Application of Information Statistical Theory to the Description of the Effect of Heat Conduction on the Chemical Reaction Rate in Gases

The effect of the heat flux on the rate of chemical reaction in dilute gases is shown to be important for reactions characterized by high activation energies and in the presence of very large temperature gradients. This effect, obtained from the second-order terms in the distribution function (similar to those obtained in the Burnett approximation to the solution of the Boltzmann equation), is derived on the basis of information theory. It is shown that the analytical results describing the effect are simpler if the kinetic definition for the nonequilibrium temperature is introduced than if the thermodynamic definition is introduced. The numerical results are nearly the same for both definitions

Characterization and Control Strategies of an Integrated Chemical-Biological System for the Remediation of Toxic Pollutants in Wastewater: A case of study

In a previous work, a hybrid system consisting of an advanced oxidation process (AOP) named Photo-Fenton (Ph-F) and a fixed bed biological treatment operating as a sequencing batch biofilm reactor (SBBR) was started-up and optimized to treat 200 mg·L-1 of 4-chlorophenol (4-CP) as a model compound. In this work, studies of reactor stability and control as well as microbial population determination by molecular biology techniques were carried out to further characterize and control the biological reactor. Results revealed that the integrated system was flexible and even able to overcome toxic shock loads. Oxygen uptake rate (OUR) in situ was shown to be a valid tool to control the SBBR operation, to detect toxic conditions to the biomass, and to assess the recovery of performance. A microbial characterization by 16S rDNA sequence analysis reveals that the biological population was varied, although about 30% of the bacteria belonged to the Wautersia genus.

L’impacte de les institucions internacionals sobre la Unió Europea: presa de decisions, integració i europeïtzació

Projecte de recerca elaborat a partir d’una estada a la Center for European Integration de la Freie Universität Berlin, Alemania, entre 2007 i 2009. El tema central del projecte consisteix en la descripció matemàtica de processos espai-temporals mitjançant la teoria dels Continuous-Time Random Walks. L'aportació més significativa del nostre treball en aquest camp consisteix en considerar per primera vegada la interacció entre diversos processos actuant de manera acoblada, ja que fins ara els models existents es limitaven a l'estudi de processos individuals o independents. Aquesta idea fa possible, per exemple, plantejar un sistema de transport en l'espai i a la vegada un procés de reacció (una reacció química, per exemple), i estudiar estadísticament com cada un pot alterar el comportament de l'altre. Això suposa un salt qualitatiu important en la descripció de processos de reacció-dispersió, ja que els nostres models permeten incorporar patrons de dispersió i comportaments temporals (cicles de vida) força realistes en comparació amb els models convencionals. Per tal de completar aquest treball teòric ha estat necessari també desenvolupar algunes eines numèriques (models de xarxa) per facilitar la implementació dels models. En la vessant pràctica, hem aplicat aquestes idees al cas de la dinàmica entre virus i el sistema immunològic que té lloc quan es produeix una infecció a l'organisme. Diferents estudis experimentals portats a terme els últims anys mostren com la resposta immunològica dels organismes superiors presenta una dinàmica temporal força complexa (per exemple, en el cas de la resposta programada). Per aquest motiu, les nostres tècniques matemàtiques són d'especial utilitat per a l'anàlisi d'aquests sistemes. Finalment, altres possibles aplicacions dels models, com ara l'estudi d'invasions biològiques, també han estat considerades.

Traveling waves and nonequilibrium stationary patterns in two-component reactive Langmuir monolayers

A simple kinetic model of a two-component phase-separating Langmuir monolayer with a chemical reaction is proposed. Its analysis and numerical simulations show that nonequilibrium periodic stationary structures and patterns of traveling stripes can spontaneously develop. The nonequilibrium phase diagram of this system is constructed and the properties of the patterns are discussed.

Compact thermal storage: a-state-of-the-art review of experimental results

Thermal energy storage (TES) can increase the thermal energy effieresa, of a process by reusing the waste heat from industrial process, solar energy or other sources. There are different ways to store thermal energy: by sensible heat, by latest heat, by sorption process or by chemical reaction. This thesrs provides a-state-of-the-art review of the experimental performance of TES systems based on solid gas sorption process and chemical reactions. The importance of theses processes is that provides a heat loss free storage system with a high energy density.

Inertial effects on reactive particles advected by turbulence

We study the problem of the advection of passive particles with inertia in a two-dimensional, synthetic, and stationary turbulent flow. The asymptotic analytical result and numerical simulations show the importance of inertial bias in collecting the particles preferentially in certain regions of the flow, depending on their density relative to that of the flow. We also study how these aggregates are affected when a simple chemical reaction mechanism is introduced through a Eulerian scheme. We find that inertia can be responsible for maintaining a stationary concentration pattern even under nonfavorable reactive conditions or destroying it under favorable ones.

