Acid-rock reaction kinetics in a two-scale model based on reaction order correction

The reaction order plays a crucial role in evaluating the response rate of acid-rock.However,the conventional two-scale model typically assumes that the reaction order is constant as one,which can lead to significant deviations from reality.To address this issue,this study proposes a novel multi-order dynamic model for acid-rock reaction by combining rotating disk experimental data with theoretical derivation.Through numerical simulations,this model allows for the investigation of the impact of acidification conditions on different orders of reaction,thereby providing valuable insights for on-site construction.The analysis reveals that higher response orders require higher optimal acid liquid flow rates,and lower optimal H+diffusion coefficients,and demonstrate no significant correlation with acid concentration.Consequently,it is recommended to increase the displacement and use high-viscosity acid for reservoirs with high calcite content,while reducing the displacement and using low-viscosity acid for reservoirs with high dolomite content.

Calcite Dissolution in Deionized Water from 50℃ to 250℃ at 10 MPa:Rate Equation and Reaction Order

Carbonate minerals and water （or geofluids） reactions are important for modeling of geochemical processes and have received considerable attention over the past decades. The calcite dissolution rates from 50℃ to 250℃ at 10 MPa in deionized water with a flow rate varying from 0.2 to 5 mL/min were experimentally measured in a continuous flow column pressure vessel reactor. The dissolution began near the equilibrium with c/ceq 〉 0.3 and finally reached the equilibrium at 100℃-250℃, so the corresponding solubility was also determined as 1.87, 2.02, 2.02 and 1.88×10^-4.mol/L at 100℃, 150℃, 200℃ and 250℃ respectively, which was first increasing and then switching to decreasing with temperature and the maximum value might occur between 150℃ and 200℃. The experimental dissolution rate not only increased with temperature, but also had a rapid increase between 150℃ and 200℃ at a constant flow rate of 4 mL/min. The measured dissolution rates can be described using rate equations of R = k（1-c/ceq）n or R = kc-n. In these equations the reaction order n changed with temperature, which indicates that n was a variable rather than a constant, and the activation energy was 13.4 kJ/mol calculated with R = k（1-c/ceq）n or 18.0 kJ/mol with R = kc^-n, which is a little lower than the surface controlled values. The varied reaction order and lower activation energy indicates that calcite dissolution in this study is a complex interplay of diffusion controlled and surface controlled processes.

A Study on the Kinetics of the Catalytic Reforming Reaction of CH4 with CO2: Determination of the Reaction Order

The kinetics of the catalytic reforming reaction of methane with carbondioxide to produce synthesis gas on a Ni/α-Al_2O_3 and a HSD-2 type commercial catalyst has beenstudied. The results indicate that the reaction orders are one and zero for methane and carbondioxide, respectively, when the carbon dioxide partial pressure was about 12.5-30.0 kPa and thetemperature was at 1123-1173 K. However, when the carbon dioxide partial pressure was changed to30.0-45.0 kPa under the same temperature range of 1123-1173 K, the reaction orders of methane andcarbon dioxide are one. Furthermore, average rate constants at different temperatures weredetermined.

A NEW APPROACH TO THE EQUATIONS FOR THE STEADY STATE CURRENTS AT MICROELECTRODES:EC'PROCESSES(SECOND ORDER REACTION)

With a new approach,the general current expressions of two typical second order catalytic reactions at microelectrodes are obtained.This allows the study of fast chemical reactions and systems where the reactants are present in similar concentrations.

Sulphur-doped ordered mesoporous carbon with enhanced electrocatalytic activity for the oxygen reduction reaction

Metal-free, heteroatom functionalized carbon-based catalysts have made remarkable progress in recent years in a wide range of applications related to energy storage and energy generation. In this study, high surface area mesoporous ordered sulphur doped carbon materials are obtained via one-pot hydrothermal synthesis of carbon/SBA-15 composite after removal of in-situ synthesized hard template SiO2. 2-thiophenecarboxy acid as sulphur source gives rise to sulphur doping level of 5.5 wt%. Comparing with pristine carbon, the sulphur doped mesoporous ordered carbon demonstrates improved electro-catalytic activity in the oxygen reduction reaction in alkaline solution. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

MATHEMATICAL MODEL FOR THERMOKINETICS OF IRREVERSIBLE CONSECUTIVE FIRST ORDER REACTIONS

The mathematical model for the thermokinetics of irreversible consecutive first order reactions has been suggested,which was used for the calculation of rate constants and molar enthalpies of the two consecutive steps.And its validity has been verified by the ex- perimental results.

