Reaction-diffusion models from the Fokker-Planck formulation ofchemical processes

A Fokker-Planck-type model is proposed to describe the kineticsof certain chemical reactions. In particular, the competitionbetween transport and reaction processes is analysed. The studyis carried out considering various scalings of interaction,measured by the exponent of a small parameter related to themean free path. In the most significant case of competitionbetween both effects, the lowest-order density in the asymptoticexpansion obeys a reaction-diffusion equation. Such an equationwas earlier considered as the starting point in the study ofthese processes by other authors (e.g. by Schlgl). For otherinteraction scalings, the prevalence of chemical processes impliesthat the lowest-order density is determined by the (algebraic)equations of chemical equilibrium. In contrast, when transportprevails, the reaction terms affect only higher-orderdensities.     

Parameterized Scalar Profile Mixing Model for Turbulent Combustion Simulations

The composition fields in turbulent reacting flows are affected by turbulent transport (macromixing), molecular diffusion (micromixing), and chemical reactions. In the joint velocity-composition probability density function transport equation the highly non-linear macromixing and chemical reaction terms appear in closed form. This is a considerable advantage over moment closure methods. Micromixing on the other hand requires modeling and especially for turbulent combustion accurate mixing models are crucial. Our approach to model the mixing of scalars, e.g. species mass fractions or temperature, is based on considering one-dimensional parameterized scalar profiles (PSP). Here, an extension of the PSP mixing model to inhomogeneous flows is presented. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Mixing Model Based on Parameterized Scalar Profiles

The composition fields in turbulent reacting flows are affected by turbulent transport (macromixing), molecular diffusion (micromixing), and chemical reactions. In the joint velocity-composition probability density function transport equation the highly nonlinear macromixing and chemical reaction terms appear in closed form. This is a considerable advantage over second moment closure methods. Micromixing on the other hand requires modelling and especially for turbulent combustion accurate mixing models are crucial. In this paper we present an approach to model the mixing of scalars, e.g. species mass fractions or temperature, based on considering one-dimensional parameterized scalar profiles (PSP). (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Eulerian–Lagrangian localized adjoint methods for reactive transport with biodegradation

The microbial degradation of organic contaminants in the subsurface holds significant potential as a mechanism for in-situ remediation strategies. The mathematical models that describe contaminant transport with biodegradation involve a set of advective–diffusive–reactive transport equations. These equations are coupled through the nonlinear reaction terms, which may involve reactions with all of the species and are themselves coupled to growth equations for the subsurface bacterial populations. In this article, we develop Eulerian–Lagrangian localized adjoint methods (ELLAM) to solve these transport equations. ELLAM are formulated to systematically adapt to the changing features of governing partial differential equations. The relative importance of retardation, advection, diffusion, and reaction is directly incorporated into the numerical method by judicious choice of the test functions that appear in the weak form of the governing equation. Different ELLAM schemes for linear variable–coefficient advective–diffusive–reactive transport equations are developed based on different operator splittings. Specific linearization techniques are discussed and are combined with the ELLAM schemes to solve the nonlinear, multispecies transport equations. © 1995 John Wiley & Sons, Inc.     

An inverse problem for an immobilized enzyme model

A method for estimating unknown kinetic parameters in a mathematical model for catalysis by an immobilized enzyme is studied. The model consists of a semilinear parabolic partial differential equation modeling the reaction‐diffusion process coupled with an ordinary differential equation for the rate transport. The well posedness of the model is proven; a PDE‐constrained optimization approach is applied to the stated inverse problem; and finally, some numerical simulations are presented.     