Inertial effects on reactive particles advected by turbulence

We study the problem of the advection of passive particles with inertia in a two-dimensional, synthetic, and stationary turbulent flow. The asymptotic analytical result and numerical simulations show the importance of inertial bias in collecting the particles preferentially in certain regions of the flow, depending on their density relative to that of the flow. We also study how these aggregates are affected when a simple chemical reaction mechanism is introduced through a Eulerian scheme. We find that inertia can be responsible for maintaining a stationary concentration pattern even under nonfavorable reactive conditions or destroying it under favorable ones.

Study of chemical modification of alkaline lignin by the glyoxalation reaction

In this study, glyoxalated alkaline lignins with a non-volatile and non-toxic aldehyde, which can be obtained from several natural resources, namely glyoxal, were prepared and characterized for its use in wood adhesives. The preparation method consisted of the reaction of lignin with glyoxal under an alkaline medium. The influence of reaction conditions such as the molar ratio of sodium hydroxide-to-lignin and reaction time were studied relative to the properties of the prepared adducts. The analytical techniques used were FTIR and 1H-NMR spectroscopies, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Results from both the FTIR and 1H-NMR spectroscopies showed that the amount of introduced aliphatic hydroxyl groups onto the lignin molecule increased with increasing reaction time and reached a maximum value at 10 h, and after they began to decrease. The molecular weights remained unchanged until 10 h of reaction time, and then started to increase, possibly due to the repolymerization reactions. DSC analysis showed that the glass transition temperature (Tg) decreased with the introduction of glyoxal onto the lignin molecule due to the increase in free volume of the lignin molecules. TGA analysis showed that the thermal stability of glyoxalated lignin is not influenced and remained suitable for wood adhesives. Compared to the original lignin, the improved lignin is reactive and a suitable raw material for adhesive formula

Nonlinear chemoconvection in the Methylene-blue-glucose system

Interfacial hydrodynamic instabilities arise in a range of chemical systems. One mechanism for instability is the occurrence of unstable density gradients due to the accumulation of reaction products. In this paper we conduct two-dimensional nonlinear numerical simulations for a member of this class of system: the methylene-blue¿glucose reaction. The result of these reactions is the oxidation of glucose to a relatively, but marginally, dense product, gluconic acid, that accumulates at oxygen permeable interfaces, such as the surface open to the atmosphere. The reaction is catalyzed by methylene-blue. We show that simulations help to disassemble the mechanisms responsible for the onset of instability and evolution of patterns, and we demonstrate that some of the results are remarkably consistent with experiments. We probe the impact of the upper oxygen boundary condition, for fixed flux, fixed concentration, or mixed boundary conditions, and find significant qualitative differences in solution behavior; structures either attract or repel one another depending on the boundary condition imposed. We suggest that measurement of the form of the boundary condition is possible via observation of oxygen penetration, and improved product yields may be obtained via proper control of boundary conditions in an engineering setting. We also investigate the dependence on parameters such as the Rayleigh number and depth. Finally, we find that pseudo-steady linear and weakly nonlinear techniques described elsewhere are useful tools for predicting the behavior of instabilities beyond their formal range of validity, as good agreement is obtained with the simulations.

The prediction of chemical reactivity from first principles: Collision and reaction dynamics

Aquest treball fa una revisió de mesures experimentals i càlculs teòrics sobre la dinàmica de col·lisions i reaccions moleculars. Els experiments se centren en col·lisions, a energies intermèdies, que involucren sistemes del tipus ió-àtom i iómolècula, per les quals es mesuren seccions eficaces totals, estat a estat, així com aquelles que discerneixen les diferents contribucions del moment angular d'espín. Els resultats obtinguts s'interpreten satisfactòriament en termes d'acoblaments no adiabàtics entre els diferents estats electrònics dels sistemes col·lisionants. Els càlculs teòrics utilitzen la metodologia quasiclàssica, així com metodologies mecanoquàntiques recentment desenvolupades, tant aproximades com exactes. S'han obtingut resultats totalment convergits per sistemes tipus, mentre que s'han analitzat, de manera detallada i extensiva, les característiques dinàmiques de sistemes triatòmic, tetraatòmic i pentaatòmic.

Experimental evidence of localized oscillations in the photosensitive chlorine dioxide-iodine-malonic acid reaction

The interaction between Hopf and Turing modes has been the subject of active research in recent years. We present here experimental evidence of the existence of mixed Turing-Hopf modes in a two-dimensional system. Using the photosensitive chlorine dioxide-iodine-malonic acid reaction (CDIMA) and external constant background illumination as a control parameter, standing spots oscillating in amplitude and with hexagonal ordering were observed. Numerical simulations in the Lengyel-Epstein model for the CDIMA reaction confirmed the results.

