Front propagation in spatially modulated media

A two-dimensional reaction-diffusion front which propagates in a modulated medium is studied. The modulation consists of a spatial variation of the local front velocity in the transverse direction to that of the front propagation. We study analytically and numerically the final steady-state velocity and shape of the front, resulting from a nontrivial interplay between the local curvature effects and the global competition process between different maxima of the control parameter. The transient dynamics of the process is also studied numerically and analytically by means of singular perturbation techniques.

Wave competition in excitable modulated media.

The propagation of an initially planar front is studied within the framework of the photosensitive Belousov-Zhabotinsky reaction modulated by a smooth spatial variation of the local front velocity in the direction perpendicular to front propagation. Under this modulation, the wave front develops several fingers corresponding to the local maxima of the modulation function. After a transient, the wave front achieves a stationary shape that does not necessarily coincide with the one externally imposed by the modulation. Theoretical predictions for the selection criteria of fingers and steady-state velocity are experimentally validated.

Evidence of chemical reactions in the hydroxyapatite laser ablation plume with a water atmosphere

The expansion dynamics of the ablation plume generated by KrF laser irradiation of hydroxyapatite targets in a 0.1 mbar water atmosphere has been studied by fast intensified charge coupled device imaging with the aid of optical bandpass filters. The aim of the filters is to isolate the emission of a single species, which allows separate analysis of its expansion. Images obtained without a filter revealed two emissive components in the plume, which expand at different velocities for delay times of up to 1.1 ¿s. The dynamics of the first component is similar to that of a spherical shock wave, whereas the second component, smaller than the first, expands at constant velocity. Images obtained through a 520 nm filter show that the luminous intensity distribution and evolution of emissive atomic calcium is almost identical to those of the first component of the total emission and that there is no contribution from this species to the emission from the second component of the plume. The analysis through a 780 nm filter reveals that atomic oxygen partially diffuses into the water atmosphere and that there is a contribution from this species to the emission from the second component. The last species studied here, calcium oxide, was analyzed by means of a 600 nm filter. The images revealed an intensity pattern more complex than those from the atomic species. Calcium oxide also contributes to the emission from the second component. Finally, all the experiments were repeated in a Ne atmosphere. Comparison of the images revealed chemical reactions between the first component of the plume and the water atmosphere.

Front propagation in spatially modulated media

A two-dimensional reaction-diffusion front which propagates in a modulated medium is studied. The modulation consists of a spatial variation of the local front velocity in the transverse direction to that of the front propagation. We study analytically and numerically the final steady-state velocity and shape of the front, resulting from a nontrivial interplay between the local curvature effects and the global competition process between different maxima of the control parameter. The transient dynamics of the process is also studied numerically and analytically by means of singular perturbation techniques.

Wave competition in excitable modulated media.

The propagation of an initially planar front is studied within the framework of the photosensitive Belousov-Zhabotinsky reaction modulated by a smooth spatial variation of the local front velocity in the direction perpendicular to front propagation. Under this modulation, the wave front develops several fingers corresponding to the local maxima of the modulation function. After a transient, the wave front achieves a stationary shape that does not necessarily coincide with the one externally imposed by the modulation. Theoretical predictions for the selection criteria of fingers and steady-state velocity are experimentally validated.

Regular wave propagation out of noise in chemical active media

A pacemaker, regularly emitting chemical waves, is created out of noise when an excitable photosensitive Belousov-Zhabotinsky medium, strictly unable to autonomously initiate autowaves, is forced with a spatiotemporal patterned random illumination. These experimental observations are also reproduced numerically by using a set of reaction-diffusion equations for an activator-inhibitor model, and further analytically interpreted in terms of genuine coupling effects arising from parametric fluctuations. Within the same framework we also address situations of noise-sustained propagation in subexcitable media.

Self-potentials in partially saturated media: the importance of explicit modeling of electrode effects

Self-potential (SP) data are of interest to vadose zone hydrology because of their direct sensitivity to water flow and ionic transport. There is unfortunately little consensus in the literature about how to best model SP data under partially saturated conditions, and different approaches (often supported by one laboratory data set alone) have been proposed. We argue that this lack of agreement can largely be traced to electrode effects that have not been properly taken into account. A series of drainage and imbibition experiments were considered in which we found that previously proposed approaches to remove electrode effects were unlikely to provide adequate corrections. Instead, we explicitly modeled the electrode effects together with classical SP contributions using a flow and transport model. The simulated data agreed overall with the observed SP signals and allowed decomposing the different signal contributions to analyze them separately. After reviewing other published experimental data, we suggest that most of them include electrode effects that have not been properly taken into account. Our results suggest that previously presented SP theory works well when considering the modeling uncertainties presently associated with electrode effects. Additional work is warranted to not only develop suitable electrodes for laboratory experiments but also to assure that associated electrode effects that appear inevitable in longer term experiments are predictable, so that they can be incorporated into the modeling framework.