Modulation equations and parabolic limits of reaction random-walk systems

Reaction random-walk systems are hyperbolic models to describe spatial motion (in one dimension) with finite speed and reactions of particles. Here we present two approaches which relate reaction random-walk equations with reaction diffusion equations. First, we consider the case of high particle speeds (parabolic limit). This leads to a singular perturbation analysis of a semilinear damped wave equation. A initial layer estimate is given. Secondly, we consider the case of a transcritical bifurcation. We use techniques similar to that of the Ginzburg–Landau method to find a modulation equation for the amplitude of the first unstable mode. It turns out that the modulation equation is Fisher's equation, hence near the bifurcation point travelling wave solutions are obtained. The approximation result and the corresponding estimate is given in terms of the bifurcation parameter. Both results are based on an a priori estimate for classical solutions which follows from explicit representations of the solution of the linear telegraph equation. © 1998 B. G. Teubner Stuttgart—John Wiley & Sons, Ltd.     

Flammes planes avec transport multi-espèce et chimie complexe

We consider plane laminar flames with multicomponent transport and complex chemistry. The governing equations are derived from the kinetic theory of gases. An arbitrary number of reversible chemical reactions and temperature dependent species specific heats are considered in the model. The most general form for multicomponent transport fluxes given by the kinetic theory is also taken into account. Upon first considering a bounded domain and then letting the size of the domain to go to infinity, we obtain an existence theorem. A priori estimates fundamentally rely on the entropy which correlates the transport fluxes and the gradients.     

Quantifying fate and transport of nitrate in saturated soil systems using fractional derivative model

Natural soil systems usually exhibit complex properties such as fractal geometry, resulting in complex dynamics for the movement of solutes and colloids in soils, such as the well-documented non-Fickian or anomalous diffusion for contaminant transport in saturated soils. The development of robust mathematical models to simulate anomalous diffusion for reactive contaminants at all relevant scales presents a contemporary problem in computational hydrology. This study aims to develop and validate a novel fractional derivative, advection-dispersion-reaction equation (fADRE) with first order decay to quantify nitrate contaminants transport in various soil systems. As an essential nutrient for crop growth, nitrogen in various forms (i.e., fertilizers) is typically applied to agricultural plots but a certain fraction or excess that is converted to nitrate or nitrite will serve as a critical pollutant to surface-water and groundwater. Applications show that the fADRE model can consider both hydrological and biogeochemical processes describing the fate and transport of nitrate in saturated soil. Here “fate” is a commonly used terminology in hydrology to describe the transformation and destination of pollutants in surface and subsurface water systems. The model is tested and validated using the results from three independent studies including: (1) nitrate transport in natural soil columns collected from the North China Plain agricultural pollution zone, (2) nitrate leaching from aridisols and entisols soil columns, and (3) two bacteria (Escherichia coli and Klebsiella sp.) transport through saturated soil columns. The qualitative relationship between model parameters and the target system properties (including soil physical properties, experimental conditions, and nitrate/bacteria physical and chemical properties) is also explored in detail, as well as the impact of chemical reactions on nitrate transport and fate dynamics. Results show that the fADRE can be a reliable mathematical model to quantify non-Fickian and reactive transport of chemicals in various soil systems, and it can also be used to describe other biological degradation and decay processes in soil. Hence, the mathematical model proposed by this study may help provide valuable insight on the quantification of various biogeochemical dynamics in complex soil systems, but needs to be tested in real-world applications in the future.     

Optimization of Batch Reactions in Series with Uncertainty

Certain types of chemical reactions, such as the global deprotection of a polypeptide, are extremely complex. As a result, it may be very difficult or expensive to develop accurate models of these chemical reactions. Without a satisfactory kinetic model for the reaction, it is difficult to develop an optimum operating policy that will maximize the profit. Stochastic optimization is applied in this work to an example process step to obtain the optimum reaction temperature and reaction time. In the case of the “here and now” problem, the optimal conditions are a lower reaction temperature and a longer reaction time than obtained from the deterministic problem. The average reaction time for the “wait and see” problem is also longer than the deterministic case, but the average reaction temperature is very close to that of the deterministic problem. Both normally and uniformly – distributed uncertain parameters are considered.     

