Recent Research Progress of Chemical Reactions under Supercritical Conditions

Chemical reactions (such as hydrogenation, hydroformylation, alkylation, esterification, etc.) at supercritical conditions afford opportunities to manipulate the solubility of reactants and products, to eliminate interphase transport limitations in the reaction systems, and to be beneficial to the environment. This review concentrates on the most recent developments after 2001 with only a brief summary of pioneering research work before 2001.

Numerical simulation of hydrothermal mineralization associated with simplified chemical reactions in Kaerqueka polymetallic deposit, Qinghai, China

The Kaerqueka polymetallic deposit, Qinghai, China, is one of the typical skarn-type polymetallic ore deposits in the Qimantage metallogenic belt. The dynamic mechanism on the formation of the Kaerqueka polymetallic deposit is always an interesting topic of research. We used the finite difference method to model the mineralizing process of the chalcopyrite in this region with considering the field geological features, mineralogy and geochemistry. In particular, the modern mineralization theory was used to quantitatively estimate the related chemical reactions associated with the chalcopyrite formation in the Kaerqueka polymetallic deposit. The numerical results indicate that the hydrothermal fluid flow is a key controlling factor of mineralization in this area and the temperature gradient is the driving force of pore-fluid flow. The metallogenic temperature of chalcopyrite in the Kaerqueka polymetallic deposit is between 250 and 350 ℃. The corresponding computational results have been verified by the field observations. It has been further demonstrated that the simulation results of coupled models in the field of emerging computational geosciences can enhance our understanding of the ore-forming processes in this area.

The application of reed-vibration mechanical spectroscopy for liquids to detect chemical reactions of an acrylic structural adhesive

There remain a number of unsolved problems about chemical reactions, and it is significant to explore new detection methods because they always offer some unique information about reactions from new points of view. For the first time, the solidification course of a modified two-component acrylic structural adhesive is measured by using reed-vibration mechanical spectroscopy for liquids （RMS-L） in this work, and results show that there are four sequential processes of mechanical spectra with time. The in-depth analyses indicate that RMS-L can detect in real-time the generation and disappearance of active free radicals, as well as the chemical cross-link processes in the adhesive. This kind of real-time detection will undoubtedly facilitate the study of the chemical reaction dynamics controlled by free radicals.

Effects of chemical reactions on MHD micropolar fluid flow past a vertical plate in slip-flow regime

Heat and mass transfer effects on the unsteady flow of a micropolar fluid through a porous medium bounded by a semi-infinite vertical plate in a slip-flow regime are studied taking into account a homogeneous chemical reaction of the first order. A uniform magnetic field acts perpendicular to the porous surface absorb micropolar fluid with a suction velocity varying with time. The free stream velocity follows an exponentially increasing or decreasing small perturbation law. Using the approximate method, the expressions for the velocity microrotation, temperature, and concentration are obtained. Futher, the results of the skin friction coefficient, the couple stress coefficient, and the rate of heat and mass transfer at the wall are presented with various values of fluid properties and flow conditions.

Stochastic Thermodynamics of Mesoscopic Electrochemical Reactions

In this work, we discussed the stochastic thermodynamics of mesoscopic electron transfer reactions between ions and electrodes. With a relationship between the reaction rate con- stant and the electrode potential, we find that the heat dissipation βq equals to the dynamic irreversibility of the reaction system minus an internal entropy change term. The total en- tropy change Ast is defined as the summation of the system entropy change As and the heat dissipation/βq such that △st=△s＋βq. Even though the heat dissipation depends linearly on the electrode potential, the total entropy change is found to satisfy the fluctuation theo- rem 〈e-△st 〉=1, and hence a second law-like inequality reads （△st）≥0. Our study provides a practical methodology for the stochastic thermodynamics of electrochemical reactions, which may find applications in biochemical and electrochemical reaction systems.

