76 resultados para Thermodynamic equilibrium
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To examine the long-term stability of Arctic and Antarctic sea ice, idealized simulations are carried out with the climate model ECHAM5/MPIOM. Atmospheric CO2 concentration is increased over 2000 years from pre-industrial levels to quadrupling, is then kept constant for 5940 years, is afterwards decreased over 2000 years to pre-industrial levels, and finally kept constant for 3940 years.Despite these very slow changes, the sea-ice response significantly lags behind the CO2 concentration change. This lag, which is caused by the ocean’s thermal inertia, implies that the sea-ice equilibrium response to increasing CO2 concentration is substantially underestimated by transient simulations. The sea-ice response to CO2 concentration change is not truly hysteretic and in principle reversible.We find no lag in the evolution of Arctic sea ice relative to changes in annual-mean northern-hemisphere surface temperature. The summer sea-ice cover changes linearly with respect to both CO2 concentration and temper...
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Changes of the equilibrium-line altitude (ELA) since the end of the Little Ice Age (LIA) in eastern Nepal have been studied using glacier inventory data. The toe-to-headwall altitude ratios (THARs) for individual glaciers were calculated for 1992, and used to estimate the ELA in 1959 and at the end of the LIA. THAR for debris-free glaciers is found to be smaller than for debris-covered glaciers. The ELAs for debris-covered glaciers are higher than those for debris-free glaciers in eastern Nepal. There is considerable variation in the reconstructed change in ELA (ΔELA) between glaciers within specific regions and between regions. This is not related to climate gradients, but results from differences in glacier aspect: southeast- and south-facing glaciers show larger ΔELAs in eastern Nepal than north- or west-facing glaciers. The data suggest that the rate of ELA rise may have accelerated in the last few decades. The limited number of climate records from Nepal, and analyses using a simple ELA–climate model, suggest that the higher rate of the ΔELA between 1959 and 1992 is a result of increased warming that occurred after the 1970s at higher altitudes in Nepal.
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Interpolymer complexes (IPCs) formed between complimentary polymers in solution have shown a wide range of applications from drug delivery to biosensors. This work describes the combined use of isothermal titration calorimetry and surface plasmon resonance to investigate the thermodynamic and kinetic processes during hydrogen-bonded interpolymer complexation. Varied polymers that are commonly used in layer-by-layer coatings and pharmaceutical preparations were selected to span a range of chemical functionalities including some known IPCs previously characterized by other techniques, and other polymer combinations with unknown outcomes. This work is the first to comprehensively detail the thermodynamic and kinetic data of hydrogen bonded IPCs, aiding understanding and detailed characterization of the complexes. The applicability of the two techniques in determining thermodynamic, gravimetric and kinetic properties of IPCs is considered.
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The incorporation of cobalt in mixed metal carbonates is a possible route to the immobilization of this toxic element in the environment. However, the thermodynamics of (Ca,Co)CO3 solid solutions are still unclear due to conflicting data from experiment and from the observation of natural ocurrences. We report here the results of a computer simulation study of the mixing of calcite (CaCO3) and spherocobaltite (CoCO3), using density functional theory calculations. Our simulations suggest that previously proposed thermodynamic models, based only on the range of observed compositions, significantly overestimate the solubility between the two solids and therefore underestimate the extension of the miscibility gap under ambient conditions. The enthalpy of mixing of the disordered solid solution is strongly positive and moderately asymmetric: calcium incorporation in spherocobaltite is more endothermic than cobalt incorporation in calcite. Ordering of the impurities in (0001) layers is energetically favourable with respect to the disordered solid solution at low temperatures and intermediate compositions, but the ordered phase is still unstable to demixing. We calculate the solvus and spinodal lines in the phase diagram using a sub-regular solution model, and conclude that many Ca1-xCoxCO3 mineral solid solutions (with observed compositions of up to x=0.027, and above x=0.93) are metastable with respect to phase separation. We also calculate solid/aqueous distribution coefficients to evaluate the effect of the strong non-ideality of mixing on the equilibrium with aqueous solution, showing that the thermodynamically-driven incorporation of cobalt in calcite (and of calcium in spherocobaltite) is always very low, regardless of the Co/Ca ratio of the aqueous environment.
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We investigate in detail the initial susceptibility, magnetization curves, and microstructure of ferrofluids in various concentration and particle dipole moment ranges by means of molecular dynamics simulations. We use the Ewald summation for the long-range dipolar interactions, take explicitly into account the translational and rotational degrees of freedom, coupled to a Langevin thermostat. When the dipolar interaction energy is comparable with the thermal energy, the simulation results on the magnetization properties agree with the theoretical predictions very well. For stronger dipolar couplings, however, we find systematic deviations from the theoretical curves. We analyze in detail the observed microstructure of the fluids under different conditions. The formation of clusters is found to enhance the magnetization at weak fields and thus leads to a larger initial susceptibility. The influence of the particle aggregation is isolated by studying ferro-solids, which consist of magnetic dipoles frozen in at random locations but which are free to rotate. Due to the artificial suppression of clusters in ferrosolids the observed susceptibility is considerably lowered when compared to ferrofluids.
