Optimisation of Kinetic Parameters for an After-treatment Catalyst

Mathematical modelling has become an essential tool in the design of modern catalytic systems. Emissions legislation is becoming increasingly stringent, and so mathematical models of aftertreatment systems must become more accurate in order to provide confidence that a catalyst will convert pollutants over the required range of conditions. 
Automotive catalytic converter models contain several sub-models that represent processes such as mass and heat transfer, and the rates at which the reactions proceed on the surface of the precious metal. Of these sub-models, the prediction of the surface reaction rates is by far the most challenging due to the complexity of the reaction system and the large number of gas species involved. The reaction rate sub-model uses global reaction kinetics to describe the surface reaction rate of the gas species and is based on the Langmuir Hinshelwood equation further developed by Voltz et al. [1] The reactions can be modelled using the pre-exponential and activation energies of the Arrhenius equations and the inhibition terms. 
The reaction kinetic parameters of aftertreatment models are found from experimental data, where a measured light-off curve is compared against a predicted curve produced by a mathematical model. The kinetic parameters are usually manually tuned to minimize the error between the measured and predicted data. This process is most commonly long, laborious and prone to misinterpretation due to the large number of parameters and the risk of multiple sets of parameters giving acceptable fits. Moreover, the number of coefficients increases greatly with the number of reactions. Therefore, with the growing number of reactions, the task of manually tuning the coefficients is becoming increasingly challenging. 
In the presented work, the authors have developed and implemented a multi-objective genetic algorithm to automatically optimize reaction parameters in AxiSuite®, [2] a commercial aftertreatment model. The genetic algorithm was developed and expanded from the code presented by Michalewicz et al. [3] and was linked to AxiSuite using the Simulink add-on for Matlab. 
The default kinetic values stored within the AxiSuite model were used to generate a series of light-off curves under rich conditions for a number of gas species, including CO, NO, C_{3H8 and C3H6. These light-off curves were used to generate an objective function.} 
This objective function was used to generate a measure of fit for the kinetic parameters. The multi-objective genetic algorithm was subsequently used to search between specified limits to attempt to match the objective function. In total the pre-exponential factors and activation energies of ten reactions were simultaneously optimized. 
The results reported here demonstrate that, given accurate experimental data, the optimization algorithm is successful and robust in defining the correct kinetic parameters of a global kinetic model describing aftertreatment processes.

Evaluation of an in situ spatial resolution instrument for fixed beds through the assessment of the invasiveness of probes and a comparison with a micro-kinetic model

This paper reports the detailed description and validation of a fully automated, computer controlled analytical method to spatially probe the gas composition and thermal characteristics in packed bed systems. This method has been designed to limit the invasiveness of the probe, a characteristic assessed using CFD. The thermocouple is aligned with the sampling holes to enable simultaneous recording of the gas composition and temperature profiles. This analysis technique has been validated by studying CO oxidation over a 1% Pt/Al2O3 catalyst. The resultant profiles have been compared with a micro-kinetic model, to further assess the strength of the technique. 

Characterisation of deuterium spectra from laser driven multi-species sources by employing differentially filtered image plate detectors in Thomson spectrometers

A novel method for characterising the full spectrum of deuteron ions emitted by laser driven multi-species ion sources is discussed. The procedure is based on using differential filtering over the detector of a Thompson parabola ion spectrometer, which enables discrimination of deuterium ions from heavier ion species with the same charge-to-mass ratio (such as C^{6 +}, O^{8 +}, etc.). Commonly used Fuji Image plates were used as detectors in the spectrometer, whose absolute response to deuterium ions over a wide range of energies was calibrated by using slotted CR-39 nuclear track detectors. A typical deuterium ion spectrum diagnosed in a recent experimental campaign is presented, which was produced from a thin deuterated plastic foil target irradiated by a high power laser.

