Structural Dynamics in (ND4)2[Cu(D2O)6](SO4)2

The extended X-ray absorption fine structure spectroscopy (EXAFS) of (ND4)(2)[CU(D2O)(6)](SO4)(2) at 5, 14,100, 200, and 298 K is reported. This indicates that the Cu-O bond lengths of the Cu(D2O)(6)(2+) ion do not change significantly within this temperature range, which contrasts with EPR results and X-ray and neutron diffraction experiments, which imply that two of the Cu-(D2O) bonds converge in length as the temperature is raised. The EXAFS measurements thus confirm that the bond distances yielded by the diffraction experiments refer to the average positions of ligands involved in a dynamic equilibrium in which the directions of the long and intermediate bonds of the Jahn-Teller distorted Cu(D2O)(6)(2+) ion are interchanged in the crystal lattice. Analysis of the displacement parameters is consistent with this interpretation, as are the wave functions calculated using a model involving Jahn-Teller vibronic coupling and the influence of lattice strain interactions.

Kinetics of baculovirus replication and release using real-time quantitative polymerase chain reaction

The study of viral-based processes is hampered by (a) their complex, transient nature, (b) the instability of products, and (c) the lack of accurate diagnostic assays. Here, we describe the use of real-time quantitative polymerase chain reaction to characterize baculoviral infection. Baculovirus DNA content doubles every 1.7 h from 6 h post-infection until replication is halted at the onset of budding. No dynamic equilibrium exists between replication and release, and the kinetics are independent of the cell density at the time of infection. No more than 16% of the intracellular virus copies bud from the cell. (C) 2002 John Wiley & Sons, Inc. Biotechnol Bioeng 77: 476-480, 2002; DOI 10.1002/bit.10126.

On the equilibrium and dynamic behavior of alcohol vapors in activated carbon

As alcohol molecules such as methanol and ethanol have both polar and non-polar groups, their adsorption behavior is governed by the contributions of dispersion interaction (alkyl group) and hydrogen bonding (OH group). In this paper, the adsorption behavior of alcohol molecules and its effect on transport processes are elucidated. From the total permeability (B-T) of alcohol molecules in activated carbon, an adsorption mechanism is proposed, describing well the experimental data, by taking combination effects of clustering, entering micropores, layering and pore filling processes. Unlike the case of non-polar compounds, it was found that at low pressures there are two rises in the BT of alcohol molecules in activated carbon. The first rise is due to the major contribution of surface diffusion to the transport (which is the case of non-polar molecules) and the second one may be associated with cluster formation at the edge of micropores and entering micropores when the clusters are sufficiently large enough to induce a dispersive energy. In addition the clusters formed may enhance surface diffusion at low pressures and hinder gas phase diffusion and flow in meso/macropores. (c) 2006 Elsevier Ltd. All fights reserved.

A dynamic mathematical model for sequential leach bed anaerobic digestion of organic fraction of municipal solid waste

A mathematical model that describes the operation of a sequential leach bed process for anaerobic digestion of organic fraction of municipal solid waste (MSW) is developed and validated. This model assumes that ultimate mineralisation of the organic component of the waste occurs in three steps, namely solubilisation of particulate matter, fermentation to volatile organic acids (modelled as acetic acid) along with liberation of carbon dioxide and hydrogen, and methanogenesis from acetate and hydrogen. The model incorporates the ionic equilibrium equations arising due to dissolution of carbon dioxide, generation of alkalinity from breakdown of solids and dissociation of acetic acid. Rather than a charge balance, a mass balance on the hydronium and hydroxide ions is used to calculate pH. The flow of liquid through the bed is modelled as occurring through two zones-a permeable zone with high flushing rates and the other more stagnant. Some of the kinetic parameters for the biological processes were obtained from batch MSW digestion experiments. The parameters for flow model were obtained from residence time distribution studies conducted using tritium as a tracer. The model was validated using data from leach bed digestion experiments in which a leachate volume equal to 10% of the fresh waste bed volume was sequenced. The model was then tested, without altering any kinetic or flow parameters, by varying volume of leachate that is sequenced between the beds. Simulations for sequencing/recirculating 5 and 30% of the bed volume are presented and compared with experimental results. (C) 2002 Elsevier Science B.V. All rights reserved.

