Rigorous Multicomponent Reactive Separations Modelling : Complete Consideration of Reaction-Diffusion Phenomena

This paper gives the first step of the development of a rigorous multicomponent reactive separation model. Such a model is highly essential to further the optimization of acid gases removal plants (CO2 capture, gas treating, etc.) in terms of size and energy consumption, since chemical solvents are conventionally used.Firstly, two main modelling approaches are presented: the equilibrium-based and the rate-based approaches. Secondly, an extended rate-based model with rigorous modelling methodology for diffusion-reaction phenomena is proposed. The film theory and the generalized Maxwell-Stefan equations are used in order to characterize multicomponent interactions. The complete chain of chemical reactions is taken into account. The reactions can be kinetically controlled or at chemical equilibrium, and they are considered for both liquid film and liquid bulk. Thirdly, the method of numerical resolution is described. Coupling the generalized Maxwell-Stefan equations with chemical equilibrium equations leads to a highly non-linear Differential-Algebraic Equations system known as DAE index 3. The set of equations is discretized with finite-differences as its integration by Gear method is complex. The resulting algebraic system is resolved by the Newton- Raphson method. Finally, the present model and the associated methods of numerical resolution are validated for the example of esterification of methanol. This archetype non-electrolytic system permits an interesting analysis of reaction impact on mass transfer, especially near the phase interface. The numerical resolution of the model by Newton-Raphson method gives good results in terms of calculation time and convergence. The simulations show that the impact of reactions at chemical equilibrium and that of kinetically controlled reactions with high kinetics on mass transfer is relatively similar. Moreover, the Fick’s law is less adapted for multicomponent mixtures where some abnormalities such as counter-diffusion take place

Quantification of the performance of chaotic micromixers on the basis of finite time Lyapunov exponents

Chaotic micromixers such as the staggered herringbone mixer developed by Stroock et al. allow efficient mixing of fluids even at low Reynolds number by repeated stretching and folding of the fluid interfaces. The ability of the fluid to mix well depends on the rate at which "chaotic advection" occurs in the mixer. An optimization of mixer geometries is a non trivial task which is often performed by time consuming and expensive trial and error experiments. In this paper an algorithm is presented that applies the concept of finite-time Lyapunov exponents to obtain a quantitative measure of the chaotic advection of the flow and hence the performance of micromixers. By performing lattice Boltzmann simulations of the flow inside a mixer geometry, introducing massless and non-interacting tracer particles and following their trajectories the finite time Lyapunov exponents can be calculated. The applicability of the method is demonstrated by a comparison of the improved geometrical structure of the staggered herringbone mixer with available literature data.Comment: 9 pages, 8 figure

Robust plasmon waveguides in strongly-interacting nanowire arrays

Arrays of parallel metallic nanowires are shown to provide a tunable, robust, and versatile platform for plasmon interconnects, including high-curvature turns with minimum signal loss. The proposed guiding mechanism relies on gap plasmons existing in the region between adjacent nanowires of dimers and multi-wire arrays. We focus on square and circular silver nanowires in silica, for which excellent agreement between both boundary element method and multiple multipolar expansion calculations is obtained. Our work provides the tools for designing plasmon-based interconnects and achieving high degree of integration with minimum cross talk between adjacent plasmon guides.Comment: 4 pages, 5 figure

Anyons in a weakly interacting system

We describe a theoretical proposal for a system whose excitations are anyons with the exchange phase pi/4 and charge -e/2, but, remarkably, can be built by filling a set of single-particle states of essentially noninteracting electrons. The system consists of an artificially structured type-II superconducting film adjacent to a 2D electron gas in the integer quantum Hall regime with unit filling fraction. The proposal rests on the observation that a vacancy in an otherwise periodic vortex lattice in the superconductor creates a bound state in the 2DEG with total charge -e/2. A composite of this fractionally charged hole and the missing flux due to the vacancy behaves as an anyon. The proposed setup allows for manipulation of these anyons and could prove useful in various schemes for fault-tolerant topological quantum computation.Comment: 7 pages with 3 figures. For related work and info visit http://www.physics.ubc.ca/~fran

Use of groundwater lifetime expectancy for the performance assessment of a deep geologic waste repository: 1. Theory, illustrations, and implications