Spitzer Space Telescope spectra of post-AGB stars in the large magellanic Cloud-polycyclic aromatic hydrocarbons at low metallicities

This paper reports variations of polycyclic aromatic hydrocarbons (PAHs) features that were found in Spitzer Space Telescope spectra of carbon-rich post-asymptotic giant branch (post-AGB) stars in the Large Magellanic Cloud (LMC). The paper consists of two parts. The first part describes our Spitzer spectral observing programme of 24 stars including post-AGB candidates. The latter half of this paper presents the analysis of PAH features in 20 carbon-rich post-AGB stars in the LMC, assembled from the Spitzer archive as well as from our own programme.We found that five post-AGB stars showed a broad feature with a peak at 7.7 μm, that had not been classified before. Further, the 10-13 μm PAH spectra were classified into four classes, one of which has three broad peaks at 11.3, 12.3 and 13.3 μm rather than two distinct sharp peaks at 11.3 and 12.7 μm, as commonly found in HII regions. Our studies suggest that PAHs are gradually processed while the central stars evolve from post-AGB phase to planetary nebulae, changing their composition before PAHs are incorporated into the interstellar medium. Although some metallicity dependence of PAH spectra exists, the evolutionary state of an object is more significant than its metallicity in determining the spectral characteristics of PAHs for LMC and Galactic post-AGB stars. © 2014 The Authors Published by Oxford University Press on behalf of the Royal Astronomical Society.

Chemistry and Mechanism of Alizarin Red S and Methylene Blue Biosorption onto Olive Stone: Equilibrium and Kinetic

The biosorption process of anionic dye Alizarin Red S (ARS) and cationic dye methylene blue (MB) as a function of solution pH, initial concentration and contact time onto olive stone (OS) biomass has been investigated. The main objectives of the current study are to: (i) study the chemistry and the mechanism of ARS and MB biosorption onto olive stone and the type of OS–ARS, MB interactions occurring, (ii) study the biosorption equilibrium and kinetic experimental data required for the design and operation of column reactors. Equilibrium biosorption isotherms and kinetics were also examined. Experimental equilibrium data were fitted to four different isotherms by non-linear regression method, however, the biosorption experimental data for ARS and MB dyes were well interpreted by the Temkin and Langmuir isotherms, respectively. The maximum monolayer adsorption capacity for ARS and MB dyes were 109.0 and 102.6 mg/g, respectively. The kinetic data of the two dyes could be better described by the pseudo second-order model. The data showed that olive stone can be effectively used for removing dyes from wastewater.

A study of the kinetic solvent isotope effect on the destruction of microcystin-LR and geosmin using TiO2 photocatalysis

We have previously reported the effectiveness of TiO₂ photocatalysis in the destruction of species generated by cyanobacteria, specifically geosmin and microcystin-LR. In this paper we report an investigation of factors which influence the rate of the toxin destruction at the catalyst surface. A primary kinetic solvent isotope effect of approximately 1.5 was observed when the destruction was performed in a heavy water solvent. This is in contrast to previous reports of a solvent isotope effect of approximately 3, however, these studies were undertaken with a different photocatalyst material. The solvent isotope effect therefore appears to be dependent on the photocatalyst material used. The results of the study support the theory that the photocatalytic decomposition occurs on the catalyst surface rather than in the bulk of the solution. Furthermore it appears that the rate determining step is not oxygen reduction as previously reported. 