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Langevin dynamics simulations are used to investigate the equilibrium magnetization properties and structure of magnetic dipolar fluids. The influence of using different boundary conditions are systematically studied. Simulation results on the initial susceptibility and magnetization curves are compared with theoretical predictions. The effect of particle aggregation is discussed in detail by performing a cluster analysis of the microstructure.
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The “cotton issue” has been a topic of several academic discussions for trade policy analysts. However the design of trade and agricultural policy in the EU and the USA has become a politically sensitive matter throughout the last five years. This study utilizing the Agricultural Trade Policy Simulation Model (ATPSM) aims to gain insights into the global cotton market, to explain why domestic support for cotton has become an issue, to quantify the impact of the new EU agricultural policy on the cotton sector, and to measure the effect of eliminating support policies on production and trade. Results indicate that full trade liberalization would lead the four West African countries to better terms of trade with the EU. If tariff reduction follows the so-called Swiss formula, world prices would increase by 3.5%.
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A method for the detection of O+ ion fluxes from topside soundings is described. The shape of the plasma scale-height profile is altered by such flows only at heights near the F2-peak, where ion-neutral drag is large. Model profiles are used to relate changes in scale height to the ratio (φ/φL) where φ is the field-aligned O+ flux (relative to the neutral air) and φL is the limiting value set by frictional drag. Values of (φ/φL) can then be determined to within a few per cent from experimental soundings, using the plasma temperature and its gradient (as deduced from the observed profile) and the MSIS model neutral temperature. It was found that 3700 topside profiles show departures from diffusive equilibrium, out of 10,000 used to obtain the global morphology of (φ/φL) near the sunspot minimum. Results reveal dynamic ion-flow effects such as the transequatorial breeze and the effects of the polar wind and protonospheric replenishment light-ion flows can be inferred.
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Observations of the Sun’s corona during the space era have led to a picture of relatively constant, but cyclically varying solar output and structure. Longer-term, more indirect measurements, such as from 10Be, coupled by other albeit less reliable contemporaneous reports, however, suggest periods of significant departure from this standard. The Maunder Minimum was one such epoch where: (1) sunspots effectively disappeared for long intervals during a 70 yr period; (2) eclipse observations suggested the distinct lack of a visible K-corona but possible appearance of the F-corona; (3) reports of aurora were notably reduced; and (4) cosmic ray intensities at Earth were inferred to be substantially higher. Using a global thermodynamic MHD model, we have constructed a range of possible coronal configurations for the Maunder Minimum period and compared their predictions with these limited observational constraints. We conclude that the most likely state of the corona during—at least—the later portion of the Maunder Minimum was not merely that of the 2008/2009 solar minimum, as has been suggested recently, but rather a state devoid of any large-scale structure, driven by a photospheric field composed of only ephemeral regions, and likely substantially reduced in strength. Moreover, we suggest that the Sun evolved from a 2008/2009-like configuration at the start of the Maunder Minimum toward an ephemeral-only configuration by the end of it, supporting a prediction that we may be on the cusp of a new grand solar minimum.
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A generalization of Arakawa and Schubert's convective quasi-equilibrium principle is presented for a closure formulation of mass-flux convection parameterization. The original principle is based on the budget of the cloud work function. This principle is generalized by considering the budget for a vertical integral of an arbitrary convection-related quantity. The closure formulation includes Arakawa and Schubert's quasi-equilibrium, as well as both CAPE and moisture closures as special cases. The formulation also includes new possibilities for considering vertical integrals that are dependent on convective-scale variables, such as the moisture within convection. The generalized convective quasi-equilibrium is defined by a balance between large-scale forcing and convective response for a given vertically-integrated quantity. The latter takes the form of a convolution of a kernel matrix and a mass-flux spectrum, as in the original convective quasi-equilibrium. The kernel reduces to a scalar when either a bulk formulation is adopted, or only large-scale variables are considered within the vertical integral. Various physical implications of the generalized closure are discussed. These include the possibility that precipitation might be considered as a potentially-significant contribution to the large-scale forcing. Two dicta are proposed as guiding physical principles for the specifying a suitable vertically-integrated quantity.