New asymptotic expansion algorithm for singularly perturbed evolution equations

A new asymptotic expansion algorithm related to the Chapman-Enskog expansion in kinetic theory is applied to systems of linear evolution equations. The uniform convergence of the asymptotic solution to the exact one is shown. The algorithm is applied to the linearized Carleman model of the Boltzmann equation, to the neutron transport equation, and to the Fokker-Planck equation.     

Time/depth dependent diffusion and chemical reaction model of chloride transportation in concrete

This study focuses on the physical and chemical processes that control the transport of chloride ions into concrete structures. An analytical solution of a diffusion reaction model is presented for determining the time/depth dependent chloride diffusivities considering both diffusion process and binding mechanism of chloride occur simultaneously. The diffusion-reaction model, which is based on the Fick’s second law of diffusion and a mathematical formulation for an irreversible first-order chemical reaction, is used to precisely describe the diffusion mechanism of chloride diffusion process. When the chemical reaction is considered, the free chloride concentration is slowly reduced since some of the free chloride ions have reacted with cement paste such that the diffusion coefficient is also reduced simultaneously. The diffusion-reaction model predicts a longer service life than the total and free chloride diffusion models that do not consider the effect of the chemical reaction during the chloride diffusion process.     

On a diffusion‐kinetic equation arising in extended kinetic theory

This paper is devoted to the study of solvability of an evolution equation obtained as a hydrodynamic limit of a linear Boltzmann equation with elastic and inelastic scattering terms. An interesting feature of this equation is that it combines the diffusion operator and a singular operator of a kinetic type. The study is carried out in the L₁ space which is natural from the physical point of view and allows to apply modifications of methods of the kinetic theory. Copyright © 2000 John Wiley & Sons, Ltd.     

Nonstandard methods for the convective transport equation with nonlinear reactions

A new nonstandard Lagrangian method is constructed for the one-dimensional, transient convective transport equation with nonlinear reaction terms. An “exact” time-stepping scheme is developed with zero local truncation error with respect to time. The scheme is based on nonlocal treatment of nonlinear reactions, and when applied at each spatial grid point gives the new fully discrete numerical method. This approach leads to solutions free from the numerical instabilities that arise because of incorrect modeling of derivatives and nonlinear reaction terms. Algorithms are developed that preserve the properties of the numerical solution in the case of variable velocity fields by using nonuniform spatial grids. Effects of different interpolation techniques are examined and numerical results are presented to demonstrate the performance of the proposed new method. © 1998 John Wiley & Sons, Inc. Numer Methods Partial Differential Eq 14: 467–485, 1998     

One-dimensional equilibrium model and source parameter determination for soil-column experiment

One-dimensional equilibrium soil-column experiment models with source (sink) reaction terms are discussed in this paper. In the case of occurring high-order chemical reactions, the zero production term in traditional models should be modified to a nonlinear term related with time (or space) and solute concentration, and then a mathematical model with nonlinear terms is put forward. Furthermore, an actual soil-column experiment in Zhangdian, Zibo is investigated. By applying an optimal perturbation algorithm, the source coefficient in the model is determined both in the cases of accurate data and inaccurate data. The inversion results show that for such inverse source coefficient problems with limited additional data, some optimal methods could be more efficient than regularization strategies, and for some real equilibrium soil-column experiments, the process of source (sink) reactions could be a key factor in the solute transportation.     

Erratum to: Integration of the Continual System of Nonlinear Interaction Waves

We derive the continual system of nonlinear interaction waves from the compatibility of the transport equation on the whole line and the equation governing the time-evolution of the eigenfunctions of the transport operator. The transport equation represents the continual generalization from the n-component system of first-order ordinary differential equations. The continual system describes a nonlinear interaction of waves. We prove that the continual system can be integrated by the inverse scattering method. The method is based on applying the results of the inverse scattering problem for the transport equation to finding the solution of the Cauchy initial-value problem for the continual system. Indeed, the transition operator for the scattering problem admits right and left Volterra factorizations. The intermediate operator for this problem determines the one-to-one correspondence between the preimages of a solution of the transport equation. This operator is related to the transition operator and admits not only right and left Volterra factorizations but also the analytic factorization. By virtue of this fact the potential in the transport equation is uniquely reconstructed in terms of the solutions of the fundamental equations in inverse problem.     

