Time-dependent master equation simulation of complex elementary reactions in combustion: Application to the reaction of (CH2)-C-1 with C2H2 from 300-2000 K

Computational simulations of the title reaction are presented, covering a temperature range from 300 to 2000 K. At lower temperatures we find that initial formation of the cyclopropene complex by addition of methylene to acetylene is irreversible, as is the stabilisation process via collisional energy transfer. Product branching between propargyl and the stable isomers is predicted at 300 K as a function of pressure for the first time. At intermediate temperatures (1200 K), complex temporal evolution involving multiple steady states begins to emerge. At high temperatures (2000 K) the timescale for subsequent unimolecular decay of thermalized intermediates begins to impinge on the timescale for reaction of methylene, such that the rate of formation of propargyl product does not admit a simple analysis in terms of a single time-independent rate constant until the methylene supply becomes depleted. Likewise, at the elevated temperatures the thermalized intermediates cannot be regarded as irreversible product channels. Our solution algorithm involves spectral propagation of a symmetrised version of the discretized master equation matrix, and is implemented in a high precision environment which makes hitherto unachievable low-temperature modelling a reality.

Time evolution in the unimolecular master equation at low temperatures: full spectral solution with scalable iterative methods and high precision

A new method is presented to determine an accurate eigendecomposition of difficult low temperature unimolecular master equation problems. Based on a generalisation of the Nesbet method, the new method is capable of achieving complete spectral resolution of the master equation matrix with relative accuracy in the eigenvectors. The method is applied to a test case of the decomposition of ethane at 300 K from a microcanonical initial population with energy transfer modelled by both Ergodic Collision Theory and the exponential-down model. The fact that quadruple precision (16-byte) arithmetic is required irrespective of the eigensolution method used is demonstrated. (C) 2001 Elsevier Science B.V. All rights reserved.

Flavour retention during high temperature short time extrusion cooking process: a review

Research on the stability of flavours during high temperature extrusion cooking is reviewed. The important factors that affect flavour and aroma retention during the process of extrusion are illustrated. A substantial number of flavour volatiles which are incorporated prior to extrusion are normally lost during expansion, this is because of steam distillation. Therefore, a general practice has been to introduce a flavour mix after the extrusion process. This extra operation requires a binding agent (normally oil), and may also result in a non-uniform distribution of the flavour and low oxidative stability of the flavours exposed on the surface. Therefore, the importance of encapsulated flavours, particularly the beta -cyclodextrin-flavour complex, is highlighted in this paper.

The effects of time delays in adaptive phase measurements

It is not possible to make measurements of the phase of an optical mode using linear optics without introducing an extra phase uncertainty. This extra phase variance is quite large for heterodyne measurements, however it is possible to reduce it to the theoretical limit of log (n) over bar (4 (n) over bar (2)) using adaptive measurements. These measurements are quite sensitive to experimental inaccuracies, especially time delays and inefficient detectors. Here it is shown that the minimum introduced phase variance when there is a time delay of tau is tau/(8 (n) over bar). This result is verified numerically, showing that the phase variance introduced approaches this limit for most of the adaptive schemes using the best final phase estimate. The main exception is the adaptive mark II scheme with simplified feedback, which is extremely sensitive to time delays. The extra phase variance due to time delays is considered for the mark I case with simplified feedback, verifying the tau /2 result obtained by Wiseman and Killip both by a more rigorous analytic technique and numerically.