Numerical Modelling and Simulation of Chemical Reactions in a Nano-Pulse Discharged Bubble for Water Treatment

A zero-dimensional model to simulate a nano-pulse-discharged bubble in water was developed. The model consists of gas and liquid phases corresponding to the inside and outside of the bubble, respectively. The diffusions of chemical species from the gas to the liquid phase through the bubble interface was also investigated. The initial gas is Ar, but includes a little H20 and 02 in the bubble. The time evolution of the OH concentration in the liquid phase was mainly investigated as an important species for water treatment. It was shown that OH was generated in the bubble and then diffused into the liquid. With the application of a continuous nano-pulse discharge, more OH radicals were generated as the frequency increased at a low voltage for a given power consumption.

Cr_2O_3 BASE CERAMIC COATING ON ALUMINUM ALLOYS FORMED BY CHEMICAL REACTIONS

A newly developed method is introduced for producing Cr 2O 3 base ceramic coating on aluminum alloys. On the basis of properly selecting base reactions, slurry is prepared and then applied onto the substrate surface. By chemical reactions taken place in situ on the surface of aluminum alloy at relative low temperature, Cr 2O 3 base ceramic coating is formed. By means of scanning electron microscopy, the coating microstructure and the bonding mechanism are studied. X ray diffraction analysis is also used to investigate the chemical composition of the coating. The coating formation mechanism is further discussed. With a pin on disk tester, wear test is made to evaluate the wear performances of the coating. The results show that by applying the coating on aluminum alloy, the wear decreases 5 times in comparation to that without coating.

Shock Induced Chemical Reactions of Intermetallic Mixture of Nickel and Aluminum and Associated Transition States

In this paper, numerical simulation of shock-induced chemical reactions of intermetallic mixtures is discussed. Specifically, the paper focuses on intermetallic mixture of nickel and aluminum. To initiate the chemical reactions, the thermal input or the shockwave should supply the energy to take the reactants, mixture of nickel and aluminum, to the transition state. Thus, for any numerical simulation or analysis of the shock or thermally induced chemical reaction in a continuum scale or a meso scale, it is necessary to identify the transition state. The transition state for the intermetallic mixture of nickel and the aluminum is identified in this paper and a result of the numerical simulation of the shock-induced chemical reaction, in a continuum scale is presented. The numerical solutions clearly show the chemical reactions, release of heat energy, increase of the temperature and the formation of products, following the transition state and the resulting shock-induced chemical reaction of a binary intermetallic energetic mixture of nickel and aluminum. The studies also show that the collapse of porosity is a mechanism that takes the reactants to the transition state, in shock-induced chemical reactions of binary intermetallic mixtures.

Transition States for Shock Induced Chemical Reactions in Binary Energetic Materials

In this paper, numerical simulation of shock induced chemical reactions of a thermite mixture of binary energetic material, aluminum and iron oxide, are discussed. To initiate the chemical reactions, the impact or the shockwave should supply the energy to take the reactants, aluminum and iron oxide, to the transition state. Thus, for any numerical simulation of the shock or impact induced chemical reaction in a continuum or mesoscale, it is necessary to identify the transition state. The transition state for the thermite mixture, of aluminum and iron oxide, is identified in this paper and a result from a numerical simulation of the shock induced chemical reaction, in a continuum scale is presented.

Linking of Chemical Reactions and Silica Nanoparticle Contact Using Synthetic Helical Molecules

Biological cells exhibit diverse phenomena induced through linking of chemical reactions of molecules and solid surface contact.It is then a significant topic in the field of chemistry to study phenomena induced through this linking using synthetic systems,which can promote our understanding of biological phenomena and can be applied to the development of novel functions.Silica nanoparticles(sNPs),which are synthetic inorganic materials,are attractive for such purposes,because of their following characteristics:they can adsorb large amounts of molecules on their surfaces,they can aggregate through contact between SNPs as well as contact between molecules and SNPs,and the molecules can be easily removed from solutions by precipitation.The contact of sNP surfaces with molecules then affects chemical reactions of molecules and also behaviors of sNPs.This article describes systems derived from synthetic helical molecules and sNPs,which exhibit notable phenomena including selective adsorption and molecular recognition,equilibrium shift,step kinetics with induction period,precipitation with flow and sweeping,and disaggregation and desorption by sonication,in which the high affinity of helical molecules with sNP surfaces plays important roles.Mechanistic models that explain the phenomena are provided.Possible applications are also discussed,including the separation of molecules,capture of intermediates,the storage and release of molecules,equilibrium shift,clocking,and the translation of mechanical stimulations into chemical reactions.