Nonstandard methods for the convective‐dispersive transport equation with nonlinear reactions

A new nonstandard Eulerian‐Lagrangian method is constructed for the one‐dimensional, transient convective‐dispersive transport equation with nonlinear reaction terms. An “exact” difference scheme is applied to the convection‐reaction part of the equation to produce a semi‐discrete approximation with zero local truncation errors with respect to time. The spatial derivatives involved in the remaining dispersion term are then approximated using standard numerical methods. This approach leads to significant, qualitative improvements in the behavior of the numerical solution. It suppresses the numerical instabilities that arise from the incorrect modeling of derivatives and nonlinear reaction terms. Numerical experiments demonstrate the scheme's ability to model convection‐dominated, reactive transport problems. © 1999 John Wiley & Sons, Inc. Numer Methods Partial Differential Eq 15: 617–624, 1999     

Vapor-liquid phase transition: The Van Der Waals model

We develop the kinetic theory of critical phenomena in the Van der Waals model. Our approach is considerably different from the traditional phenomenological approach based on the scaling invariance hypothesis and the renormalization group method. From the analysis of the kinetic equation, we can calculate the dynamic and fluctuation characteristics and thus explain a number of experimental observations. The dynamic processes are investigated using self-consistent equations for the first and second moments of the distribution function. We use the corresponding Langevin equation to describe the fluctuation processes. The structure of the dissipative terms in the kinetic equation determines the source intensities. Analysis of experimental data for the temperature dependence of the heat capacity and for the molecular scattering spectra confirms the conclusions derived from the kinetic theory. This paper is published for discussion. Editorial Board. Translated from Teoreticheskaya i Matematicheskaya Fizika Vol. 115, No. 3, pp.437–458, June, 1998.     

Thermofluiddynamics in liquid media during biotechnological processes under high pressure

In bio/ chemical engineering high pressure (HP) processing up to several GPa represents a novel technique to selectively influence (bio–)chemical reactions resulting from temperature and pressure sensitivities differing between the occuring reactions. Therefore, thermofluiddynamical effects leading to inhomogeneous process conditions (pressure, temperature) show an important influence on the process results. To predict and improve mass, momentum and energy transport within the HP vessel and the impact on desired chemical reactions spatiotemporal numerical simulations are a useful tool in process analysis and design. The present contribution deals with mathematical modelling of the enzyme inactivation in HP processing of liquid biotechnological media. For the first time a transport equation for the scalar quantity “enzyme activity” is deduced. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

A thermodynamical framework for chemically reacting systems

In this paper, we develop a thermodynamic framework that is capable of describing the response of viscoelastic materials that are undergoing chemical reactions that takes into account stoichiometry. Of course, as a special sub-case, we can also describe the response of elastic materials that undergo chemical reactions. The study generalizes the framework developed by Rajagopal and co-workers to study the response of a disparate class of bodies undergoing entropy producing processes. One of the quintessential feature of this framework is that the second law of thermodynamics is formulated by introducing Gibbs?? potential, which is the natural way to study problems involving chemical reactions. The Gibbs potential?Cbased formulation also naturally leads to implicit constitutive equations for the stress tensor. Another feature of the framework is that the constraints due to stoichiometry can also be taken into account in a consistent manner. The assumption of maximization of the rate of entropy production due to dissipation, heat conduction, and chemical reactions is invoked to determine an equation for the evolution of the natural configuration ?? _p(t)(B), the heat flux vector and a novel set of equations for the evolution of the concentration of the chemical constituents. To determine the efficacy of the framework with regard to chemical reactions, those occurring during vulcanization, a challenging set of chemical reactions, are chosen. More than one type of reaction mechanism is considered and the theoretically predicted distribution of mono, di and polysulfidic cross-links agree reasonably well with available experimental data.