71 resultados para semi empirical calculations

em University of Queensland eSpace - Australia


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A semi-empirical linear equation has been developed to optimise the amount of maltodextrin additive (DE 6) required to successfully spray dry a sugar-rich product on the basis of its composition. Based on spray drying experiments, drying index values for individual sugars (sucrose, glucose, frutose) and citric acid were determined, and us;ng these index values an equation for model mixtures of these components was established. This equation has been tested with two sugar-rich natural products, pineapple juice and honey. The relationship was found to be valid for these products.

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The Dubinin-Radushkevich (DR) equation is widely used for description of adsorption in microporous materials, especially those of a carbonaceous origin. The equation has a semi-empirical origin and is based on the assumptions of a change in the potential energy between the gas and adsorbed phases and a characteristic energy of a given solid. This equation yields a macroscopic behaviour of adsorption loading for a given pressure. In this paper, we apply a theory developed in our group to investigate the underlying mechanism of adsorption as an alternative to the macroscopic description using the DR equation. Using this approach, we are able to establish a detailed picture of the adsorption in the whole range of the micropore system. This is different from the DR equation, which provides an overall description of the process. (C) 2001 Elsevier Science Ltd. All rights reserved.

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This paper proposes an integrated methodology for modelling froth zone performance in batch and continuously operated laboratory flotation cells. The methodology is based on a semi-empirical approach which relates the overall flotation rate constant to the froth depth (FD) in the flotation cell; from this relationship, a froth zone recovery (R,) can be extracted. Froth zone recovery, in turn, may be related to the froth retention time (FRT), defined as the ratio of froth volume to the volumetric flow rate of concentrate from the cell. An expansion of this relationship to account for particles recovered both by true flotation and entrainment provides a simple model that may be used to predict the froth performance in continuous tests from the results of laboratory batch experiments. Crown Copyright (C) 2002 Published by Elsevier Science B.V. All rights reserved.

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A review of spontaneous rupture in thin films with tangentially immobile interfaces is presented that emphasizes the theoretical developments of film drainage and corrugation growth through the linearization of lubrication theory in a cylindrical geometry. Spontaneous rupture occurs when corrugations from adjacent interfaces become unstable and grow to a critical thickness. A corrugated interface is composed of a number of waveforms and each waveform becomes unstable at a unique transition thickness. The onset of instability occurs at the maximum transition thickness, and it is shown that only upper and lower bounds of this thickness can be predicted from linear stability analysis. The upper bound is equivalent to the Freakel criterion and is obtained from the zeroth order approximation of the H-3 term in the evolution equation. This criterion is determined solely by the film radius, interfacial tension and Hamaker constant. The lower bound is obtained from the first order approximation of the H-3 term in the evolution equation and is dependent on the film thinning velocity A semi-empirical equation, referred to as the MTR equation, is obtained by combining the drainage theory of Manev et al. [J. Dispersion Sci. Technol., 18 (1997) 769] and the experimental measurements of Radoev et al. [J. Colloid Interface Sci. 95 (1983) 254] and is shown to provide accurate predictions of film thinning velocity near the critical thickness of rupture. The MTR equation permits the prediction of the lower bound of the maximum transition thickness based entirely on film radius, Plateau border radius, interfacial tension, temperature and Hamaker constant. The MTR equation extrapolates to Reynolds equation under conditions when the Plateau border pressure is small, which provides a lower bound for the maximum transition thickness that is equivalent to the criterion of Gumerman and Homsy [Chem. Eng. Commun. 2 (1975) 27]. The relative accuracy of either bound is thought to be dependent on the amplitude of the hydrodynamic corrugations, and a semiempirical correlation is also obtained that permits the amplitude to be calculated as a function of the upper and lower bound of the maximum transition thickness. The relationship between the evolving theoretical developments is demonstrated by three film thickness master curves, which reduce to simple analytical expressions under limiting conditions when the drainage pressure drop is controlled by either the Plateau border capillary pressure or the van der Waals disjoining pressure. The master curves simplify solution of the various theoretical predictions enormously over the entire range of the linear approximation. Finally, it is shown that when the Frenkel criterion is used to assess film stability, recent studies reach conclusions that are contrary to the relevance of spontaneous rupture as a cell-opening mechanism in foams. (C) 2003 Elsevier Science B.V. All rights reserved.

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The solubility of ethyl propionate, ethyl butyrate, and ethyl isovalerate in supercritical carbon dioxide was measured at temperature ranging from 308.15 to 333.15 K and pressure ranging from 85 to 195 bar. At the same temperature, the solubility of these compounds increases with pressure. The crossover pressure region was also observed in this study. The experimental data were correlated by the semi-empirical Chrastil equation and Peng-Robinson equation of state (EOS) using several mixing rules. The Peng-Robinson EOS gives better solubility prediction than the empirical Chrastil equation. (C) 2002 Elsevier Science B.V. All rights reserved.

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A review is given on the fundamental studies of gas-carbon reactions using electronic structure methods in the last several decades. The three types of electronic structure methods including semi-empirical, ab initio and density functional theory, methods are briefly introduced first, followed by the studies on carbon reactions with hydrogen and oxygen-containing gases (non-catalysed and catalysed). The problems yet to solve and possible promising directions are discussed. (C) 2002 Elsevier Science Ltd. All rights reserved.

