Chemical Reaction Model Research Articles

Construction of a numerical model for cigarette smoking and combustion and simulation of combustion cone shape

Abstract Understanding the thermal conditions inside a burning cigarette is a top priority for controlling chemical emissions and cigarette design. Since experimental methods are difficult to observe in depth, this paper starts from the perspective of numerical simulation and models the structure of the tobacco distribution of the cigarette, integrating the end surface ignition model, puffing model, chemical reaction model, heat and mass transfer and diffusion model have established a three-dimensional comprehensive model that can represent the changes in combustion cone morphology during cigarette combustion. The model covers chemical reaction and mass transfer as well as generation, flow and reaction mechanism. The simulation results show that the model can better predict the temperature distribution, component distribution and combustion cone morphology changes during cigarette smoking and combustion. It provides an effective means for in-depth research on cigarette combustion.

Effects of water injection on reaction temperature and hydrogen production in horizontal co-axial underground coal gasification

Underground coal gasification (UCG) is process of directly recovering energy as combustible gases such as hydrogen and carbon monoxide by combusting unmined coal resources in situ. During UCG process, the temperature in the gasification zone can exceed 1,300 °C, raising concerns about the potential melting of the steel pipe for oxidant injection. To control the temperature in the gasification zone, the use of water injection as an injection agent can be an option. Injecting water during UCG process serves two purposes: it decreases the temperature in the reaction zone by the endothermic effect of water, and it enhances the production of H2 by the reduction reaction of water. However, injecting excessive amounts of water may lead to a significant decrease in the temperature in the reaction zone, consequently cannot maintain the temperature range required for the UCG reaction. This study discusses the effects of water injection on the temperature of the gasification zone and the product gas by developing a chemical reaction model of UCG using COMSOL Multiphysics® software. The model was developed based on the temperature and produced gas results obtained from laboratory-scale artificial coal seam UCG experiments. Our findings reveal that water injection significantly influences the gasification process, controlling temperature in the reaction zone and promoting H2 production through steam gasification and water-gas shift reactions. Moreover, under the experiment and analysis conditions of this study, it is revealed that water injection up to an H2O/O2 molar ratio of 3.9 can effectively control the temperature of the gasification zone with enhancing H2 production.

Cyclohexane dehydrogenation: Critical evaluation of parameter estimation procedures for kinetic modeling

In the present paper a comparison between different parameter estimation procedures commonly used for the kinetic modeling of chemical reaction is performed, based on experimental measurements of the cyclohexane dehydrogenation to benzene. The obtained results show that, when the Arrhenius equation parameters are estimated from estimates of the rate constant taken at different temperatures, larger parameter uncertainties and correlations are obtained, particularly when the variances of the experimental measurements are not considered during the estimation process. It is also observed that an apparent kinetic compensation effect occurs when the experimental data are separated according to the inlet partial pressure and catalyst mass in the reactor, mainly due to the existing and unavoidable experimental uncertainties and parameter correlations. Additionally, it is shown that larger uncertainties and correlations are obtained when the parameter estimates are computed through the differential method, which can also lead to poorer model predictions of the experimental data. Finally, it is shown that the simultaneous one-step estimation of all model parameters through the integral method and considering the available experimental uncertainties can provide the most accurate parameter estimates, making use of mathematical expressions that describe how variances of the experimental measurements depend on the experimental conditions.

(Invited) Numerical Simulation of an Atmospheric Pressure Streamer Discharge and Induced Chemical Reactions

