103 resultados para Thermodynamic functions

em CentAUR: Central Archive University of Reading - UK


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By eliminating the short range negative divergence of the Debye–Hückel pair distribution function, but retaining the exponential charge screening known to operate at large interparticle separation, the thermodynamic properties of one-component plasmas of point ions or charged hard spheres can be well represented even in the strong coupling regime. Predicted electrostatic free energies agree within 5% of simulation data for typical Coulomb interactions up to a factor of 10 times the average kinetic energy. Here, this idea is extended to the general case of a uniform ionic mixture, comprising an arbitrary number of components, embedded in a rigid neutralizing background. The new theory is implemented in two ways: (i) by an unambiguous iterative algorithm that requires numerical methods and breaks the symmetry of cross correlation functions; and (ii) by invoking generalized matrix inverses that maintain symmetry and yield completely analytic solutions, but which are not uniquely determined. The extreme computational simplicity of the theory is attractive when considering applications to complex inhomogeneous fluids of charged particles.

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Oceanography is concerned with understanding the mechanisms controlling the movement of seawater and its contents. A fundamental tool in this process is the characterization of the thermophysical properties of seawater as functions of measured temperature and electrical conductivity, the latter used as a proxy for the concentration of dissolved matter in seawater. For many years a collection of algorithms denoted the Equation of State 1980 (EOS-80) has been the internationally accepted standard for calculating such properties. However, modern measurement technology now allows routine observations of temperature and electrical conductivity to be made to at least one order of magnitude more accurately than the uncertainty in this standard. Recently, a new standard has been developed, the Thermodynamical Equation of Seawater 2010 (TEOS-10). This new standard is thermodynamically consistent, valid over a wider range of temperature and salinity, and includes a mechanism to account for composition variations in seawater. Here we review the scientific development of this standard, and describe the literature involved in its development, which includes many of the articles in this special issue.

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We describe the use of bivariate 3d empirical orthogonal functions (EOFs) in characterising low frequency variability of the Atlantic thermohaline circulation (THC) in the Hadley Centre global climate model, HadCM3. We find that the leading two modes are well correlated with an index of the meridional overturning circulation (MOC) on decadal timescales, with the leading mode alone accounting for 54% of the decadal variance. Episodes of coherent oscillations in the sub-space of the leading EOFs are identified; these episodes are of great interest for the predictability of the THC, and could indicate the existence of different regimes of natural variability. The mechanism identified for the multi-decadal variability is an internal ocean mode, dominated by changes in convection in the Nordic Seas, which lead the changes in the MOC by a few years. Variations in salinity transports from the Arctic and from the North Atlantic are the main feedbacks which control the oscillation. This mode has a weak feedback onto the atmosphere and hence a surface climatic influence. Interestingly, some of these climate impacts lead the changes in the overturning. There are also similarities to observed multi-decadal climate variability.

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1. We compared the baseline phosphorus (P) concentrations inferred by diatom-P transfer functions and export coefficient models at 62 lakes in Great Britain to assess whether the techniques produce similar estimates of historical nutrient status. 2. There was a strong linear relationship between the two sets of values over the whole total P (TP) gradient (2-200 mu g TP L-1). However, a systematic bias was observed with the diatom model producing the higher values in 46 lakes (of which values differed by more than 10 mu g TP L-1 in 21). The export coefficient model gave the higher values in 10 lakes (of which the values differed by more than 10 mu g TP L-1 in only 4). 3. The difference between baseline and present-day TP concentrations was calculated to compare the extent of eutrophication inferred by the two sets of model output. There was generally poor agreement between the amounts of change estimated by the two approaches. The discrepancy in both the baseline values and the degree of change inferred by the models was greatest in the shallow and more productive sites. 4. Both approaches were applied to two lakes in the English Lake District where long-term P data exist, to assess how well the models track measured P concentrations since approximately 1850. There was good agreement between the pre-enrichment TP concentrations generated by the models. The diatom model paralleled the steeper rise in maximum soluble reactive P (SRP) more closely than the gradual increase in annual mean TP in both lakes. The export coefficient model produced a closer fit to observed annual mean TP concentrations for both sites, tracking the changes in total external nutrient loading. 5. A combined approach is recommended, with the diatom model employed to reflect the nature and timing of the in-lake response to changes in nutrient loading, and the export coefficient model used to establish the origins and extent of changes in the external load and to assess potential reduction in loading under different management scenarios. 6. However, caution must be exercised when applying these models to shallow lakes where the export coefficient model TP estimate will not include internal P loading from lake sediments and where the diatom TP inferences may over-estimate TP concentrations because of the high abundance of benthic taxa, many of which are poor indicators of trophic state.

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Empirical orthogonal function (EOF) analysis is a powerful tool for data compression and dimensionality reduction used broadly in meteorology and oceanography. Often in the literature, EOF modes are interpreted individually, independent of other modes. In fact, it can be shown that no such attribution can generally be made. This review demonstrates that in general individual EOF modes (i) will not correspond to individual dynamical modes, (ii) will not correspond to individual kinematic degrees of freedom, (iii) will not be statistically independent of other EOF modes, and (iv) will be strongly influenced by the nonlocal requirement that modes maximize variance over the entire domain. The goal of this review is not to argue against the use of EOF analysis in meteorology and oceanography; rather, it is to demonstrate the care that must be taken in the interpretation of individual modes in order to distinguish the medium from the message.

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We study generalised prime systems P (1 < p(1) <= p(2) <= ..., with p(j) is an element of R tending to infinity) and the associated Beurling zeta function zeta p(s) = Pi(infinity)(j=1)(1 - p(j)(-s))(-1). Under appropriate assumptions, we establish various analytic properties of zeta p(s), including its analytic continuation, and we characterise the existence of a suitable generalised functional equation. In particular, we examine the relationship between a counterpart of the Prime Number Theorem (with error term) and the properties of the analytic continuation of zeta p(s). Further we study 'well-behaved' g-prime systems, namely, systems for which both the prime and integer counting function are asymptotically well-behaved. Finally, we show that there exists a natural correspondence between generalised prime systems and suitable orders on N-2. Some of the above results are relevant to the second author's theory of 'fractal membranes', whose spectral partition functions are given by Beurling-type zeta functions, as well as to joint work of that author and R. Nest on zeta functions attached to quasicrystals.