Analytical considerations and dimensionless analysis for a description of particle interactions in high pressure processes

High pressures of up to several hundreds of MPa are utilized in a wide range of applications in chemical, bio-, and food engineering, aiming at selective control of (bio-)chemical reactions. Non-uniformity of process conditions may threaten the safety and quality of the resulting products because processing conditions such as pressure, temperature, and treatment history are crucial for the course of (bio-)chemical reactions. Therefore, thermofluid-dynamical phenomena during the high pressure process have to be examined, and numerical tools to predict process uniformity and to optimize the processes have to be developed. Recently applied mathematical models and numerical simulations of laboratory and industrial scale high pressure processes investigating the mentioned crucial phenomena are based on continuum balancing models of thermofluid dynamics. Nevertheless, biological systems are complex fluids containing the relevant (bio-)chemical compounds (enzymes and microorganisms). These compounds are particles that interact with the surrounding medium and between each other. This contribution deals with thermofluid-dynamical interactions of the relevant particulate (bio-)chemical compounds (enzymes and microorganisms) with the surrounding fluid. By consideration of characteristic time and length scales and particle forces, the motion of the (bio-)chemical compounds is characterized.     

The importance of chemical mechanisms in sonochemical modelling

A state-of-the-art chemical mechanism is introduced to properly describe chemical processes inside a harmonically excited spherical bubble placed in water and saturated with oxygen. The model uses up-to-date Arrhenius-constants, collision efficiency factors and takes into account the pressure-dependency of the reactions. Duplicated reactions are also applied, and the backward reactions rates are calculated via suitable thermodynamic equilibrium conditions. Our proposed reaction mechanism is compared to three other chemical models that are widely applied in sonochemistry and lack most of the aforementioned modelling issues. In the governing equations, only the reaction mechanisms are compared, all other parts of the models are identical. The chemical yields obtained by the different modelling techniques are taken at the maximum expansion of the bubble. A brief parameter study is made with different pressure amplitudes and driving frequencies at two equilibrium bubble sizes. The results show that due to the deficiencies of the former reaction mechanisms employed in the sonochemical literature, several orders of magnitude differences of the chemical yields can be observed. In addition, the trends along a control parameter can also have dissimilar characteristics that might lead to false optimal operating conditions. Consequently, an up-to-date and accurate chemical model is crucial to make qualitatively and quantitatively correct conclusions in sonochemistry.     

Thermal Control Simulation in High Pressure Treatment of Foods

High hydrostatic pressure (HHP) has become in the last few years a promising technology for food processing and preservation. Pressure treatment of foods always results in a temperature increase due to the work of compression. After compression, heat loss through the metal wall of the high-pressure vessel causes temperature gradients in the processed product. So, it is absolutely necessary to know how thermal exchanges in high-pressure treatments are produced and at what rate in order to establish the real conditions at which a given process is realised. In this paper, a modelling/simulation of the thermal exchanges taking place in a high-pressure pilot unit during different processes of pressurisation and depressurisation is presented. Good agreement between simulated and experimental values is found. This work involves an important advance in optimisation and regulation of high-pressure processes in food industry.     

Calculation of the probability for ionic association and dissociation reactions by molecular dynamics and umbrella sampling

Investigating chemical reactions by computational techniques and finding new ways to study these reactions is an important necessity in the fields of chemistry, chemical engineering and biology. In this study, we have presented a new procedure for studying the interactions between divalent metal ions and carboxylates by using umbrella sampling. In some cases, it is more convenient to use variable coordinate reaction probabilities instead of potential energy or free energy curves, which in general are more widely used and available in the literature. Particularly, for practical purposes in building multi-scale models it could be more convenient to use the probability of reaction as a function of the separation distance between two carboxylate moieties when they are simultaneously associated to a metal ion. In this work, we have modelled the interactions between two carboxylates (propanoate ions) and divalent metal ions (calcium or magnesium) in order to obtain the probability of reaction as a function of the separation distance between the two carboxylates. By calculating the probability, it also became apparent that in the system containing calcium, the carboxylates have higher probability of reaction compared to the system containing magnesium. Furthermore, the presented probability could be also used for other multi-scale modelling purposes where these interactions are of main importance. The proposed procedure could also have application in other systems of interest.     