Streamer discharges are a type of non-thermal plasma produced by high-voltage electrical discharges, and have great potential as highly reactive chemical reaction fields. This is mainly due to the generation of high energy electrons that produce chemically active species. The applications of non-thermal plasma have attracted considerable interest in a wide range of industries. However, each radical has a different role in the plasma application and their reaction mechanism is also different. It's therefore important to understand exactly when, where and how much of these reactive species are produced in order to improve the treatment efficiency of atmospheric pressure plasma applications. Against this background, the aim of this study is to develop a simulation model capable of accurately predicting the chemical reactions of radicals. With a sufficiently validated simulation model, it would be possible to use such a model to design chemical reaction fields.The model consists of the first-order electrohydrodynamic model for electrons and positive and negative ions within the drift-diffusion approximation. Axis-symmetric coordinates were used to simulate the streamer discharge in air at atmospheric pressure. The electron transport and source parameters were calculated using two-term bltzmann equation and published electron impact cross-sections. The chemical reaction model used in this study includes electron impact collisions (excitation, ionisation, dissociation, recombination, attachment and detachment), ion recombination and the reactions of neutrals. In order to demonstrate the validity of the simulation, the light emission of the discharge is first compared between experiment and simulation. Then the spatial and temporal variations of each radical are simulated and compared with the simulation. In this talk, I will present the process of validation and verification (V&V) of the streamer discharge simulation and then the mechanism of radical production revealed by the simulation.

Discerning the magnetization reversal mechanism and magnetic interactions in arrays of FeNi nanowires

FeNi nanowires (NWs), 40 nm in diameter, were grown by electrodeposition. Compositional analysis showed Fe anomalous co-deposition, with different trends across the different potentials and electrolytes used. Those trends were explained within a modified Bocris-Drazic-Despic chemical reactions model, highlighting the importance of the electrochemical theory in understanding Fe-Ni electrodeposited systems. Structural characterization showed a change from a body-centred cubic structure for Fe-rich NWs to face-centred cubic at mid and low Fe content. Magnetic hysteresis measurements showed a range of coercivities from 20 mT for Fe-rich to 100 mT for Ni-rich NWs. Angular measurements allowed to determine that the magnetization reversal mechanism was dominated by transverse domain wall reversal. The analysis also hinted at the non-shape anisotropy acting as a demagnetizing force. First-order reversal curves (FORCs) showed that arrays with a high absolute value for the non-shape anisotropy had higher magnetic interactions, and vice versa. The non-shape anisotropy is dominated by the magnetostatic interactions between NWs, causing a weakening of the magnetic hardness. In combination with the coercivity angular measurements, the FORC analysis explained the shift in easy axis preference depending on NW chemical composition observed in the hysteresis loops of the samples.

Simulation study of the effect of electrode polarity on microscale corona discharge characteristics

Abstract The occurrence and application scenarios of micro-scale corona discharge are diverse, and the effect of micro-scale corona discharge mechanism and needle electrode polarity on corona discharge characteristics is still unclear. This paper establishes a microscale simulation model of pin-plate DC positive and negative corona fluid chemical reactions. The phenomenon of positive and negative corona discharge is being investigated. The internal discharge mechanism is analyzed from the microscopic point of view. Results demonstrate that positive corona discharge generates space charges that reduce the electric field strength between the needle electrode and amplify it between the plate electrodes. In contrast, negative corona discharge exhibits the opposite effect. The number of charged particles produced by microscale negative corona discharge is larger than that produced by positive corona, and the discharge phenomenon is more intense than that of positive corona. Under the simulation conditions in this paper, the ionization reaction rate of micro-scale positive and negative corona rises rapidly at the initial discharge. It will gradually remain stable after experiencing an upward pulse. The pulse peak value generated by micro-scale negative corona discharge is much higher than that of positive corona, and the pulse width of negative corona discharge is about half smaller than that of positive corona, which can reach a stable corona discharge state faster.

Dynamics and stability analysis of enzymatic cooperative chemical reactions in biological systems with time-delayed effects

The mathematical modeling and dynamic analysis of time-delayed enzymatic chemical reactions in biological systems are presented in this research. The objective is to examine the function of time lags in these reactions and to get a complete knowledge of the behavior of biological systems in a reaction to modifications in the quantity present of reactants and products. The model, which is based on delay differential equations, includes a time delay term to account for the lag between changes in the concentration of reactants, reaction rate constants and product responses. The findings give insight into how enzymatic processes behave dynamically and how stability is impacted by time lags, oscillation and general efficiency of the system. These results have significant importance for our comprehension of how biological processes are regulated and for the creation of biological control structures.

