Exact theory of sedimentation equilibrium made useful

The exact description of the thermodynamics of solutions has been used to describe, without approximation, the distribution of all the components of an incompressible solution in a centrifuge cell at sedimentation equilibrium. Thermodynamic parameters describing the interactions between solute components of known molar mass can be obtained by direct analysis of the experimental data. Interpretation of the measured thermodynamic parameters in terms of molecular interactions requires that an arbitrary distinction be made between nonassociative forces, like hard-sphere volume-exclusion and mean-field electrostatic repulsion or attraction, and specific short-range forces of association that give rise to the formation of molecular aggregates. Provided the former can be accounted for adequately, the effects of the latter can be elucidated in the form of good estimates of the equilibrium constants for the reactions of aggregation.

Remitting behaviour of Nepalese rural-to-urban migrants: Implications for theory and policy

This article uses data for Nepal to test contemporary hypotheses about the remitting behaviour and associated motives of rural-to-urban migrants and to consider the likely impact of such remittances on rural development. Possibilities for inheritance, degree of family attachment, likelihood of eventual return to place of origin and family investment in the education of the migrants are found to be significant influences on levels of remittances by Nepalese migrants. However, in Nepal, remittances do not seem to result in long-term capital investment in rural areas and so may not promote long-term development of these areas.

Kinetics of adsorption on activated carbon: application of heterogeneous vacancy solution theory

The kinetics of single component adsorption on activated carbon is investigated here using a heterogeneous vacancy solution theory (VST) of adsorption. The adsorption isotherm is developed to account for the adsorbate non-ideality due to the size difference between the adsorbate molecule and the vacant site, while incorporating adsorbent heterogeneity through a pore-width-related potential energy. The transport process in the bidisperse carbon considers coupled mass transfer in both macropore and micropore phases simultaneously. Adsorbate diffusion in the micropore network is modeled through effective medium theory, thus considering pore network connectivity in the adsorbent, with the activation energy for adsorbate diffusion related to the adsorption energy, represented by the Steele 10-4-3 potential for carbons. Experimental data of five hydrocarbons, CO2 and SO2 on Ajax carbon at multiple temperatures, as well as three hydrocarbons on Norit carbon at three temperatures are first fitted by the heterogeneous VST model to obtain the isotherm parameters, followed by application of the kinetic model to uptake data on carbon particles of different sizes and geometry at various temperatures. For the hydrocarbons studied, the model can successfully correlate the experimental data for both adsorption equilibrium and kinetics. However, there is some deviation in the fit of the desorption kinetics for polar compounds such as CO2 and SO2, due to the inadequacy of the L-J potential model in this case. The significance of viscous transport in the micropores is also considered here and found to be negligible, consistent with recent molecular simulation studies. (C) 2002 Elsevier Science Ltd. All rights reserved.

Vacancy solution theory for binary adsorption equilibria in heterogeneous carbon

A heterogeneous modified vacancy solution model of adsorption developed is evaluated. The new model considers the adsorption process through a mass-action law and is thermodynamically consistent, while maintaining the simplicity in calculation of multicomponent adsorption equilibria, as in the original vacancy solution theory. It incorporates the adsorbent heterogeneity through a pore-width-related potential energy, represented by Steele's 10-4-3 potential expression. The experimental data of various hydrocarbons, CO2 and SO2 on four different activated carbons - Ajax, Norit, Nuxit, and BPL - at multiple temperatures over a wide range of pressures were studied by the heterogeneous modified VST model to obtain the isotherm parameters and micropore-size distribution of carbons. The model successfully correlates the single-component adsorption equilibrium data for all compounds studied on various carbons. The fitting results for the vacancy occupancy parameter are consistent with the pressure change on different carbons, and the effect of pore heterogeneity is important in adsorption at elevated pressure. It predicts binary adsorption equilibria better than the IAST scheme, reflecting the significance of molecular size nonideality.

Density functional theory analysis of the influence of pore wall heterogeneity on adsorption in carbons

Density functional theory for adsorption in carbons is adapted here to incorporate a random distribution of pore wall thickness in the solid, and it is shown that the mean pore wall thickness is intimately related to the pore size distribution characteristics. For typical carbons the pore walls are estimated to comprise only about two graphene layers, and application of the modified density functional theory approach shows that the commonly used assumption of infinitely thick walls can severely affect the results for adsorption in small pores under both supercritical and subcritical conditions. Under supercritical conditions the Henry's law coefficient is overpredicted by as much as a factor of 2, while under subcritical conditions pore wall heterogeneity appears to modify transitions in small pores into a sequence of smaller ones corresponding to pores with different wall thicknesses. The results suggest the need to improve current pore size distrubution analysis methods to allow for pore wall heterogeneity. The density functional theory is further extended here to allow for interpore adsorbate interactions, and it appears that these interaction are negligible for small molecules such as nitrogen but significant for more strongly interacting heavier molecules such as butane, for which the traditional independent pore model may not be adequate.