Self-Interactions of Strands and Sheets

Physical strands or sheets that can be modelled as curves or surfaces embedded in three dimensions are ubiquitous in nature, and are of fundamental importance in mathematics, physics, biology, and engineering. Often the physical interpretation dictates that self-avoidance should be enforced in the continuum model, i.e., finite energy configurations should not self-intersect. Current continuum models with self-avoidance frequently employ pairwise repulsive potentials, which are of necessity singular. Moreover the potentials do not have an intrinsic length scale appropriate for modelling the finite thickness of the physical systems. Here we develop a framework for modelling self-avoiding strands and sheets which avoids singularities, and which provides a way to introduce a thickness length scale. In our approach pairwise interaction potentials are replaced by many-body potentials involving three or more points, and the radii of certain associated circles or spheres. Self-interaction energies based on these many-body potentials can be used to describe the statistical mechanics of self-interacting strands and sheets of finite thickness.     

Multi-species simple exclusion processes

A motility mechanism based on a simple exclusion process, where the movement of discrete agents on a lattice is either unbiased (symmetric) or biased (asymmetric) is considered. Estimates of diffusivities from tracking data do not describe the population-level response of the system. This mismatch between the individual-level and population-level behaviour can be resolved by averaging the individual-level mechanism in terms of an expected site occupancy. New insight into simple exclusion processes is obtained by representing the system as a series of interacting subpopulations. This formalism leads to a system of nonlinear advection-diffusion equations which can be interpreted in terms of the agent fluxes. These interactions have consequences for both agent-based modelling and continuum modelling in cell biology, such as tracking subpopulations of cells within a total cell population.     

Deuteron disintegration, thermonuclear and nuclear fission reactions induced by γ-quanta in D-saturated palladium and dense deuterium gas with synthesis of new structures

The results obtained by investigating the chemical composition and structure of Pd sample sur-faces, chamber components, and a new synthesized object (NSO) are presented. The NSO is produced in the chamber with a high-pressure (about 3 kbar) deuterium gas under irradiation by γ-quanta with an energy of 8.8 MeV. The measured concentrations of chemical elements arisen from nuclear reactions initiated by γ-quanta have made it possible to develop the phenomenological approach to describing the process whereby deuterium atoms are heated by the protons and neutrons of a deuteron photofission reaction, hot D-D fusion, Oppenheimer reactions, and palladium nuclear fission. The coefficient of the process efficiency greatly exceeds unity. A new type of reactors (deuterated nuclear fission reactor) is proposed.     

Quantum chemical modelling case studies relevant to metal oxide dissolution and catalysis

Over the past 20 years quantum-chemical methods have been developed sufficiently so that they can now be applied to the elucidation of the complex mechanistic processes that occur during metal oxide dissolution and catalysis reactions. Many of the reactions occurring during these processes are not directly accessible to experimental techniques and therefore quantum-chemical modelling can be applied to probe the individual reaction steps involved in the overall mechanism. Quantum chemistry provides the means of calculating the electronic properties of solids (e.g. band structures) structural properties of solids and surfaces (for instance surface relaxation and rumpling) heats of formation and reaction, activation energies, spectroscopic excitation energies and vibrational frequencies. Three case studies are described, which have been chosen to cover a range of quantum chemical applications and methodologies. These case studies are a) the dissolution mechanism of MgO, b) the parameterisation of titanium dioxide for the determination of electronic properties and c) the mechanism and energetics of adsorption of Pd onto rutile. These case studies utilise Hartree-Fock semiempirical andab initio quantum-chemical methods as well as density functional methodologies. A range of model types are used, namely cluster models embedded in pseudo-atoms, 3-dimensional periodic models and 2-dimensional periodic surface models.     