Modelling chemical processes in explicit solvents with machine learning potentials

Solvent effects influence all stages of the chemical processes, modulating the stability of intermediates and transition states, as well as altering reaction rates and product ratios. However, accurately modelling these effects remains challenging. Here, we present a general strategy for generating reactive machine learning potentials to model chemical processes in solution. Our approach combines active learning with descriptor-based selectors and automation, enabling the construction of data-efficient training sets that span the relevant chemical and conformational space. We apply this strategy to investigate a Diels-Alder reaction in water and methanol. The generated machine learning potentials enable us to obtain reaction rates that are in agreement with experimental data and analyse the influence of these solvents on the reaction mechanism. Our strategy offers an efficient approach to the routine modelling of chemical reactions in solution, opening up avenues for studying complex chemical processes in an efficient manner.

Computation Implemented by the Interaction of Chemical Reaction, Clustering, and De-Clustering of Molecules.

A chemical reaction and its reaction environment are intrinsically linked, especially within the confines of narrow cellular spaces. Traditional models of chemical reactions often use differential equations with concentration as the primary variable, neglecting the density heterogeneity in the solution and the interaction between the reaction and its environment. We model the interaction between a chemical reaction and its environment within a geometrically confined space, such as inside a cell, by representing the environment through the size of molecular clusters. In the absence of fluctuations, the interplay between cluster size changes and the activation and inactivation of molecules induces oscillations. However, in unstable environments, the system reaches a fluctuating steady state. When an enzyme is introduced to this steady state, oscillations akin to action potential spike trains emerge. We examine the behavior of these spike trains and demonstrate that they can be used to implement logic gates. We discuss the oscillations and computations that arise from the interaction between a chemical reaction and its environment, exploring their potential for contributing to chemical intelligence.

Simulation of hexavalent chromium removal by electrocoagulation using iron anode in flow-through reactor

An electrocoagulation (EC) model is developed for hexavalent chromium reduction and precipitation, using iron electrodes. Parallel removal mechanisms such as adsorption of chromium on ferrihydrite and direct reduction at the cathode is assumed negligible due to low concentration of Cr(VI). The reaction model presented for batch system represents species complexation, precipitation/dissolution, acid/base, and oxidation-reduction reactions. Batch reactor simulation is verified using experimental data obtained by Sarahney et al. (2012), where the effect of initial chromium concentration, pH, volumetric current density, and ionic strength is considered (Sarahney et al., 2012). The model couples multicomponent ionic transport in MATLAB with chemical reaction model in PHREEQC, as a widely used computational programming tool and a geochemical reaction simulator with comprehensive geochemistry databases. The suggested current density is 0.05−0.3mA/cm2 and the surface to volume ratio in batch reactor is considered 0.017 1/cm. Design parameters are presented for operation of a flow-through hexavalent chromium removal using electrocoagulation by iron electrode to treat Cr(VI) in range of 10–50 mg/L. The operational parameters for a flow-through EC reactor for Cr(VI) removal is suggested to follow 0.05mA/cm2≤3nFeQcCrVIinlet≤0.3mA/cm2.

Amplitude equations for wave bifurcations in reaction–diffusion systems

A wave bifurcation is the counterpart to a Turing instability in reaction–diffusion systems, but where the critical wavenumber corresponds to a pure imaginary pair rather than a zero temporal eigenvalue. Such bifurcations require at least three components and give rise to patterns that are periodic in both space and time. Depending on boundary conditions, these patterns can comprise either rotating or standing waves. Restricting to systems in one spatial dimension, complete formulae are derived for the evaluation of the coefficients of the weakly nonlinear normal form of the bifurcation up to order five, including those that determine the criticality of both rotating and standing waves. The formulae apply to arbitrary n-component systems ( n⩾3 ) and their evaluation is implemented in software which is made available as supplementary material. The theory is illustrated on two different versions of three-component reaction–diffusion models of excitable media that were previously shown to feature super- and subcritical wave instabilities and on a five-component model of two-layer chemical reaction. In each case, two-parameter bifurcation diagrams are produced to illustrate the connection between complex dispersion relations and different types of Hopf, Turing, and wave bifurcations, including the existence of several codimension-two bifurcations.