Influences of chemical reactions on polysulfide reduction reaction process on promotor surface in Li-S batteries

Polar promotors have been proven effective in catalyzing the polysulfide(PS)reduction reaction(PSRR)process in lithium-sulfur(Li-S)batteries.However,the promotor surface tends to be poisoned due to the accumulation of insoluble discharging products of lithium disulfide(Li_(2)S_(2))and lithium sulfide(Li_(2)S)during Li-S battery operation.Herein,we investigate the detailed PSRR mechanism on the surface of manganese sulfides(MnS)as a representative promoter by performing in-situ Raman mapping measurements.The catalytic ability of MnS enables thorough electrochemical reduction of PSs to Li_(2)S_(2) and Li_(2)S on the MnS surface.The generated Li_(2)S_(2) and Li_(2)S then adsorb the dissolved PSs via chemical reactions among sulfur species during the subsequent PSRR process.This phenomenon mitigates promotor poisoning and continuously improves the reversible capacity.Consequently,the assembled Li-S cell demonstrates excellent electrochemical performance after introducing a conductive interlayer containing a thin piece of carbon nanotube film and MnS promotors.

Multi-Objective Optimization of Multi-Product Parallel Disassembly Line Balancing Problem Considering Multi-Skilled Workers Using a Discrete Chemical Reaction Optimization Algorithm

This work investigates a multi-product parallel disassembly line balancing problem considering multi-skilled workers.A mathematical model for the parallel disassembly line is established to achieve maximized disassembly profit and minimized workstation cycle time.Based on a product’s AND/OR graph,matrices for task-skill,worker-skill,precedence relationships,and disassembly correlations are developed.A multi-objective discrete chemical reaction optimization algorithm is designed.To enhance solution diversity,improvements are made to four reactions:decomposition,synthesis,intermolecular ineffective collision,and wall invalid collision reaction,completing the evolution of molecular individuals.The established model and improved algorithm are applied to ball pen,flashlight,washing machine,and radio combinations,respectively.Introducing a Collaborative Resource Allocation(CRA)strategy based on a Decomposition-Based Multi-Objective Evolutionary Algorithm,the experimental results are compared with four classical algorithms:MOEA/D,MOEAD-CRA,Non-dominated Sorting Genetic Algorithm Ⅱ(NSGA-Ⅱ),and Non-dominated Sorting Genetic Algorithm Ⅲ(NSGA-Ⅲ).This validates the feasibility and superiority of the proposed algorithm in parallel disassembly production lines.

Shock-induced chemical reaction characteristics of PTFE-Al-Bi_(2)O_(3)reactive materials

A ternary system of PTFE/Al/Bi_(2)O_(3)is constructed by incorporating PTFE-based reactive material and thermite for enhancing the energy release of the PTFE-based reactive material.The effects of Bi_(2)O_(3)in the PTFE/Al/Bi_(2)O_(3)on both mechanical properties and the energy release were investigated through various tests such as thermogravimetry-differential scanning calorimetry,adiabatic oxygen bomb test and split Hopkinson pressure bar test.The microstructure observed through scanning electron microscope and Xray diffraction results are used to analyze the ignition and reaction mechanism of PTFE/Al/Bi_(2)O_(3).The results indicate that the PTFE/Al/Bi_(2)O_(3)are capable of triggering the exothermic reaction of molten PTFE/Bi_(2)O_(3)and Al/Bi_(2)O_(3)over the PTFE/Al reactive materials,thereby promoting reactions.The excessive aluminum in the ternary system is beneficial for increasing energy release.The ignition of shock-induced chemical reactions in PTFE/Al/Bi_(2)O_(3)is closely related to the material fracture.The dominant mechanism for hot-spot generation under Split Hopkinson Pressure Bar test is the frictional temperature rise at the microcrack after failure.

