A master equation model for bimolecular reaction via multi-well isomerization intermediates

A reversible linear master equation model is presented for pressure- and temperature-dependent bimolecular reactions proceeding via multiple long-lived intermediates. This kinetic treatment, which applies when the reactions are measured under pseudo-first-order conditions, facilitates accurate and efficient simulation of the time dependence of the populations of reactants, intermediate species and products. Detailed exploratory calculations have been carried out to demonstrate the capabilities of the approach, with applications to the bimolecular association reaction C3H6 + H reversible arrow C3H7 and the bimolecular chemical activation reaction C2H2 +(CH2)-C-1--> C3H3+H. The efficiency of the method can be dramatically enhanced through use of a diffusion approximation to the master equation, and a methodology for exploiting the sparse structure of the resulting rate matrix is established.

On the validity of the shrinking core model in noncatalytic gas solid reaction

By using a matched asymptotic expansion technique, the shrinking core model (SCM) used in non-catalytic gas solid reactions with general kinetic expression is rigorously justified in this paper as a special case of the homogeneous model when the reaction rate is much faster than that of diffusion. The time-pendent velocity of the moving reacted-unreacted interface is found to be proportional to the gas flux at that interface for all geometries of solid particles, and the thickness order of the reaction zone and also the degree of chemical reaction at the interface is discussed in this paper.

Using the level set method to model endogenous lava dome growth

Modeling volcanic phenomena is complicated by free-surfaces often supporting large rheological gradients. Analytical solutions and analogue models provide explanations for fundamental characteristics of lava flows. But more sophisticated models are needed, incorporating improved physics and rheology to capture realistic events. To advance our understanding of the flow dynamics of highly viscous lava in Peléean lava dome formation, axi-symmetrical Finite Element Method (FEM) models of generic endogenous dome growth have been developed. We use a novel technique, the level-set method, which tracks a moving interface, leaving the mesh unaltered. The model equations are formulated in an Eulerian framework. In this paper we test the quality of this technique in our numerical scheme by considering existing analytical and experimental models of lava dome growth which assume a constant Newtonian viscosity. We then compare our model against analytical solutions for real lava domes extruded on Soufrière, St. Vincent, W.I. in 1979 and Mount St. Helens, USA in October 1980 using an effective viscosity. The level-set method is found to be computationally light and robust enough to model the free-surface of a growing lava dome. Also, by modeling the extruded lava with a constant pressure head this naturally results in a drop in extrusion rate with increasing dome height, which can explain lava dome growth observables more appropriately than when using a fixed extrusion rate. From the modeling point of view, the level-set method will ultimately provide an opportunity to capture more of the physics while benefiting from the numerical robustness of regular grids.

Combining GIS and Expert Opinion to Model Landscapes for a Smallholder Forest Extension Program in Leyte, the Philippines

A Geographic Information System (GIS) was used to model datasets of Leyte Island, the Philippines, to identify land which was suitable for a forest extension program on the island. The datasets were modelled to provide maps of the distance of land from cities and towns, land which was a suitable elevation and slope for smallholder forestry and land of various soil types. An expert group was used to assign numeric site suitabilities to the soil types and maps of site suitability were used to assist the selection of municipalities for the provision of extension assistance to smallholders. Modelling of the datasets was facilitated by recent developments of the ArcGIS® suite of computer programs and derivation of elevation and slope was assisted by the availability of digital elevation models (DEM) produced by the Shuttle Radar Topography (SRTM) mission. The usefulness of GIS software as a decision support tool for small-scale forestry extension programs is discussed.

Parliament House Competition Model, Canberra

View of model for competition entry.

Adsorption characteristics of carbonized bark for phenol and pentachlorophenol

The potential of using carbonized slash pine bark as a substitute for activated carbon was examined in this study. The bark was carbonized by slow heating in nitrogen for 6.5 h to 672 degrees C. The BET-N-2 surface area, average micropore and mesopore diameter, and micropore volume were 332 m(2) g(-1) 21.7 Angstrom, and 0.125 cm(3) g(-1), respectively. The adsorption capacities for phenol and pentachlorophenol (PCP) at pH 2 and pH 8 were evaluated. The Langmuir equation provided a slightly better fit than the Freundlich equation to two sets of phenol data. The calculated Freundlich constants, K = 0.41 - 0.58 mmol/g/(mmol dm(-3))(1/n) and 1/n = 0.30 - 0.41, were lower and higher, respectively, than literature values for activated carbons. The adsorption capacity of the carbonized bark was much lower for PCP than for phenol. The protonated and anionic PCP isotherms were Type II or III, respectively, in the Brunauer classification. The BET equation provided the best fit to protonated PCP isotherm data. The anionic PCP data were fitted to both the BET model and an equation used in the literature to represent phosphate adsorption on activated carbons. Nonlinear regression of the data for both phenol and PCP adsorption with the Freundlich, Langmuir and BET equations generally gave more accurate parameters, compared with the use of linearized equations to obtain the parameters. (C) 1998 SCI.