Role of lipid reactions in quality of oat products

Selostus: Rasvojen reaktiot prosessoiduissa kauratuotteissa

'Freakish Fat', 'Wretched Black': Female abject beings in contemporary Colombian media and culture

This paper explores the construction of female abject beings in Colombian contemporary media and culture comparing a character in the 2010 telenovela Chepe Fortuna named Venezuela, and the cultural representation of Piedad Córdoba. I argue that the construction of these two characters as abject beings is coherent with the dominant discourse of Alvaro Uribe's national project, which relied on a strong nationalist rhetoric based on binary oppositions of the type "we/other." In this context both Chepe Fortuna's Venezuela and Piedad Córdoba are constructed as "other." While Venezuela's abjection is partly effected on the basis of her being fat and black, Córdoba's is on the basis of her being a left-wing politician, and mediated through her being a black female. These two instances evidence an approach to femaleness that goes hand-in-hand with particular understandings of female subjectivity within current post-feminist paradigms.

FAST GC-FID METHOD FOR MONITORING ACIDIC AND BASIC CATALYTIC TRANSESTERIFICATION REACTIONS IN VEGETABLE OILS TO METHYL ESTER BIODIESEL PREPARATION

A fast gas chromatography with a flame ionisation detector (GC-FID) method for the simultaneous analysis of methyl palmitate (C16:0), stearate (C18:0), oleate (C18:1), linoleate (C18:2) and linolenate (C18:3) in biodiesel samples was proposed. The analysis was conducted in a customised ionic-liquid stationary-phase capillary, SLB-IL 111, with a length of 14 m, an internal diameter of 0.10 mm, a film thickness of 0.08 µm and operated isothermally at 160 °C using hydrogen as the carrier gas at a rate of 50 cm s-1 in run time about 3 min. Once methyl myristate (C14:0) is present lower than 0.5% m/m in real samples it was used as an internal standard. The method was successful applied to monitoring basic and acidic catalysis transesterification reactions of vegetable oils such as soybean, canola, corn, sunflower and those used in frying process.

Kinetic modeling of mechanisms of industrially important organic reactions in gas and liquid phase

This dissertation is based on 5 articles which deal with reaction mechanisms of the following selected industrially important organic reactions: 1. dehydrocyclization of n-butylbenzene to produce naphthalene 2. dehydrocyclization of 1-(p-tolyl)-2-methylbutane (MB) to produce 2,6-dimethylnaphthalene 3. esterification of neopentyl glycol (NPG) with different carboxylic acids to produce monoesters 4. skeletal isomerization of 1-pentene to produce 2-methyl-1-butene and 2-methyl-2-butene The results of initial- and integral-rate experiments of n-butylbenzene dehydrocyclization over selfmade chromia/alumina catalyst were applied when investigating reaction 2. Reaction 2 was performed using commercial chromia/alumina of different acidity, platina on silica and vanadium/calcium/alumina as catalysts. On all catalysts used for the dehydrocyclization, major reactions were fragmentation of MB and 1-(p-tolyl)-2-methylbutenes (MBes), dehydrogenation of MB, double bond transfer, hydrogenation and 1,6-cyclization of MBes. Minor reactions were 1,5-cyclization of MBes and methyl group fragmentation of 1,6- cyclization products. Esterification reactions of NPG were performed using three different carboxylic acids: propionic, isobutyric and 2-ethylhexanoic acid. Commercial heterogeneous gellular (Dowex 50WX2), macroreticular (Amberlyst 15) type resins and homogeneous para-toluene sulfonic acid were used as catalysts. At first NPG reacted with carboxylic acids to form corresponding monoester and water. Then monoester esterified with carboxylic acid to form corresponding diester. In disproportionation reaction two monoester molecules formed NPG and corresponding diester. All these three reactions can attain equilibrium. Concerning esterification, water was removed from the reactor in order to prevent backward reaction. Skeletal isomerization experiments of 1-pentene were performed over HZSM-22 catalyst. Isomerization reactions of three different kind were detected: double bond, cis-trans and skeletal isomerization. Minor side reaction were dimerization and fragmentation. Monomolecular and bimolecular reaction mechanisms for skeletal isomerization explained experimental results almost equally well. Pseudohomogeneous kinetic parameters of reactions 1 and 2 were estimated by usual least squares fitting. Concerning reactions 3 and 4 kinetic parameters were estimated by the leastsquares method, but also the possible cross-correlation and identifiability of parameters were determined using Markov chain Monte Carlo (MCMC) method. Finally using MCMC method, the estimation of model parameters and predictions were performed according to the Bayesian paradigm. According to the fitting results suggested reaction mechanisms explained experimental results rather well. When the possible cross-correlation and identifiability of parameters (Reactions 3 and 4) were determined using MCMC method, the parameters identified well, and no pathological cross-correlation could be seen between any parameter pair.