The application of Raman and anti-stokes Raman spectroscopy for in situ monitoring of structural changes in laser irradiated titanium dioxide materials

The use of Raman and anti-stokes Raman spectroscopy to investigate the effect of exposure to high power laser radiation on the crystalline phases of TiO₂ has been investigated. Measurement of the changes, over several time integrals, in the Raman and anti-stokes Raman of TiO₂ spectra with exposure to laser radiation is reported. Raman and anti-stokes Raman provide detail on both the structure and the kinetic process of changes in crystalline phases in the titania material. The effect of laser exposure resulted in the generation of increasing amounts of the rutile crystalline phase from the anatase crystalline phase during exposure. The Raman spectra displayed bands at 144 cm^-1 (A1g), 197 cm^-1 (Eg), 398 cm^-1 (B1g), 515 cm^-1 (A1g), and 640 cm^-1 (Eg) assigned to anatase which were replaced by bands at 143 cm^-1 (B1g), 235 cm^-1 (2 phonon process), 448 cm^-1 (Eg) and 612 cm^-1 (A1g) which were assigned to rutile. This indicated that laser irradiation of TiO₂ changes the crystalline phase from anatase to rutile. Raman and anti-stokes Raman are highly sensitive to the crystalline forms of TiO₂ and allow characterisation of the effect of laser irradiation upon TiO₂. This technique would also be applicable as an in situ method for monitoring changes during the laser irradiation process

Vlasov-kinetic computer simulations of electrostatic waves in dusty plasmas: an overview of recent results

A series of numerical simulations based on a recurrence-free Vlasov kinetic model using kinetic phase point trajectories are presented. Electron-ion plasmas and three-component (electron-ion-dust) dusty or complex plasmas are considered, via independent simulations. Considering all plasma components modeled through a kinetic approach, the linear and nonlinear behavior of ion-acoustic excitations is investigated. Maxwellian and kappa-type (superthermal) distribution functions are assumed, as initial conditions, in separate simulations for the sake of comparison. The focus is on the parametric dependence of ion-acoustic waves on the electron-to-ion temperature ratio and on the dust concentration. © 2014 EDP Sciences, SIF, Springer-Verlag Berlin Heidelberg.

Multicomponent kinetic simulation of Bernstein-Greene-Kruskal modes associated with ion acoustic and dust-ion acoustic excitations in electron-ion and dusty plasmas

A series of numerical simulations based on a recurrence-free Vlasov kinetic algorithm presented earlier [Abbasi et al., Phys. Rev. E 84, 036702 (2011)] are reported. Electron-ion plasmas and three-component (electron-ion-dust) dusty, or complex, plasmas are considered, via independent simulations. Considering all plasma components modeled through a kinetic approach, the nonlinear behavior of ionic scale acoustic excitations is investigated. The focus is on Bernstein-Greene-Kruskal (BGK) modes generated during the simulations. In particular, we aim at investigating the parametric dependence of the characteristics of BGK structures, namely of their time periodicity (τ trap) and their amplitude, on the electron-to-ion temperature ratio and on the dust concentration. In electron-ion plasma, an exponential relation between τ trap and the amplitude of BGK modes and the electron-to-ion temperature ratio is observed. It is argued that both characteristics, namely, the periodicity τ trap and amplitude, are also related to the size of the phase-space vortex which is associated with BGK mode creation. In dusty plasmas, BGK modes characteristics appear to depend on the dust particle density linearly

Intensity Enhancement of O VI Ultraviolet Emission Lines in Solar Spectra due to Opacity

Opacity is a property of many plasmas. It is normally expected that if an emission line in a plasma becomes optically thick, then its intensity ratio to that of another transition that remains optically thin should decrease. However, radiative transfer calculations undertaken both by ourselves and others predict that under certain conditions the intensity ratio of an optically thick to an optically thin line can show an increase over the optically thin value, indicating an enhancement in the former. These conditions include the geometry of the emitting plasma and its orientation to the observer. A similar effect can take place between lines of differing optical depths. While previous observational studies have focused on stellar point sources, here we investigate the spatially resolved solar atmosphere using measurements of the I(1032 Å)/I(1038 Å) intensity ratio of O VI in several regions obtained with the Solar Ultraviolet Measurements of Emitted Radiation instrument on board the Solar and Heliospheric Observatory satellite. We find several I(1032 Å)/I(1038 Å) ratios observed on the disk to be significantly larger than the optically thin value of 2.0, providing the first detection (to our knowledge) of intensity enhancement in the ratio arising from opacity effects in the solar atmosphere. The agreement between observation and theory is excellent and confirms that the O VI emission originates from a slab-like geometry in the solar atmosphere, rather than from cylindrical structures.