Casson Nanofluid Flow with Cattaneo-Christov Heat Flux and Chemical Reaction Past a Stretching Sheet in the Presence of Porous Medium

In the current work,inclined magnetic field,thermal radiation,and the Cattaneo-Christov heat flux are taken into account as we analyze the impact of chemical reaction on magneto-hydrodynamic Casson nanofluid flow on a stretching sheet.Modified Buongiorno’s nanofluid model has been used to model the flow governing equations.The stretching surface is embedded in a porousmedium.By using similarity transformations,the nonlinear partial differential equations are transformed into a set of dimensionless ordinary differential equations.The numerical solution of transformed dimensionless equations is achieved by applying the shooting procedure together with Rung-Kutta 4th-order method employing MATLAB.The impact of significant parameters on the velocity profile f(ζ),temperature distributionθ(ζ),concentration profileϕ(ζ),skin friction coefficient(Cf),Nusselt number(Nux)and Sherwood number(Shx)are analyzed and displayed in graphical and tabular formats.With an increase in Casson fluid 0.5<β<2,the motion of the Casson fluid decelerates whereas the temperature profile increases.As the thermal relation factor expands 0.1<γ1<0.4,the temperature reduces,and consequently thermal boundary layer shrinks.Additionally,by raising the level of thermal radiation 1<Rd<7,the temperature profile significantly improves,and an abrupt expansion has also been observed in the associated thermal boundary with raise thermal radiation strength.It was observed that higher permeability 0<K<4 hinders the acceleration of Casson fluid.Higher Brownian motion levels 0.2<Nb<0.6 correspond to lower levels of the Casson fluid concentration profile.Moreover,it is observed that chemical reaction 0.2<γ2<0.5 has an inverse relation with the concentration level of Casson fluid.The current model’s significant uses include heat energy enhancement,petroleum recovery,energy devices,food manufacturing processes,and cooling device adjustment,among others.Furthermore,present outcomes have been found in great agreementwith already publishedwork.

A PRELIMINARY STUDY ON THE THEORY OF THE SECOND AND THIRD ORDER DERIVATIVE ADSORPTION CHRONOPOTENTIOMETRY FOR A REVERSIBLE REACTION

The equations of the second and third order derivative curves of time with respect to potential for a reversible process in adsorption chronopotentiometry are derived and experimentally verified.

Nitrogen-doped cobalt nanoparticles/nitrogen-doped plate-like ordered mesoporous carbons composites as noble-metal free electrocatalysts for oxygen reduction reaction

In this work, nitrogen-doped cobalt nanoparticlesinitrogen-doped plate-like ordered mesoporous carbons (N/Co/OMCs) were used as noble-metal free electrocatalysts with high catalytic efficiency. Compared with OMCs with long channel length, due to more entrances for catalytic target accessibility and a short pathway for rapid diffusion, the utilization efficiency of cobalt nanoparticles inside the plate-like OMCs with short pore length is well improved, which can take full advantage of porous structure in electrocatalysis and increase the utilization of catalysts. The active sites in N/Co/OMCs for oxygen reduction reaction (ORR) are highly exposed to oxygen molecule, which results in a high activity for ORR. By combination of the catalytic properties of nitrogen dopant, incorporation of Co nanoparticles, and structural properties of OMCs, the N/Co/plate-like OMCs are highly active noble-metal free catalysts for ORR in alkaline solution. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

A Second Order Characteristic Mixed Finite Element Method for Convection Diffusion Reaction Equations

A combined approximate scheme is defined for convection-diffusion-reaction equations. This scheme is constructed by two methods. Standard mixed finite element method is used for diffusion term. A second order characteristic finite element method is presented to handle the material derivative term, that is, the time derivative term plus the convection term. The stability is proved and the L2-norm error estimates are derived for both the scalar unknown variable and its flux. The scheme is of second order accuracy in time increment, symmetric, and unconditionally stable.