On the generation of picosecond light continua depending on various nonlinear processes

The generation of picosecond light continua depends on various nonlinear processes such as parametric four-photon interaction, self-phase modulation, self-focusing, and avalanche ionization. In order to systematize the influence of these processes we have indicated both the threshold for continuum generation measured by various authors and the threshold for the nonlinear processes in a power diameter diagram characterizing the laser beam. The result is that all the thresholds for continuum measured under very different experimental conditions are situated nearly on one curve given by the nonlinear process with the lowest threshold. We have carried out measurements on the spectral energy distribution and on the angular distribution of the continuum generated in water and alkali halides by a mode-locked single-pulse Nd-glass laser. Under our experimental conditions both self-phase modulation and parametric four-photon interaction contribute to continuum generation.     

Doorway states in nuclear reactions as a manifestation of the “super-radiant” mechanism

A mechanism is considered for generating doorway states and intermediate structure in low-energy nuclear reactions as a result of collectivization of widths of unstable intrinsic states coupled to common decay channels. At the limit of strong continuum coupling, the segregation of broad (“super-radiating”) and narrow (“trapped”) states occurs revealing the separation of direct and compound processes. We discuss the conditions for the appearance of intermediate structure in this process and doorways related to certain decay channels.     

Observation of chemical reactions between alkaline-earth oxides and tungsten at high pressure and high temperature

The potential chemical reactions of alkaline-earth oxides (AeO with Ae: Mg, Ca, Sr, and Ba) and tungsten are studied at high pressure and high temperature. At pressures ranging from 5 to 10 GPa and temperatures of 2000 K, a noticeable reaction between AeO and powder tungsten (W) was detected. As a product of the reaction, scheelite-structured orthotungstates (AeWO₄) were formed. The reactivity of alkaline-earth oxides with tungsten increases in the order Ca<Sr<Ba, being the reaction not detected for MgO. Possible chemical reactions leading to the formation of alkaline-earth orthotungstates have been considered. Our results support the conclusion that the most probable reaction occurring under high-pressure and high-temperature conditions is AeO+W+3/2 O₂→AeWO₄.     

Computational analysis of the roles of biochemical reactions in anomalous diffusion dynamics

Most biochemical processes in cells are usually modeled by reaction–diffusion(RD) equations. In these RD models,the diffusive process is assumed to be Gaussian. However, a growing number of studies have noted that intracellular diffusion is anomalous at some or all times, which may result from a crowded environment and chemical kinetics. This work aims to computationally study the effects of chemical reactions on the diffusive dynamics of RD systems by using both stochastic and deterministic algorithms. Numerical method to estimate the mean-square displacement(MSD) from a deterministic algorithm is also investigated. Our computational results show that anomalous diffusion can be solely due to chemical reactions. The chemical reactions alone can cause anomalous sub-diffusion in the RD system at some or all times.The time-dependent anomalous diffusion exponent is found to depend on many parameters, including chemical reaction rates, reaction orders, and chemical concentrations.     

Geometrical study of spark ignition in two dimensions

Spark ignition, as the first step during the combustion in Otto engines, has a profound impact on the further development of the flame kernel. Over the last ten years growing concern for environment protection, including low emission of pollutants has increased the interest in the numerical simulation of ignition phenomena to guarantee successful flame kernel development even for lean mixtures.

However, the process of spark ignition in a combustible mixture is not yet fully understood. The use of detailed reaction mechanisms, combined with electrodynamical modelling of the spark, is necessary to optimize ignition of lean mixtures.

This work presents simulations of the coupling of flow, chemical reactions and transport with discharge processes in order to investigate the development of a stable flame kernel initiated by an electrical spark. A two-dimensional code to simulate the early stages of flame kernel formation, shortly after the breakdown discharge, has been developed. The model includes Joule heating. The spark plasma channel formed as a consequence of the breakdown is incorporated into the initial conditions. The computations include the initial phase (1–5 µs), which is governed by pressure wave formation, but also the transition to flame propagation. A thorough study of the influence of the electrodes' geometry, i.e. shape and size, and gap width, has been performed for air and a lean H₂–air mixture. Also a detailed methane-air mechanism was chosen as another example including combustion.

Due to the fast expansion of the plasma channel, together with the geometrical complexity of the electrodes, a complicated flow field develops after the emission of a pressure wave by the expanding channel. Special numerical methods, including artificial viscosity, are required to resolve the complicated flow field during these first 1–5 µs. The heat release through chemical reactions and transport processes is almost negligible during this short phase. The second phase, i.e. the development of a propagating flame and the flame kernel expansion, can last up to several milliseconds and is dominated by diffusive processes and chemical reactions. It has been found that the geometry greatly influences the developing flame kernel and the flow field. As soon as chemical reactions begin to contribute significantly to the heat release, the effect becomes smaller.     