Aza-annulation of enaminones with itaconic anhydride:kinetic preference for exocyclic enamide products

Enaminones react with itaconic anhydride in methylene chloride at room temperature to give exocyclic enamides sis the major products. These can be readily equilibrated to the thermodynamically more stable endocyclic enamides. In substrates where the exocyclic isomer could not be formed only intractable materials were produced from this reaction. An intermediate in this two step process was detected and identified by proton and C-13 NMR spectroscopy. In two cases chiral enaminones were employed and the relative stereochemistry at the new chiral centre in the product was established by a crystal structure of compound 27.

Sputtering of oxygen ice by low energy ions

Naturally occurring ices lie on both interstellar dust grains and on celestial objects, such as those in the outer Solar system. These ices are continuously subjected to irradiation by ions from the solar wind and/or cosmic rays, which modify their surfaces. As a result, new molecular species may form which can be sputtered off into space or planetary atmospheres. We determined the experimental values of sputtering yields for irradiation of oxygen ice at 10 K by singly (He+, C+, N+, O+ and Ar+) and doubly (C2 +, N2 + and O2 +) charged ions with 4 keV kinetic energy. In these laboratory experiments, oxygen ice was deposited and irradiated by ions in an ultra high vacuum chamber at low temperature to simulate the environment of space. The number of molecules removed by sputtering was observed by measurement of the ice thickness using laser interferometry. Preliminary mass spectra were taken of sputtered species and of molecules formed in the ice by temperature programmed desorption (TPD). We find that the experimental sputtering yields increase approximately linearly with the projectile ion mass (or momentum squared) for all ions studied. No difference was found between the sputtering yields for singly and doubly charged ions of the same atom within the experimental uncertainty, as expected for a process dominated by momentum transfer. The experimental sputter yields are in good agreement with values calculated using a theoretical model except in the case of oxygen ions. Preliminary studies have shown molecular oxygen as the dominant species sputtered and TPD measurements indicate ozone formation.

Rapid Oscillations in the Solar Atmosphere: Spectra and Physical Effects

High-frequency fluctuations are observed with the Rapid Oscillations in the Solar Atmosphere (ROSA) instrument (Jess et al. 2010, Solar Phys, 261, 363) at the Dunn Solar Telescope. This can produce simultaneous observations in up to six channels, at different heights in the photosphere and chromosphere, at an unprecedentedly high cadence of 0.5 seconds, and at a spatial resolution of 100 km after photometrically correct speckle reconstruction. Here we concentrate on observations at two levels. The first is in the G-band of the CH radical at 4305.5Å, bandpass 9.2Å, with height of formation z <250 km at a cadence of 0.525 sec corresponding to Nyquist frequency 950 mHz. The second is in the Ca II K-line core at 3933.7Å, bandpass 1.0Å, with height of formation z <1300 km, and cadence 4.2 sec giving Nyquist frequency 120 mHz. The data span 53 min, and the maximum field of view is 45 Mm. The data were taken on 28 May 2009 in internetwork and network near disk center. Using both Fourier and Morlet wavelet methods we find evidence in the G-band spectra for intensity fluctuations above noise out to frequencies f >> 100 mHz. The K-line signal is noisier and is seen only for f <50 mHz. With wavelet techniques we find that G-band spectral power with 20 <f <100 mHz is clearly concentrated in the intergranular lanes and especially at the locations of magnetic elements indicated by G-band bright points. This wavelet power is highly intermittent in time. By cross-correlating the data we find that pulses of high-frequency G-band power in the photosphere tend to be followed by increases in K-line emission in the chromosphere with a time lag of about 2 min.