Higher Order Implicit Scheme for Nonlinear Time-Dependent Convection-Diffusion- Reaction Equation

A mathematical model comprising of nonlinear reaction, diffusion, and convection mechanisms seen in natural and anthropogenic processes is numerically investigated here. It is proposed that a higher order numerical scheme of finite difference method be used in conjunction with an iterative approach in order to solve the nonlinear one dimensional convection-diffusion-reaction equation. To account for the wide variety of physical characteristics and boundary conditions, an iterative approach is presented that yields a reliable and precise solution every time. We examined the accuracy and operational efficiency of two distinct finite difference approaches. The efficiency of the system is determined by comparing the estimated results to the appropriate analytical solution by adhering to established norms. Coherence and convergence were analyzed for each approach. The simulation results demonstrate the efficacy and accuracy of these methods in solving nonlinear convection- diffusion-reaction equations. Convection-diffusion-reaction equation modeling is critical for employing the offered results in heat and mass transport processes.

Effect of montmorillonite on kinetics of polyurethane preparation reaction

The prepolymerization and curing reaction kinetics of polyurethane/montmorillonite have been studied with end group analysis and FTIR respectively. It was found that the prepolymerization and curing reaction followed the 2nd-order kinetics. But the activation energy of prepolymerization increased from 42.7 kJ/mol to 56.5 kJ/rnol after the montmorillonite was added in the reaction system, and activation energy of curing reaction decreased from 64.4 kJ/mol to 17.5 kJ/mol. 2007 Bing Liao. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Effect of order/disorder transformation on the sensitivity to environmental embrittlement of intermetallics

The mechanism involving the effect of disorder/order transformation on the environmental embrittlement in gaseous H2 is summarized. It is shown that there is no hydrogen embrittlement in disordered state of Kurnakov type intermetallics in gaseous H2. However, the H2-induced environmental embrittlement for the ordered alloy having identical chemical composition becomes severer as the degree of the order increases. The results of testing on the ion gage turned on and off during tensile testing show that the more sensitive to H2-induced hydrogen embrittlement for ordered alloy than disordered one is attributed to the fact that atomic ordering may accelerate the kinetics of the catalytic reaction to produce more atomic hydrogen. The results on simultaneous hydrogen charging show that disordered alloys embrittled as hydrogen atoms are forced into the material implying that the embrittlement of ordered alloy in gaseous H2 is also due to the acceleration of the kinetics of catalytic reaction. The above suggestion was further verified by the adsorption tests of Ni3Fe intermetallics powder. It is shown that the amount of chemically adsorbed hydrogen in ordered state is significantly larger than that adsorbed by the disordered alloy, indicating that the more sensitive to H2-induced embrittlement in the ordered state of alloy is essentially due to the accelerated catalytic reaction.

Computer Data Processing of the Hydrogen Peroxide Decomposition Reaction

Two methods of computer data processing, linear fitting and nonlinear fitting, are applied to compute the rate constant for hydrogen peroxide decomposition reaction. The results indicate that not only the new methods work with no necessity to measure the final oxygen volume, but also the fitting errors decrease evidently.

Research on charge ordering and magnetic properties in La_(0.3)Ca_(0.7)Mn_(1-x)W_xO_3 system

The perovskite manganite sample La0.3Ca0.7Mn1-xWxO3 （x = 0.08, 0.12） was prepared by the solid-state reaction method. The effect of W doping on the Mn site to La0.3Ca0.7MnO3 charge ordering phase and the changing process of magnetic properties were studied through the measurement of the M-T curve, M-H curves, and ESR curves of the sample. The results showed that when x = 0.08, the charge ordering （CO） phase exists in the system, the transition temperature Tco= 275 K, and the system exhibits PM when T 〉 275 K. The system transforms from spin-disordering paramagnetism to spin-ordering antiferromagnetism in the charge ordering state with the temperature decreasing from 275 K to 230 K. The long-range antiferromagnetism forms and AFM/CO states coexist between 230 K and 5 K. There is a little ferromagnetic component in the AFM/CO background in a low temperature range. When x = 0.12, the CO phase in the system has almost melted completely. There is a little remnant of the CO phase below 150 K. The system exhibits paramagnetism when T 〉 150 K and transforms from paramagnetism to ferromagnetism when T〈 150 K.