Long-term solutions for the disposal of toxic wastes usually involve isolation of the wastes in a deep subsurface geologic environment. In the case of spent nuclear fuel, if radionuclide leakage occurs from the engineered barrier, the geological medium represents the ultimate barrier that is relied upon to ensure safety. Consequently, an evaluation of radionuclide travel times from a repository to the biosphere is critically important in a performance assessment analysis. In this study, we develop a travel time framework based on the concept of groundwater lifetime expectancy as a safety indicator. Lifetime expectancy characterizes the time that radionuclides will spend in the subsurface after their release from the repository and prior to discharging into the biosphere. The probability density function of lifetime expectancy is computed throughout the host rock by solving the backward-in-time solute transport adjoint equation subject to a properly posed set of boundary conditions. It can then be used to define optimal repository locations. The risk associated with selected sites can be evaluated by simulating an appropriate contaminant release history. The utility of the method is illustrated by means of analytical and numerical examples, which focus on the effect of fracture networks on the uncertainty of evaluated lifetime expectancy.Comment: 11 pages, 8 figures; Water Resources Research, Vol. 44, 200

Atomic-scale confinement of optical fields

In the presence of matter there is no fundamental limit preventing confinement of visible light even down to atomic scales. Achieving such confinement and the corresponding intensity enhancement inevitably requires simultaneous control over atomic-scale details of material structures and over the optical modes that such structures support. By means of self-assembly we have obtained side-by-side aligned gold nanorod dimers with robust atomically-defined gaps reaching below 0.5 nm. The existence of atomically-confined light fields in these gaps is demonstrated by observing extreme Coulomb splitting of corresponding symmetric and anti-symmetric dimer eigenmodes of more than 800 meV in white-light scattering experiments. Our results open new perspectives for atomically-resolved spectroscopic imaging, deeply nonlinear optics, ultra-sensing, cavity optomechanics as well as for the realization of novel quantum-optical devices

Understanding bottom-up continuous hydrothermal synthesis of nanoparticles using empirical measurement and computational simulation

Continuous hydrothermal synthesis was highlighted in a recent review as an enabling technology for the production of nanoparticles. In recent years, it has been shown to be a suitable reaction medium for the synthesis of a wide range of nanomaterials. Many single and complex nanomaterials such as metals, metal oxides, doped oxides, carbonates, sulfides, hydroxides, phosphates, and metal organic frameworks can be formed using continuous hydrothermal synthesis techniques. This work presents a methodology to characterize continuous hydrothermal flow systems both experimentally and numerically, and to determine the scalability of a counter current supercritical water reactor for the large scale production (>1,000 T·year–1) of nanomaterials. Experiments were performed using a purpose-built continuous flow rig, featuring an injection loop on a metal salt feed line, which allowed the injection of a chromophoric tracer. At the system outlet, the tracer was detected using UV/Vis absorption, which could be used to measure the residence time distribution within the reactor volume. Computational fluid dynamics (CFD) calculations were also conducted using a modeled geometry to represent the experimental apparatus. The performance of the CFD model was tested against experimental data, verifying that the CFD model accurately predicted the nucleation and growth of the nanomaterials inside the reactor

Unstationary film model for the determination of absolute gas-liquid kinetic rate constants: ozonation of Acid Red 27, Acid Orange 7, and Acid Blue 129

A method for the determination of absolute kinetic rate constants is proposed using an unstationary film model. This methodology avoids the experimental determination of parameters like the enhancement factor or the Hatta number which are usually model-dependent. The mathematical model is general for gas-liquid systems with irreversible second order reactions. An optimization procedure based on artificial neural networks is used to estimate the initial guess of the parameters and the subsequent application of Gauss-Newton algorithm for the final nonlinear parameter estimation. The model is tested with the ozonation reaction of Acid Red 27, Acid Orange 7 and Acid Blue 129. The second-order kinetic rate constants for the direct reaction with O3 are 1615±93, 609±83, and 49±2M−1s−1, respectivelyJF acknowledges the support of the doctoral fellowship from the Universitat Politecnica de Valencia (UPV-PAID-FPI-2010-04).Ferre Aracil, J.; Cardona Navarrete, SC.; López Pérez, MF.; Abad Sempere, A.; Navarro-Laboulais, J. (2013). Unstationary film model for the determination of absolute gas-liquid kinetic rate constants: ozonation of Acid Red 27, Acid Orange 7, and Acid Blue 129. Ozone: Science and Engineering. 35(6):423-437. https://doi.org/10.1080/01919512.2013.815104S423437356Biń, A. K. (2006). Ozone Solubility in Liquids. Ozone: Science & Engineering, 28(2), 67-75. doi:10.1080/01919510600558635Cardona, S. C., López, F., Abad, A., & Navarro-Laboulais, J. (2010). On bubble column reactor design for the determination of kinetic rate constants in gas-liquid systems. The Canadian Journal of Chemical Engineering, 88(4), 491-502. doi:10.1002/cjce.20327Chang, C. 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