Chemically Radiative MHD Flow of a Micropolar Nanofluid over a Stretching/ Shrinking Sheet with a Heat Source or Sink

This study examines the behavior of a micropolar nanofluidflowing over a sheet in the presence of a transverse magneticfield and thermal effects.In addition,chemical(first-order homogeneous)reactions are taken into account.A similarity transformation is used to reduce the system of governing coupled non-linear partial differ-ential equations(PDEs),which account for the transport of mass,momentum,angular momentum,energy and species,to a set of non-linear ordinary differential equations(ODEs).The Runge-Kutta method along with shoot-ing method is used to solve them.The impact of several parameters is evaluated.It is shown that the micro-rota-tional velocity of thefluid rises with the micropolar factor.Moreover,the radiation parameter can have a remarkable influence on theflow and temperature profiles and on the angular momentum distribution.

Hydromagnetic Squeezing Nanofluid Flow between Two Vertical Plates in Presence of a Chemical Reaction

In this study, Hydromagnetic Squeezing Nanofluid flow between two vertical plates in presence of a chemical reaction has been investigated. The governing equations were transformed by similarity transformation and the resulting ordinary differential equations were solved by collocation method. The velocity, temperature, concentration and magnetic induction profiles were determined with help of various flow parameters. The numerical scheme was simulated with aid of MATLAB. The results showed that increasing the squeeze number only boosts velocity and concentration while lowering temperature. Conversely, increasing the Hartmann number, Reynold’s magnetic number, Eckert number and Thermal Grashof number generally increases temperature but decreases both velocity and concentration. Chemical reaction rate and Soret number solely elevate concentration while Schmidt number only reduces it. The results of this study will be useful in the fields of oil and gas industry, plastic processing industries, filtration, food processing, lubrication system in machinery, Microfluidics devices for drug delivery and other related fields of nanotechnology.

Numerical simulation and experimental verification of chemical reactions for SCR DeNOx

Selective catalytic reduction(SCR)is a major commercial technology for NOx removal in power plants.There are a lot of complex chemical reactions in SCR reactors,and it is of great significance to understand the internal process of chemical reactions for SCR DeNOx and study the impact of various factors on NOx removal efficiency.In this paper,the impact of reaction temperature,ammonia-nitrogen molar ratio and resident time in the catalyst bed layer on NOx removal efficiency were studied by simulation of chemical reactions.Then calculated results were compared with catalyst activity test data in a power plant,which proved that the simulated results were accurate.As a result,the reaction conditions were optimized in order to get the best removal efficiency of NO,so that we can provide a reference for optimal running of SCR in power plants.

Review on Chemical Stability of Lead Halide Perovskite Solar Cells

Lead halide perovskite solar cells(PSCs) have become a promising next-generation photovoltaic technology due to their skyrocketed power conversion efficiency. However, the device stability issues may restrict their commercial applications, which are dominated by various chemical reactions of perovskite layers. Hence, a comprehensive illustration on the stability of perovskite films in PSCs is urgently needed. In this review article, chemical reactions of perovskite films under different environmental conditions(e.g., moisture,oxygen, light) and with charge transfer materials and metal electrodes are systematically elucidated. Effective strategies for suppressing the degradation reactions of perovskites, such as buffer layer introduction and additives engineering,are specified. Finally, conclusions and outlooks for this field are proposed. The comprehensive review will provide a guideline on the material engineering and device design for PSCs.

Catalysts and thermodynamic coupling of chemical reactions

The condition of occurrence of the thermodynamic coupling of chemical reactions is analysed from kinetics. It is found that the thermodynamic coupling is impossible for those reactions which obey kinetically the mass action law. The thermodynamic coupling of chemical reactions is further analysed in the case with catalyst. It is found that the thermodynamic coupling which is impossible without catalyst may become possible by introducing proper catalyst into the system. This implies that the catalysts can change not only the rates of chemical reactions, but also the behaviors of thermodynamic coupling of chemical reactions, including the direction of some reactions. Such role of catalysts comes into play not by changing the total free energy of the system, but by changing the reaction mechanism.