Synthesis, Structure and Third-order Non-linear Optical Properties of Tungsten Dioxo Complex with 8-Hydroxyquinoline Ligand WO_2(C_9H_6NO)_2

Tungsten dioxo complex WO 2(C 9H 6NO) 2 was obtained via the low temperature solid-state reaction of(NH 4) 2WS 4, 8-hydroxyquinoline(8-hq) and(CH 3) 4NI, and it was characterized by means of elemental analyses, IR spectroscopy and X-ray diffraction analysis. The crystal of the title compound belongs to monoclinic, space group C2/c, with the crystal cell parameters: a=1.3316(3) nm, b=0.94444(19) nm, c=1.3485(3) nm, β=109.66(3)°, V=1.5970(6) nm 3, Z=6. The title compound possesses a supramolecular structure formed through hydrogen bonds and π-π stacking interactions. The third-order non-linear optical(NLO) properties of the title compound were also investigated. The third-order non-linear absorption coefficient α 2 and refractive index n 2 are 0.85×10 -11 m/W -1 and -1.5×10 -19 m 2/W, respectively. The third-order non-linear susceptibility χ (3) is 3.03×10 -13 esu for 3.8×10 -5 mol/L sample concentration.

Approximate Solution of Non-Linear Reaction Diffusion Equations in Homogeneous Processes Coupled to Electrode Reactions for CE Mechanism at a Spherical Electrode

A mathematical model of CE reaction schemes under first or pseudo-first order conditions with different diffusion coefficients at a spherical electrode under non-steady-state conditions is described. The model is based on non-stationary diffusion equation containing a non-linear reaction term. This paper presents the complex numerical method (Homotopy perturbation method) to solve the system of non-linear differential equation that describes the homogeneous processes coupled to electrode reaction. In this paper the approximate analytical expressions of the non-steady-state concentrations and current at spherical electrodes for homogeneous reactions mechanisms are derived for all values of the reaction diffusion parameters. These approximate results are compared with the available analytical results and are found to be in good agreement.

S-ZVI处理亚甲基蓝染料废水的好氧实验研究

采用零价铁与Na2S在厌氧条件下制备硫化零价铁(S-ZVI)颗粒,并对其处理亚甲基蓝废水影响因素进行研究。结果表明S-ZVI表面粗糙附有硫化物薄膜,具有壳核结构;S-ZVI颗粒对亚甲基蓝的去除率随着S/Fe比的增加先增加后下降,当S/Fe比为0.025时对亚甲基蓝的去除效果最好,去除率为98.02%,整体反应在150 min基本达吸附平衡,且遵循伪二级动力学反应;在应用S-ZVI去除亚甲基蓝废水时最佳pH在6~8之间。好氧条件对亚甲基蓝的去除率为厌氧的1.46倍,氧的存在有助于提高S-ZVI对亚甲基蓝的去除效果。

高压电缆绝缘低密度聚乙烯交联过程中级数和自催化反应的逆向调控

在保证交联度的前提下提升耐焦烧性能是进一步发展国产高压电缆低密度聚乙烯绝缘料的关键之一。焦烧和交联度本质上是交联反应及其结果的反映,该文基于高分子化学流变学和凝胶理论,提出了绝缘料耐焦烧性能的定量表征方法,结合实验分析和交联反应动力学模型,首次全面探讨了交联反应与焦烧和交联度的关联机理,提出了提升耐焦烧性能并保证交联度的优化策略。研究发现,低密度聚乙烯交联过程中有级数反应和自催化反应,低温下级数反应的级数越低,越有利于延缓交联反应,增加凝胶时间,提高耐焦烧性能;而高温下自催化反应的级数越高,越有利于加速交联反应,提高交联度。单一添加剂只能同向改变级数反应和自催化反应的级数,复合添加剂的协同作用则能逆向改变级数反应和自催化反应的级数,从而实现了在保证交联度的前提下提升绝缘料的耐焦烧性能。该研究为推进高压电缆低密度聚乙烯绝缘料国产化提供了重要理论支撑。

氯丁橡胶硫化反应动力学

以1,2-亚乙基硫脲为促进剂、氧化锌和氧化镁为硫化剂对氯丁橡胶进行硫化,采用差示扫描量热法研究了氯丁橡胶的非等温硫化反应动力学,通过Kissinger方程和Crane方程计算了硫化反应的动力学参数,并采用硫化仪法研究了等温硫化反应的动力学,计算了硫化反应热硫化阶段的表观活化能。结果表明,n级动力学模型可以有效描述氯丁橡胶的非等温硫化过程,硫化反应的表观活化能为92.78 kJ/mol,反应级数为0.93;氯丁橡胶的等温硫化过程可以分为焦烧阶段、热硫化阶段和平坦硫化阶段,其中热硫化阶段符合一级反应动力学特征,此时表观活化能为53.38 kJ/mol。