Modelling of combustion and sorbent reactions in three-dimensional flow environment of a circulating fluidized bed furnace

This thesis presents a three-dimensional, semi-empirical, steady state model for simulating the combustion, gasification, and formation of emissions in circulating fluidized bed (CFB) processes. In a large-scale CFB furnace, the local feeding of fuel, air, and other input materials, as well as the limited mixing rate of different reactants produce inhomogeneous process conditions. To simulate the real conditions, the furnace should be modelled three-dimensionally or the three-dimensional effects should be taken into account. The only available methods for simulating the large CFB furnaces three-dimensionally are semi-empirical models, which apply a relatively coarse calculation mesh and a combination of fundamental conservation equations, theoretical models and empirical correlations. The number of such models is extremely small. The main objective of this work was to achieve a model which can be applied to calculating industrial scale CFB boilers and which can simulate all the essential sub-phenomena: fluid dynamics, reactions, the attrition of particles, and heat transfer. The core of the work was to develop the model frame and the required sub-models for determining the combustion and sorbent reactions. The objective was reached, and the developed model was successfully used for studying various industrial scale CFB boilers combusting different types of fuel. The model for sorbent reactions, which includes the main reactions for calcitic limestones, was applied for studying the new possible phenomena occurring in the oxygen-fired combustion. The presented combustion and sorbent models and principles can be utilized in other model approaches as well, including other empirical and semi-empirical model approaches, and CFD based simulations. The main achievement is the overall model frame which can be utilized for the further development and testing of new sub-models and theories, and for concentrating the knowledge gathered from the experimental work carried out at bench scale, pilot scale and industrial scale apparatus, and from the computational work performed by other modelling methods.

Modeling study of limestone reactions in fluidized bed conditions

Traditionally limestone has been used for the flue gas desulfurization in fluidized bed combustion. Recently, several studies have been carried out to examine the use of limestone in applications which enable the removal of carbon dioxide from the combustion gases, such as calcium looping technology and oxy-fuel combustion. In these processes interlinked limestone reactions occur but the reaction mechanisms and kinetics are not yet fully understood. To examine these phenomena, analytical and numerical models have been created. In this work, the limestone reactions were studied with aid of one-dimensional numerical particle model. The model describes a single limestone particle in the process as a function of time, the progress of the reactions and the mass and energy transfer in the particle. The model-based results were compared with experimental laboratory scale BFB results. It was observed that by increasing the temperature from 850 °C to 950 °C the calcination was enhanced but the sulfate conversion was no more improved. A higher sulfur dioxide concentration accelerated the sulfation reaction and based on the modeling, the sulfation is first order with respect to SO2. The reaction order of O2 seems to become zero at high oxygen concentrations.

Limestone Reactions in a Fluidized Bed Heat Exchanger of an Oxy-fuel Circulating Fluidized Bed Boiler

Oxy-fuel combustion in a circulating fluidized bed (CFB) boiler appears to be a promising option for capturing CO2 in power plants. Oxy-fuel combustion is based on burning of fuel in the mixture of oxygen and re-circulated flue gas instead of air. Limestone (CaCO3) is typically used for capturing of SO2 in CFB boilers where limestone calcines to calcium oxide (CaO). Because of high CO2 concentration in oxy-fuel combustion, calcination reaction may be hindered or carbonation, the reverse reaction of calcination, may occur. Carbonation of CaO particles can cause problems especially in the circulation loop of a CFB boiler where temperature level is lower than in the furnace. The aim of the thesis was to examine carbonation of CaO in a fluidized bed heat exchanger of a CFB boiler featuring oxy-fuel combustion. The calculations and analyzing were based on measurement data from an oxy-fuel pilot plant and on 0-dimensional (0D) gas balance of a fluidized bed heat exchanger. Additionally, the objective was to develop a 1-dimensional (1D) model of a fluidized bed heat exchanger by searching a suitable pre-exponential factor for a carbonation rate constant. On the basis of gas measurement data and the 0D gas balance, it was found that the amount of fluidization gas decreased as it flew through the fluidized bed heat exchanger. Most likely the reason for this was carbonation of CaO. It was discovered that temperature has a promoting effect on the reaction rate of carbonation. With the 1D model, a suitable pre-exponential factor for the equation of carbonation rate constant was found. However, during measurements there were several uncertainties, and in the calculations plenty of assumptions were made. Besides, the temperature level in the fluidized bed heat exchanger was relatively low during the measurements. Carbonation should be considered when fluidized bed heat exchangers and the capacity of related fans are designed for a CFB boiler with oxy-fuel combustion.