Temperature dependence of the crystal structure and g-values of [(HC(Ph2PO)(3))(2)Cu] (ClO4)(2)center dot 2H(2)O: Influence of dynamic Jahn-Teller coupling and lattice strain interactions

The temperature dependence of the X-ray crystal structure and powder EPR spectrum of [(HC(Ph2PO)(3))(2)CU]-(ClO4)(2)center dot 2H(2)O is reported, and the structure at room temperature confirms that reported previously. Below similar to 100 K, the data imply a geometry with near elongated tetragonal symmetry for the [(HC(Ph2PO)(3))(2)Cu](2+) complex, but on warming the two higher Cu-O bond lengths and g-values progressively converge, and by 340 K the bond lengths correspond to a compressed tetragonal geometry. The data may be interpreted satisfactorily assuming an equilibrium among the energy levels of a Cu-O-6 polyhedron subjected to Jahn-Teller vibronic coupling and a lattice strain. However, agreement with the experiment is obtained only if the orthorhombic component of the lattice strain decreases to a negligible value as the temperature approaches 340 K.

Stochastic dynamic programming for election timing: A game theory approach

In this paper, we consider dynamic programming for the election timing in the majoritarian parliamentary system such as in Australia, where the government has a constitutional right to call an early election. This right can give the government an advantage to remain in power for as long as possible by calling an election, when its popularity is high. On the other hand, the opposition's natural objective is to gain power, and it will apply controls termed as "boosts" to reduce the chance of the government being re-elected by introducing policy and economic responses. In this paper, we explore equilibrium solutions to the government, and the opposition strategies in a political game using stochastic dynamic programming. Results are given in terms of the expected remaining life in power, call and boost probabilities at each time at any level of popularity.

The Equilibrium Flux Method for the calculation of flows with non-equilbrium chemical reactions

The Equilibrium Flux Method [1] is a kinetic theory based finite volume method for calculating the flow of a compressible ideal gas. It is shown here that, in effect, the method solves the Euler equations with added pseudo-dissipative terms and that it is a natural upwinding scheme. The method can be easily modified so that the flow of a chemically reacting gas mixture can be calculated. Results from the method for a one-dimensional non-equilibrium reacting flow are shown to agree well with a conventional continuum solution. Results are also presented for the calculation of a plane two-dimensional flow, at hypersonic speed, of a dissociating gas around a blunt-nosed body.

The importance of wet-powder dynamic mechanical properties in understanding granulation

Granule impact deformation has long been recognised as important in determining whether or not two colliding granules will coalesce. Work in the last 10 years has highlighted the fact that viscous effects are significant in granulation. The relative strengths of different formulations can vary with strain rate. Therefore, traditional strength measurements made at pseudo-static conditions give no indication, even qualitatively, of how materials will behave at high strain rates, and hence are actually misleading when used to model granule coalescence. This means that new standard methods need to be developed for determining the strain rates encountered by granules inside industrial equipment and also for measuring the mechanical properties of granules at these strain rates. The constitutive equations used in theoretical models of granule coalescence also need to be extended to include strain-rate dependent components.

Review of Contact and Dynamic Phenomena in Cold Roll Forming

This review reflects the state of the art in study of contact and dynamic phenomena occurring in cold roll forming. The importance of taking these phenomena into account is determined by significant machine time and tooling costs spent on worn out forming rolls replacement and equipment adjustment in cold roll forming. Predictive modelling of the tool wear caused by contact and dynamic phenomena can reduce the production losses in this technological process.

Non-Equilibrium Reaction Rates in the Macroscopic Chemistry Method for DSMC Calculations

