-0.2 nPa） in the ionization region is obtained by using multiple ultrahigh vacuum pumps. Compared with similar instruments built previously by others~ the H2, CH4 background in the ionization region can be reduced by about two orders of magnitude, and other residual gases in the ionization region can be reduced by about an order of magnitude. Therefore, the signal-to-noise ratio for the temperature programmed desorption （TPD） and time of flight （TOF） spectra is substantially enhanced, making experimental studies of pho- tocatalytic processes on surfaces much easier. In this work, we describe the new apparatus in detail and present some preliminary studies on the photo-induced oxygen vacancy defects on TiO2（110） at 266 nm by using the TPD and TOF methods. Preliminary results suggest that the apparatus is a powerful tool for studying kinetics and mechanism of photochemical processes.

初始种子电子团对短空气间隙流注放电行为的影响

流注放电过程中初始种子电子团的形成数量及位置具有随机性,为揭示初始种子电子团对流注放电行为的影响,建立流体动力学-化学反应混合模型,数值仿真大气压下棒-板间隙为5 mm的流注放电过程。模型包括电子、正负离子连续性方程、电子平均能量方程和电场的泊松方程以及23种粒子间化学反应。分别在模型中对密度峰值和分布位置预设置3个不同数值,研究初始种子电子团密度峰值和分布位置对空气间隙流注放电行为的影响。结果表明:初始种子电子团密度峰值的增加只会加速流注的形成,不会影响流注的时空变化规律;而分布位置的改变会影响流注的时空发展特性,初始位置与棒电极的距离越远,形成的流注到达板电极的时间愈短。

The Kinetics for Electrochemical Removal of Ammonia in Coking Wastewater

Electrochemical removal of ammonia is a new and effective method in coking wastewater.The reaction mechanism of ammonia removal was proved by stable polarization curve in this paper.First,the supposing of reaction steps of the electrode were proposed.And then reaction parameter of the electrode was measured by Tafel curve.Finally,the reaction mechanism was determined by quasi-equilibrium approach.The results showed that Cl2+H2O→HOCl+H++Cl was the rate-determining step,the calculated apparent transfer coefficient was uniform to the experimental value.

Modeling of Soot Formation in Gas Burner Using Reduced Chemical Kinetics Coupled with CFD Code

A computational study of soot formation in ethylene/air coflow jet diffusion flame at atmospheric pres-sure was conducted using a reduced mechanism and soot formation model. A 20-step mechanism was derived from the full mechanism using sensitivity analysis,reaction path analysis and quasi steady state(QSS) approximation. The model in premixed flame was validated and with computing savings in diffusion flame was applied by incor-porating into a CFD code. Simulations were performed to explore the effect of coflow air on flame structure and soot formation. Thermal radiation was calculated by a discrete-ordinates method,and soot formation was predicted by a simple two-equation soot model. Model results are in good agreement with those from experiment data and detailed mechanism at atmospheric conditions. The soot nucleation,growth,and oxidation by OH are all enhanced by decrease in coflow air velocity. The peak soot volume fraction region appears in the lower annular region be-tween the peak flame temperature and peak acetylene concentration locations,and the high soot oxidation rate due to the OH attack occurs in the middle annular region because of high temperature.

Gel time of calcium acrylate grouting material

Calcium acrylate is a polymerized grout, and can polymerize in an aqueous solution. The polymerization reaction utilizes ammonium persulfate as a catalyst and sodium thiosulfate as the activator. Based on the theory of reaction kinetics, this study on the relation between gel time and concentration of activator and catalyst showed that gel time of calcium acrylate is inversely proportional to activator and catalyst concentration. A formula of gel time is proposed, and an example is provided to verify the proposed formula.

Kinetic Studies on Wheat Straw Hydrolysis to Levulinic Acid

Levulinic acid is considered as a promising green platform chemical derived from biomass.The kinetics of levulinic acid accumulation in the hydrolysis process of wheat straw was investigated in the study.Using dilute sulfuric acid as a catalyst,the kinetic experiments were performed in a temperature range of 190-230°C and an acid concentration range of 1%-5% (by mass) .A simple model of first-order series reactions was developed,which provided a satisfactory interpretation of the experimental results.The kinetics of main intermediates including sugar and 5-hydroxymethylfurfural(5-HMF) were also established.The kinetic parameters provided useful information for understanding the hydrolysis process.

Statistical deduction and experimental verification on kinetic equations for the curing reactions of epoxy resins/amines

Based on three typical mechanisms (second-order, third-order and competitive mechanisms) for the curing reactions of the epoxy resins with amines, a pair of the kinetic equations (for primary and secondary aminations) was presented to explain the uniformity and relationship among the three different kinetic mechanisms of the reactions. The presented macro-equations were deduced from the kinetic micro-equations by the statistics method. And the constitutive equations were verified by experimental data at different reaction times and temperatures (95°C, 60°C and 39°C), taking diglycidyl ether of bisphenol A (DGEBA) /ethyleneamine (EA) as a model.