Solution of chemical reaction model using Haar wavelet method with Caputo derivative

Solution of chemical reaction model using Haar wavelet method with Caputo derivative

Study of combustion flow field in a scramjet engine under inflow oscillation variations based on OpenFOAM

In this study, a compressible supersonic numerical model was established based on the open-source computational fluid dynamics software OpenFOAM. The supersonic air inflow was set in sinusoidal variation and gas hydrogen was employed as fuel for the DLR engine numerical simulation. The SST k-ω model and a 9-species 27-reaction hydrogen/oxygen chemical reaction model was employed as the turbulence and reaction mechanical kinetics models respectively. The effect of continuous variable inflow on the combustion performance for the scramjet engine was analyzed and the results showed that the combustion flame inside the scramjet engine exhibited significant partitioning phenomena around the combustion stabilization zones under periodic continuous variable inflow conditions. It was found that intense combustion zones were formed at both upstream and downstream flow as the induction of intersecting shock waves. When the flame was stabilized in the engine, the initiation position of the intense combustion zone at the upstream was transferred to the distance of twice the strut length, while the initiation position of the intense combustion zone at the downstream was anchored at a distance of about five times the strut length.

Distinguishing homolytic vs heterolytic bond dissociation of phenylsulfonium cations with localized active space methods

Modeling chemical reactions with quantum chemical methods is challenging when the electronic structure varies significantly throughout the reaction and when electronic excited states are involved. Multireference methods, such as complete active space self-consistent field (CASSCF), can handle these multiconfigurational situations. However, even if the size of the needed active space is affordable, in many cases, the active space does not change consistently from reactant to product, causing discontinuities in the potential energy surface. The localized active space SCF (LASSCF) is a cheaper alternative to CASSCF for strongly correlated systems with weakly correlated fragments. The method is used for the first time to study a chemical reaction, namely the bond dissociation of a mono-, di-, and triphenylsulfonium cation. LASSCF calculations generate smooth potential energy scans more easily than the corresponding, more computationally expensive CASSCF calculations while predicting similar bond dissociation energies. Our calculations suggest a homolytic bond cleavage for di- and triphenylsulfonium and a heterolytic pathway for monophenylsulfonium.

Influence of inhomogeneous distribution of inflow equivalence ratio on oblique detonation morphology and characteristic

In this paper, numerical simulations using Euler equations coupled detailed chemical reaction model are performed to reveal the influence of inhomogeneous distribution of inflow equivalence ratio (ER) on the morphology and characteristic of oblique detonation in hydrogen/oxygen/argon mixtures. The purpose of this study is to better understand the key parameters’ variation law of oblique detonation flow field under practical flight conditions so as to guide the design of oblique detonation chamber. Within the scope of our simulations, the results show that the oblique detonation wave (ODW) can still be standing under a large ER gradient. The thermodynamic state and characteristic sizes of the flow field reach the maximum value around ER = 0.8. First, the ODW angle and the post-wave temperature/pressure increase with the homogeneous inflow ER. Then, the inhomogeneity of inflow ER is introduced by assuming a lateral linear distribution covering the whole inflow boundary. When the ER increases along the inflow boundary with ER = 0 at the wedge tip, the overall morphology of the ODW presents a concave structure. Inversely, the ODW is convex with ER = 0 at the top outlet. The morphology and characteristic sizes of ODW are determined by the mixture composition in front of the corresponding wave surface. The transition mode of ODW is mainly determined by the ER of the incoming flow in front of the induction region.