Effect of surface acoustic waves on activity in heterogeneous catalysis

A synopsis of the recent developments in acoustically influencing and controlling gas-surface interactions is presented. The cleaning effect of ultrasound and its surface activation play an important role for the sonochemical enhancement of reactivity in chemical processes involving solid and liquid phases. So far, there have only been a few studies on the effects of surface acoustic waves on surface chemical reactions under high-vacuum conditions by the application of piezoelectric surface acoustic wave transducers. Very recently, metal films deposited between InterDigital Transducer (IDT) electrodes on a LiNbO₃ substrate have shown a significant inerease in catalytic activity during surface acoustic excitation and Edge-Bonded Transducers (EBT) with a metal single crystal as a substrate have been used to acoustically influence the rate in the oscillatory reaction for CO oxidation. Tunable narrowband surface acoustic excitation is anticipated to be an efficient route to control catalytic processes, and in our work this approach is being used to investigate the physical basis of this process.     

模板对异构体选择性生长的动力学控制作用与化学气相沉积金刚石的生长机理

阐述了模板的动力学控制作用对大尺度有序结构特别是亚稳相的生长，对自由能相差很小的异构体的选择生长所具有的重要作用.汲取现有金刚石生长理论的合理思想，以模板概念为基础给出了对化学气相沉积(CVD)过程的动力学热力学综合描述：1)碳原子在碳氢化合物中的化学势高于固相碳，气相碳氢化合物的碳原子有可能落到化学势较低的固态碳的各种异构体.2)气相碳通过表面反应实现向固相碳的转化.3)表面的模板作用是控制气相碳原子转换方式的主要动力学因素，不同的表面(石墨各种取向的表面及金刚石不同取向的表面)选择了落入其上的碳原子的结构方式及能量状态.4)因此,衬底的不同区域可发生几种不同的独立的表面反应过程,这些反应对应于不同表面的生长.5）而这些表面反应的方向性及速度受表面临域热力学因素的影响，反应的方向性决定了某种晶面是生长或刻蚀，在特定的温度、压强及各种气体分压下可以实现金刚石的生长和石墨的刻蚀.6)衬底局域晶格结构及键价结构和衬底表面气相的温度、压强及各种气体分压等热力学条件共同决定了成核的临界条件.7）与外界有能量和物质交换的等离子体系统，以及气相中发生的一系列化学反应，仅起到了维持某种固相表面生长所需要的非平衡热力学条件和化学条件的作用.金刚石和石墨表面具有的模板动力学控制作用，在特定热力学条件下主导自身外延层的生长方式；异质衬底的某些局域微观结构可以作为新相生长成核的局域模板；不同材料、不同的处理方法、及不同的化学环境下的衬底具有不同的局域微观结构，从而决定了多晶薄膜的取向优势. 关键词： 模板 异构体 选择性生长 金刚石薄膜     

Modelling of chemical vapour deposition for optical fibre manufacture

A study of numerical modelling has been carried out for chemical vapour deposition processes with applications to manufacture of optical fibres. Temperature distributions and thermophoretic particle deposition have been calculated for the modified chemical vapour deposition (MCVD) and the outside vapour deposition (OVD) processes. A two torch formulation and a heat flux boundary condition are used for MCVD and the present model is shown to be capable of predicting tube wall temperatures and deposition profiles correctly. The present results are in agreement with experimental data. For OVD modelling, nonorthogonal body-fitted coordinates have been utilized to solve a conjugate problem including the jet flow and heat conduction through a two-layered cylinder that consists of an original target and the deposited porous layers. Surface temperatures and efficiencies of particle deposition have been obtained.     