Hormone physiology of pea mutants prevented from flowering by mutations gi or veg1

The veg1 (vegetative) mutant in pea (Pisum sativum L.) does not flower under any circumstances and gi (gigas) mutants remain vegetative under certain conditions. gi plants are deficient in production of floral stimulus, whereas veg1 plants lack a response to floral stimulus. During long days in particular, these non-flowering mutant plants eventually enter a stable compact phase characterised by a large reduction in internode length, small leaves and growth of lateral shoots from the upper-stem (aerial) nodes. The first-order laterals in turn produce second-order laterals and so on in a reiterative pattern. The apical bud is reduced in size but continues active growth. Endogenous hormone measurements and gibberellin application studies with gi-1, gi-2 and veg1 plants indicate that a reduction in gibberellin and perhaps indole-3-acetic acid level may account, at least partially, for the compact aerial shoot phenotype. In the gi-1 mutant, the compact phenotype is rescued by transfer from a 24- to an 8-h photoperiod. We propose that in plants where flowering is prevented by a lack of floral stimulus or an inability to respond, the large reduction in photoperiod gene activity during long days may lead to a reduction in apical sink strength that is manifest in an altered hormone profile and weak apical dominance.

Mass balance characterisation of Al-7Si-Mg alloy microstructures as a function of solution treatment time

Mass balance calculations were performed to model the effect of solution treatment time on A356 and A357 alloy microstructures. Image analysis and electron probe microanalysis were used to characterise microstructures and confirm model predictions. In as-cast microstructures, up to 8 times more Mg is tied up in the pi-phase than in Mg2Si. The dissolution of pi is accompanied by a corresponding increase in the amount of beta-phase. This causes the rate of pi dissolution to be limited by the rate of beta formation. It is predicted that solution treatments of the order of tens of minutes at 540degreesC produce near-maximum T6 yield strengths, and that Mg contents in excess of 0.52 wt% have no advantage.

Materialized view selection under the maintenance time constraint

A data warehouse is a data repository which collects and maintains a large amount of data from multiple distributed, autonomous and possibly heterogeneous data sources. Often the data is stored in the form of materialized views in order to provide fast access to the integrated data. One of the most important decisions in designing a data warehouse is the selection of views for materialization. The objective is to select an appropriate set of views that minimizes the total query response time with the constraint that the total maintenance time for these materialized views is within a given bound. This view selection problem is totally different from the view selection problem under the disk space constraint. In this paper the view selection problem under the maintenance time constraint is investigated. Two efficient, heuristic algorithms for the problem are proposed. The key to devising the proposed algorithms is to define good heuristic functions and to reduce the problem to some well-solved optimization problems. As a result, an approximate solution of the known optimization problem will give a feasible solution of the original problem. (C) 2001 Elsevier Science B.V. All rights reserved.

Rate and timing of vegetative growth, flowering and fruit development of Persoonia virgata (Proteaceae)

Persoonia virgata R. Br. is harvested from the wild in both its vegetative and flowering stages. There has been no systematic study published on the annual growth cycle and anecdotal reports are conflicting. The growth pattern, flowering and fruit development of P. virgata in its natural habitat was recorded monthly for two consecutive years. The main growth period occurred in late spring-mid-autumn (November-May) when the shrubs were producing little or no fruit. Very few open flowers were observed at the site over the 2 years, with only 6.7 and 12.7% of stems bearing open flowers in January and February 1996, respectively. A second study of flowering on container-grown shrubs showed that individual flowers were open for only 2-5 days, with individual stems taking 3-8.5 weeks to complete flowering. The main fruit growth period occurred from May to September, and in June and July 1996 the total fruit set per stem was 41.6 and 36.1%, respectively. The fruit took at least 6 months to develop during which vegetative growth was minimal. The harvesting of plants in the flowering or fruiting stages removes the annual seed crop, which may reduce regeneration of this obligate seed regenerator and threaten its survival after fire.

Estimating economic relationships subject to firm- and time-varying equality and inequality constraints

Applied econometricians often fail to impose economic regularity constraints in the exact form economic theory prescribes. We show how the Singular Value Decomposition (SVD) Theorem and Markov Chain Monte Carlo (MCMC) methods can be used to rigorously impose time- and firm-varying equality and inequality constraints. To illustrate the technique we estimate a system of translog input demand functions subject to all the constraints implied by economic theory, including observation-varying symmetry and concavity constraints. Results are presented in the form of characteristics of the estimated posterior distributions of functions of the parameters. Copyright (C) 2001 John Wiley Sons, Ltd.