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A review of thin film drainage models is presented in which the predictions of thinning velocities and drainage times are compared to reported values on foam and emulsion films found in the literature. Free standing films with tangentially immobile interfaces and suppressed electrostatic repulsion are considered, such as those studied in capillary cells. The experimental thinning velocities and drainage times of foams and emulsions are shown to be bounded by predictions from the Reynolds and the theoretical MTsR equations. The semi-empirical MTsR and the surface wave equations were the most consistently accurate with all of the films considered. These results are used in an accompanying paper to develop scaling laws that bound the critical film thickness of foam and emulsion films. (c) 2005 Elsevier B.V. All rights reserved.

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In natural estuaries, contaminant transport is driven by the turbulent momentum mixing. The predictions of scalar dispersion can rarely be predicted accurately because of a lack of fundamental understanding of the turbulence structure in estuaries. Herein detailed turbulence field measurements were conducted at high frequency and continuously for up to 50 hours per investigation in a small subtropical estuary with semi-diurnal tides. Acoustic Doppler velocimetry was deemed the most appropriate measurement technique for such small estuarine systems with shallow water depths (less than 0.5 m at low tides), and a thorough post-processing technique was applied. The estuarine flow is always a fluctuating process. The bulk flow parameters fluctuated with periods comparable to tidal cycles and other large-scale processes. But turbulence properties depended upon the instantaneous local flow properties. They were little affected by the flow history, but their structure and temporal variability were influenced by a variety of mechanisms. This resulted in behaviour which deviated from that for equilibrium turbulent boundary layer induced by velocity shear only. A striking feature of the data sets is the large fluctuations in all turbulence characteristics during the tidal cycle. This feature was rarely documented, but an important difference between the data sets used in this study from earlier reported measurements is that the present data were collected continuously at high frequency during relatively long periods. The findings bring new lights in the fluctuating nature of momentum exchange coefficients and integral time and length scales. These turbulent properties should not be assumed constant.

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Popper's explications of 'ad hoc' in relation to hypotheses and explanations turn out to be either trivial, confused or mistaken. One such explication I discuss at length is circularity; another is reduction in empirical content. I argue that non-circularity is preferable to non-ad hocness for an acceptable explanation or explanans, and I isolate some persistent errors in his analysis. Second, Popper is barking up the wrong tree in proscribing reductions in empirical content in novel hypotheses. Such reductions may constitute scientific progress. He fails to show that ad hoc hypothesis are the threat to science he claims.

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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.

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This paper reviews the potential use of three types of spatial technology to land managers, namely satellite imagery, satellite positioning systems and supporting computer software. Developments in remote sensing and the relative advantages of multispectral and hyperspectral images are discussed. The main challenge to the wider use of remote sensing as a land management tool is seen as uncertainty whether apparent relationships between biophysical variables and spectral reflectance are direct and causal, or artefacts of particular images. Developments in satellite positioning systems are presented in the context of land managers’ need for position estimates in situations where absolute precision may or may not be required. The role of computer software in supporting developments in spatial technology is described. Spatial technologies are seen as having matured beyond empirical applications to the stage where they are useful and reliable land management tools. In addition, computer software has become more user-friendly and this has facilitated data collection and manipulation by semi-expert as well as specialist staff.

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A new cyclic octapeptide, cyclo(Ile-Ser-(Gly)Thz-Ile-Thr-(Gly)Thz) (PatN), related to patellamide A, has been synthesized and reacted with copper(II) and base to form mono- and dinuclear complexes. The coordination environments around copper(TI) have been characterized by EPR spectroscopy. The solution structure of the thermodynamically most stable product, a purple dicopper(TI) compound, has been examined by simulating weakly dipole-dipole coupled EPR spectra based upon structural parameters obtained from force field (MM and MD) calculations. The MM-EPR method produces a saddle-shaped structure for [Cu-2(PatN)(OH2)(6)] that is similar to the known solution structure of patellamide A and the known solid-state structure of [Cu-2(AscidH(2))CO3(OH2)(2)]. Compared with the latter, [Cu-2(PatN)] has no carbonate bridge and a significantly flatter topology. The MM-EPR approach to solution-structure determination for paramagnetic metallopeptides may find wide applications to other metallopeptides and metalloproteins.

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This paper describes a hybrid numerical method for the design of asymmetric magnetic resonance imaging magnet systems. The problem is formulated as a field synthesis and the desired current density on the surface of a cylinder is first calculated by solving a Fredholm equation of the first kind. Nonlinear optimization methods are then invoked to fit practical magnet coils to the desired current density. The field calculations are performed using a semi-analytical method. A new type of asymmetric magnet is proposed in this work. The asymmetric MRI magnet allows the diameter spherical imaging volume to be positioned close to one end of the magnet. The main advantages of making the magnet asymmetric include the potential to reduce the perception of claustrophobia for the patient, better access to the patient by attending physicians, and the potential for reduced peripheral nerve stimulation due to the gradient coil configuration. The results highlight that the method can be used to obtain an asymmetric MRI magnet structure and a very homogeneous magnetic field over the central imaging volume in clinical systems of approximately 1.2 m in length. Unshielded designs are the focus of this work. This method is flexible and may be applied to magnets of other geometries. (C) 1999 Academic Press.

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Reports a pilot study of the relative importance of import decision variables as rated by Australian managers. A systematic sample qi 104 Australian managers representing different companies participated in the study. Australian importers rated product quality as the most important variable when importing products from overseas followed by long-term suppliers' dependability, product style/feature, price, and timely delivery. Australian managers who import consumer products find the domestic import duties and tariffs to be more important than did those who import industrial products. Larger volume importers regard the product brand name reputation to be more important than did those who import smaller volumes.