Combustion in the future: The importance of chemistry

Combustion involves chemical reactions that are often highly exothermic. Combustion systems utilize the energy of chemical compounds released during this reactive process for transportation, to generate electric power, or to provide heat for various applications. Chemistry and combustion are interlinked in several ways. The outcome of a combustion process in terms of its energy and material balance, regarding the delivery of useful work as well as the generation of harmful emissions, depends sensitively on the molecular nature of the respective fuel. The design of efficient, low-emission combustion processes in compliance with air quality and climate goals suggests a closer inspection of the molecular properties and reactions of conventional, bio-derived, and synthetic fuels. Information about flammability, reaction intensity, and potentially hazardous combustion by-products is important also for safety considerations. Moreover, some of the compounds that serve as fuels can assume important roles in chemical energy storage and conversion. Combustion processes can furthermore be used to synthesize materials with attractive properties.A systematic understanding of the combustion behavior thus demands chemical knowledge. Desirable information includes properties of the thermodynamic states before and after the combustion reactions and relevant details about the dynamic processes that occur during the reactive transformations from the fuel and oxidizer to the products under the given boundary conditions. Combustion systems can be described, tailored, and improved by taking chemical knowledge into account. Combining theory, experiment, model development, simulation, and a systematic analysis of uncertainties enables qualitative or even quantitative predictions for many combustion situations of practical relevance.This article can highlight only a few of the numerous investigations on chemical processes for combustion and combustion-related science and applications, with a main focus on gas-phase reaction systems. It attempts to provide a snapshot of recent progress and a guide to exciting opportunities that drive such research beyond fossil combustion.     

Sono-leather technology with ultrasound: a boon for unit operations in leather processing - review of our research work at Central Leather Research Institute (CLRI), India

Ultrasound is a sound wave with a frequency above the human audible range of 16Hz to 16kHz. In recent years, numerous unit operations involving physical as well as chemical processes are reported to have been enhanced by ultrasonic irradiation. There have been benefits such as improvement in process efficiency, process time reduction, performing the processes under milder conditions and avoiding the use of some toxic chemicals to achieve cleaner processing. These could be a better way of augmentation for the processes as an advanced technique. The important point here is that ultrasonic irradiation is physical method activation rather than using chemical entities. Detailed studies have been made in the unit operations related to leather such as diffusion rate enhancement through porous leather matrix, cleaning, degreasing, tanning, dyeing, fatliquoring, oil-water emulsification process and solid-liquid tannin extraction from vegetable tanning materials as well as in precipitation reaction in wastewater treatment. The fundamental mechanism involved in these processes is ultrasonic cavitation in liquid media. In addition to this there also exist some process specific mechanisms for the enhancement of the processes. For instance, possible real-time reversible pore-size changes during ultrasound propagation through skin/leather matrix could be a reason for diffusion rate enhancement in leather processing as reported for the first time. Exhaustive scientific research work has been carried out in this area by our group working in Chemical Engineering Division of CLRI and most of these benefits have been proven with publications in valued peer-reviewed international journals. The overall results indicate that about 2-5-fold increase in the process efficiency due to ultrasound under the given process conditions for various unit operations with additional benefits. Scale-up studies are underway for converting these concepts in to a real viable larger scale operation. In the present paper, summary of our research findings from employing this technique in various unit operations such as cleaning, diffusion, emulsification, particle-size reduction, solid-liquid leaching (tannin and natural dye extraction) as well as precipitation has been presented.     

Laser spectroscopy for studying chemical processes

In recent years, various methods have been developed to observe and to influence the course of chemical reactions using laser radiation. By selectively increasing the translational, rotational, and vibrational energies and by controlling the relative orientation of the reaction partners with tunable infrared and UV lasers, direct insight can be gained into the molecular course of the breaking and re-forming of chemical bonds. As exmaples for the application of lasers in chemical synthesis the production of monomers and catalysts is discussed. The application of linear and nonlinear laser spectroscopic methods, such as laser-induced fluorescence (LIF), Coherent anti-Stokes Raman Scattering (CARS), infrared-absorption measurements with tunable diode and molecular lasers is described for non-intrusive observation of the interaction of transport processes with chemical reactions used in industrial processes with high temporal, spectral and spatial resolution. Finally the application of a UV laser microbeam apparatus in genetic engineering for laser-induced cell fusion, genetic transformation of plant cells as well as diagnosis of human diseases by laser-microdissection of chromosomes is described.