The Direct Simulation Monte Carlo (DSMC) method is used to simulate the flow of rarefied gases. In the Macroscopic Chemistry Method (MCM) for DSMC, chemical reaction rates calculated from local macroscopic flow properties are enforced in each cell. Unlike the standard total collision energy (TCE) chemistry model for DSMC, the new method is not restricted to an Arrhenius form of the reaction rate coefficient, nor is it restricted to a collision cross-section which yields a simple power-law viscosity. For reaction rates of interest in aerospace applications, chemically reacting collisions are generally infrequent events and, as such, local equilibrium conditions are established before a significant number of chemical reactions occur. Hence, the reaction rates which have been used in MCM have been calculated from the reaction rate data which are expected to be correct only for conditions of thermal equilibrium. Here we consider artificially high reaction rates so that the fraction of reacting collisions is not small and propose a simple method of estimating the rates of chemical reactions which can be used in the Macroscopic Chemistry Method in both equilibrium and non-equilibrium conditions. Two tests are presented: (1) The dissociation rates under conditions of thermal non-equilibrium are determined from a zero-dimensional Monte-Carlo sampling procedure which simulates ‘intra-modal’ non-equilibrium; that is, equilibrium distributions in each of the translational, rotational and vibrational modes but with different temperatures for each mode; (2) The 2-D hypersonic flow of molecular oxygen over a vertical plate at Mach 30 is calculated. In both cases the new method produces results in close agreement with those given by the standard TCE model in the same highly nonequilibrium conditions. We conclude that the general method of estimating the non-equilibrium reaction rate is a simple means by which information contained within non-equilibrium distribution functions predicted by the DSMC method can be included in the Macroscopic Chemistry Method.

Dynamic Similarity and Scale Effects Affecting Air Bubble Entrainment in Hydraulic Jumps

In an open channel, the transition from super- to sub-critical flow is a flow singularity (the hydraulic jump) characterised by a sharp rise in free-surface elevation, strong turbulence and air entrainment in the roller. A key feature of the hydraulic jump flow is the strong free-surface aeration and air-water flow turbulence. In the present study, similar experiments were conducted with identical inflow Froude numbers Fr1 using a geometric scaling ratio of 2:1. The results of the Froude-similar experiments showed some drastic scale effects in the smaller hydraulic jumps in terms of void fraction, bubble count rate and bubble chord time distributions. Void fraction distributions implied comparatively greater detrainment at low Reynolds numbers yielding some lesser aeration of the jump roller. The dimensionless bubble count rates were significantly lower in the smaller channel, especially in the mixing layer. The bubble chord time distributions were quantitatively close in both channels, and they were not scaled according to a Froude similitude. Simply the hydraulic jump remains a fascinating two-phase flow motion that is still poorly understood.

Dynamic processes in contingent valuation: A case study involving the mahogany glider

This paper reports the results of an experiment involving a sample of 204 members of the public who were assessed on three occasions about their willingness to pay for the conservation of the mahogany glider. They were asked this question prior to information being provided to them about the glider and other focal wildlife species; after such information was provided, and finally after participants had had an opportunity to see live specimens of this glider. The mean willingness to pay of the relevant samples are compared and found to show significant variations. Theories are considered that help explain the dynamics of these variations. Serious concerns are raised about the capacity of information provision to reveal ‘true’ contingent valuations of public goods.

Regulation of photosynthetic pigments in micro-algae by multiple environmental factors: a dynamic balance hypothesis

Environmental effects on the concentration of photosynthetic pigments in micro-algae can be explained by dynamics of photosystem synthesis and deactivation. A model that couples photosystem losses to the relative cellular rates of energy harvesting (light absorption) and assimilation predicts optimal concentrations of light-harvesting pigments and balanced energy flow under environmental conditions that affect light availability and metabolic rates. Effects of light intensity, nutrient supply and temperature on growth rate and pigment levels were similar to general patterns observed across diverse micro-algal taxa. Results imply that dynamic behaviour associated with photophysical stress, and independent of gene regulation, might constitute one mechanism for photo-acclimation of photosynthesis.

Two dimensional computational fluid dynamic models for waste stabilisation ponds

Traditional waste stabilisation pond (WSP) models encounter problems predicting pond performance because they cannot account for the influence of pond features, such as inlet structure or pond geometry, on fluid hydrodynamics. In this study, two dimensional (2-D) computational fluid dynamics (CFD) models were compared to experimental residence time distributions (RTD) from literature. In one of the-three geometries simulated, the 2-D CFD model successfully predicted the experimental RTD. However, flow patterns in the other two geometries were not well described due to the difficulty of representing the three dimensional (3-D) experimental inlet in the 2-D CFD model, and the sensitivity of the model results to the assumptions used to characterise the inlet. Neither a velocity similarity nor geometric similarity approach to inlet representation in 2-D gave results correlating with experimental data. However. it was shown that 2-D CFD models were not affected by changes in values of model parameters which are difficult to predict, particularly the turbulent inlet conditions. This work suggests that 2-D CFD models cannot be used a priori to give an adequate description of the hydrodynamic patterns in WSP. (C) 1998 Elsevier Science Ltd. All rights reserved.