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A general circulation model of intermediate complexity with an idealized Earth-like aquaplanet setup is used to study the impact of changes in the oceanic heat transport on the global atmospheric circulation. Focus is on the atmospheric mean meridional circulation and global thermodynamic properties. The atmosphere counterbalances to a large extent the imposed changes in the oceanic heat transport, but, nonetheless, significant modifications to the atmospheric general circulation are found. Increasing the strength of the oceanic heat transport up to 2.5 PW leads to an increase in the global mean near-surface temperature and to a decrease in its equator-to-pole gradient. For stronger transports, the gradient is reduced further, but the global mean remains approximately constant. This is linked to a cooling and a reversal of the temperature gradient in the tropics. Additionally, a stronger oceanic heat transport leads to a decline in the intensity and a poleward shift of the maxima of both the Hadley and Ferrel cells. Changes in zonal mean diabatic heating and friction impact the properties of the Hadley cell, while the behavior of the Ferrel cell is mostly controlled by friction. The efficiency of the climate machine, the intensity of the Lorenz energy cycle and the material entropy production of the system decline with increased oceanic heat transport. This suggests that the climate system becomes less efficient and turns into a state of reduced entropy production as the enhanced oceanic transport performs a stronger large-scale mixing between geophysical fluids with different temperatures, thus reducing the available energy in the climate system and bringing it closer to a state of thermal equilibrium.
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Idealized explicit convection simulations of the Met Office Unified Model exhibit spontaneous self-aggregation in radiative-convective equilibrium, as seen in other models in previous studies. This self-aggregation is linked to feedbacks between radiation, surface fluxes, and convection, and the organization is intimately related to the evolution of the column water vapor field. Analysis of the budget of the spatial variance of column-integrated frozen moist static energy (MSE), following Wing and Emanuel [2014], reveals that the direct radiative feedback (including significant cloud longwave effects) is dominant in both the initial development of self-aggregation and the maintenance of an aggregated state. A low-level circulation at intermediate stages of aggregation does appear to transport MSE from drier to moister regions, but this circulation is mostly balanced by other advective effects of opposite sign and is forced by horizontal anomalies of convective heating (not radiation). Sensitivity studies with either fixed prescribed radiative cooling, fixed prescribed surface fluxes, or both do not show full self-aggregation from homogeneous initial conditions, though fixed surface fluxes do not disaggregate an initialized aggregated state. A sensitivity study in which rain evaporation is turned off shows more rapid self-aggregation, while a run with this change plus fixed radiative cooling still shows strong self-aggregation, supporting a “moisture memory” effect found in Muller and Bony [2015]. Interestingly, self-aggregation occurs even in simulations with sea surface temperatures (SSTs) of 295 K and 290 K, with direct radiative feedbacks dominating the budget of MSE variance, in contrast to results in some previous studies.
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Previous versions of the Consortium for Small-scale Modelling (COSMO) numerical weather prediction model have used a constant sea-ice surface temperature, but observations show a high degree of variability on sub-daily timescales. To account for this, we have implemented a thermodynamic sea-ice module in COSMO and performed simulations at a resolution of 15 km and 5 km for the Laptev Sea area in April 2008. Temporal and spatial variability of surface and 2-m air temperature are verified by four automatic weather stations deployed along the edge of the western New Siberian polynya during the Transdrift XIII-2 expedition and by surface temperature charts derived from Moderate Resolution Imaging Spectroradiometer (MODIS) satellite data. A remarkable agreement between the new model results and these observations demonstrates that the implemented sea-ice module can be applied for short-range simulations. Prescribing the polynya areas daily, our COSMO simulations provide a high-resolution and high-quality atmospheric data set for the Laptev Sea for the period 14-30 April 2008. Based on this data set, we derive a mean total sea-ice production rate of 0.53 km3/day for all Laptev Sea polynyas under the assumption that the polynyas are ice-free and a rate of 0.30 km3/day if a 10-cm-thin ice layer is assumed. Our results indicate that ice production in Laptev Sea polynyas has been overestimated in previous studies.
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Melts of ABA triblock copolymer molecules with identical end blocks are examined using self-consistent field theory (SCFT). Phase diagrams are calculated and compared with those of homologous AB diblock copolymers formed by snipping the triblocks in half. This creates additional end segments which decreases the degree of segregation. Consequently, triblock melts remain ordered to higher temperatures than their diblock counterparts. We also find that middle-block domains are easier to stretch than end-block domains. As a result, domain spacings are slightly larger, the complex phase regions are shifted towards smaller A-segment compositions, and the perforated-lamellar phase becomes more metastable in triblock melts as compared to diblock melts. Although triblock and diblock melts exhibit very similar phase behavior, their mechanical properties can differ substantially due to triblock copolymers that bridge between otherwise disconnected A domains. We evaluate the bridging fraction for lamellar, cylindrical, and spherical morphologies to be about 40%–45%, 60%–65%, and 75%–80%, respectively. These fractions only depend weakly on the degree of segregation and the copolymer composition.