Insights into chemical kinetics of hybrid chemical reaction models in hypersonic rarefied flow

Insights into chemical kinetics of hybrid chemical reaction models in hypersonic rarefied flow

Validity, Verifiability, and Confirmability: A Critique of Multiphase Packed Bed Modeling

The pseudocontinuum models of reactions in packed beds are complicated, and an assessment of the reliability of the predictability of their numerical solution is difficult. The predictability reliability depends on validity and verifiability, whereas the numerical solutions of models of reactions in packed beds cannot be validated or verified. Scientific acceptability cannot commence by metaphysics alone, and the truth of the speculative justifications of the results of the numerical models without robust empirical confirmation is a matter of chance occurrence. Adherence to the principles of noncontradiction and mathematical consistency seems to be the minimal criterion if a pseudocontinuum model is to demonstrate a degree of reliability in prediction, simulation, and design. This article is an exposition of the verifiability, validity, and confirmability characteristics of multiphase multidimensional models of reactions in packed beds. It addresses the difficulties of validation and the complexities of construction of models of reactions in packed beds by modeling kinetic data directly to show that often the claims of validity, verifiability, or confirmability of the results of multidimensional or even one-dimensional models of chemical reactions in packed beds, in spite of robust statistical tools, should be viewed with some degree of skepticism.

Study on the impact of heat loss on premixed hydrogen/air deflagration in closed pipelines

This study developed a one-step chemical reaction model for hydrogen combustion and investigated the effect of heat loss on premixed hydrogen/air deflagration in closed pipelines using numerical simulations with the CFD code GASFLOW-MPI. The simulation results were compared and verified with experimental data. The numerical simulations accurately predicted the flame front structure, pressure, and flame tip position during the deflagration of premixed hydrogen/air. Furthermore, a comparison of adiabatic simulation and heat transfer simulation results revealed that large-scale vortices within the turbulent flow were closely linked to heat loss during the tulip flame stage. Simultaneously, heat loss reduced pressure and flame tip position by diminishing the flame wrinkling factor caused by thermodiffusive instability. Finally, convective heat transfer identified as the most critical factor contributing to heat loss during the deflagration of premixed hydrogen/air in closed pipelines. Specifically, during the tulip flame stage, heat loss was mainly due to convective heat transfer (73.8%∼76.3%), with radiation playing a minor role (23.7%∼26.2%). Therefore, accurate prediction of characteristic parameters during the deflagration of premixed hydrogen/air requires numerical simulations that account for both convective and radiative heat transfer.

Graph realization of sets of integers

Graph theory is used in many areas of chemical sciences, especially in molecular chemistry. It is particularly useful in the structural analysis of chemical compounds and in modeling chemical reactions. One of its applications concerns determining the structural formula of a chemical compound. This can be modeled as a variant of the well-known graph realization problem. In the classical version of the problem, a sequence of natural numbers is given, and the question is whether there exists a graph in which the vertices have degrees equal to the given numbers. In the variant considered in this paper, instead of a sequence of natural numbers, a sequence of sets of natural numbers is given, and the question is whether there exists a multigraph such that each of its vertices has a degree equal to a number from one of the sets. This variant of the graph realization problem matches the nature of the problem of determining the structural formula of a chemical compound better than other variants considered in the literature. We propose a polynomial time exact algorithm solving this variant of the problem.

Molecular modeling of reactive systems with REACTER

From batteries to biology, many important technologies and physical phenomena operate as out-of-equilibrium reactive systems. Accurately modeling the nanoscale dynamics of non-equilibrium reactive systems and how they respond to external stimuli is challenging, especially if both atomistic resolution and large scales (>105 atoms) are required. REACTER is a protocol for modeling chemical reactions during classical molecular dynamics (MD) simulations. Coupling traditional fixed-valence force fields with heuristic reactive MD is advantageous for large-scale simulations of dynamic systems that can include the complex reaction mechanisms common in organic chemistry. This paper details the current features of the LAMMPS implementation of REACTER, known as fix bond/react, and surveys recent applications of the protocol in a variety of fields, including photopolymers, high-performance composites, and membranes. Conceived as a tool for modeling polymerization processes, the scope of REACTER is expanding as it is applied to new materials and supporting features are implemented. Three new case studies are presented that highlight the capabilities of REACTER, including modeling hierarchical materials, the mechanics of molecular machines, and large-scale dynamics of heterogeneous catalysis.