Model-based diagnosis system: application to constructed wetlands

Report for the scientific sojourn carried out at the Model-based Systems and Qualitative Reasoning Group (Technical University of Munich), from September until December 2005. Constructed wetlands (CWs), or modified natural wetlands, are used all over the world as wastewater treatment systems for small communities because they can provide high treatment efficiency with low energy consumption and low construction, operation and maintenance costs. Their treatment process is very complex because it includes physical, chemical and biological mechanisms like microorganism oxidation, microorganism reduction, filtration, sedimentation and chemical precipitation. Besides, these processes can be influenced by different factors. In order to guarantee the performance of CWs, an operation and maintenance program must be defined for each Wastewater Treatment Plant (WWTP). The main objective of this project is to provide a computer support to the definition of the most appropriate operation and maintenance protocols to guarantee the correct performance of CWs. To reach them, the definition of models which represent the knowledge about CW has been proposed: components involved in the sanitation process, relation among these units and processes to remove pollutants. Horizontal Subsurface Flow CWs are chosen as a case study and the filtration process is selected as first modelling-process application. However, the goal is to represent the process knowledge in such a way that it can be reused for other types of WWTP.

Modelització i control d'un reactor de producció d'hidrogen per a l'alimentació de piles de combustible

Les piles de combustible permeten la transformació eficient de l’energia química de certs combustibles a energia elèctrica a través d’un procés electroquímic. De les diferents tecnologies de piles de combustible, les piles de combustible de tipus PEM són les més competitives i tenen una gran varietat d’aplicacions. No obstant, han de ser alimentades únicament per hidrogen. Per altra banda, l’etanol, un combustible interessant en el marc dels combustibles renovables, és una possible font d’hidrogen. Aquest treball estudia la reformació d’etanol per a l’obtenció d’hidrogen per a alimentar piles de combustible PEM. Només existeixen algunes publicacions que tractin l’obtenció d’hidrogen a partir d’etanol, i aquestes no inclouen l’estudi dinàmic del sistema. Els objectius del treball són el modelat i l’estudi dinàmic de reformadors d’etanol de baixa temperatura. Concretament, proposa un model dinàmic d’un reformador catalític d’etanol amb vapor basat en un catalitzador de cobalt. Aquesta reformació permet obtenir valors alts d’eficiència i valors òptims de monòxid de carboni que evitaran l’enverinament d’una la pila de combustible de tipus PEM. El model, no lineal, es basa en la cinètica obtinguda de diferents assaigs de laboratori. El reformador modelat opera en tres etapes: deshidrogenació d’etanol a acetaldehid i hidrogen, reformat amb vapor d’acetaldehid, i la reacció WGS (Water Gas Shift). El treball també estudia la sensibilitat i controlabilitat del sistema, caracteritzant així el sistema que caldrà controlar. L’anàlisi de controlabilitat es realitza sobre la resposta de dinàmica ràpida obtinguda del balanç de massa del reformador. El model no lineal és linealitzat amb la finalitat d’aplicar eines d’anàlisi com RGA, CN i MRI. El treball ofereix la informació necessària per a avaluar la possible implementació en un laboratori de piles de combustibles PEM alimentades per hidrogen provinent d’un reformador d’etanol.

Thermodynamics and log–contrast analysis in fluid geochemistry

There are two principal chemical concepts that are important for studying the naturalenvironment. The first one is thermodynamics, which describes whether a system is atequilibrium or can spontaneously change by chemical reactions. The second main conceptis how fast chemical reactions (kinetics or rate of chemical change) take place wheneverthey start. In this work we examine a natural system in which both thermodynamics andkinetic factors are important in determining the abundance of NH+4 , NO−2 and NO−3 insuperficial waters. Samples were collected in the Arno Basin (Tuscany, Italy), a system inwhich natural and antrophic effects both contribute to highly modify the chemical compositionof water. Thermodynamical modelling based on the reduction-oxidation reactionsinvolving the passage NH+4 -& NO−2 -& NO−3 in equilibrium conditions has allowed todetermine the Eh redox potential values able to characterise the state of each sample and,consequently, of the fluid environment from which it was drawn. Just as pH expressesthe concentration of H+ in solution, redox potential is used to express the tendency of anenvironment to receive or supply electrons. In this context, oxic environments, as thoseof river systems, are said to have a high redox potential because O2 is available as anelectron acceptor.Principles of thermodynamics and chemical kinetics allow to obtain a model that oftendoes not completely describe the reality of natural systems. Chemical reactions may indeedfail to achieve equilibrium because the products escape from the site of the rectionor because reactions involving the trasformation are very slow, so that non-equilibriumconditions exist for long periods. Moreover, reaction rates can be sensitive to poorly understoodcatalytic effects or to surface effects, while variables as concentration (a largenumber of chemical species can coexist and interact concurrently), temperature and pressurecan have large gradients in natural systems. By taking into account this, data of 91water samples have been modelled by using statistical methodologies for compositionaldata. The application of log–contrast analysis has allowed to obtain statistical parametersto be correlated with the calculated Eh values. In this way, natural conditions in whichchemical equilibrium is hypothesised, as well as underlying fast reactions, are comparedwith those described by a stochastic approach

Irreversible thermodynamics of Poisson processes with reaction

A kinetic model is derived to study the successive movements of particles, described by a Poisson process, as well as their generation. The irreversible thermodynamics of this system is also studied from the kinetic model. This makes it possible to evaluate the differences between thermodynamical quantities computed exactly and up to second-order. Such differences determine the range of validity of the second-order approximation to extended irreversible thermodynamics