Modeling of phase equilibrium and vapor adsorption on carbon black based on a combination of a lattice theory and equation of state

A thermodynamic approach is developed in this paper to describe the behavior of a subcritical fluid in the neighborhood of vapor-liquid interface and close to a graphite surface. The fluid is modeled as a system of parallel molecular layers. The Helmholtz free energy of the fluid is expressed as the sum of the intrinsic Helmholtz free energies of separate layers and the potential energy of their mutual interactions calculated by the 10-4 potential. This Helmholtz free energy is described by an equation of state (such as the Bender or Peng-Robinson equation), which allows us a convenient means to obtain the intrinsic Helmholtz free energy of each molecular layer as a function of its two-dimensional density. All molecular layers of the bulk fluid are in mechanical equilibrium corresponding to the minimum of the total potential energy. In the case of adsorption the external potential exerted by the graphite layers is added to the free energy. The state of the interface zone between the liquid and the vapor phases or the state of the adsorbed phase is determined by the minimum of the grand potential. In the case of phase equilibrium the approach leads to the distribution of density and pressure over the transition zone. The interrelation between the collision diameter and the potential well depth was determined by the surface tension. It was shown that the distance between neighboring molecular layers substantially changes in the vapor-liquid transition zone and in the adsorbed phase with loading. The approach is considered in this paper for the case of adsorption of argon and nitrogen on carbon black. In both cases an excellent agreement with the experimental data was achieved without additional assumptions and fitting parameters, except for the fluid-solid potential well depth. The approach has far-reaching consequences and can be readily extended to the model of adsorption in slit pores of carbonaceous materials and to the analysis of multicomponent adsorption systems. (C) 2002 Elsevier Science (USA).

Analysis of adsorption data of graphitized thermal carbon black with a DFT-lattice gas theory

In this paper we analyzed the adsorption of gases and vapors on graphitised thermal carbon black by using a modified DFT-lattice theory, in which we assume that the behavior of the first layer in the adsorption film is different from those of second and higher layers. The effects of various parameters on the topology of the adsorption isotherm were first investigated, and the model was then applied in the analysis of adsorption data of numerous substances on carbon black. We have found that the first layer in the adsorption film behaves differently from the second and higher layers in such a way that the adsorbate-adsorbate interaction energy in the first layer is less than that of second and higher layers, and the same is observed for the partition function. Furthermore, the adsorbate-adsorbate and adsorbate-adsorbent interaction energies obtained from the fitting are consistently lower than the corresponding values obtained from the viscosity data and calculated from the Lorentz-Berthelot rule, respectively.

Practical and economic advantages of choice feeding systems for laying poultry

Poultry can be managed under different feeding systems, depending on the husbandry skills and the feed available. These systems include the following: (1) a complete dry feed offered as a mash ad libitum; (2) the same feed offered as pellets or crumbles ad libitum; (3) a complete feed with added whole grain; (4) a complete wet feed given once or twice a day; (5) a complete feed offered on a restricted basis; (6) choice feeding. Of all these, an interesting alternative to offering complete diets is choice feeding which can be applied on both a small or large commercial scale. Under choice feeding or free-choice feeding birds are usually offered a choice between three types of feedstuffs: (a) an energy source (e.g. maize, rice bran, sorghum or wheat); (b) a protein source (e.g. soyabean meal, meat meal, fish meal or coconut meal) plus vitamins and minerals and (c), in the case of laying hens, calcium in granular form (i.e. oyster-shell grit). This system differs from the modern commercial practice of offering a complete diet comprising energy and protein sources, ground and mixed together. Under the complete diet system, birds are mainly only able to exercise their appetite for energy. When the environmental temperature varies, the birds either over- or under-consume protein and calcium. The basic principle behind practising choice feeding with laying hens is that individual hens are able to select from the various feed ingredients on offer and compose their own diet, according to their actual needs and production capacity. A choice-feeding system is of particular importance to small poultry producers in developing countries, such as Indonesia, because it can substantially reduce the cost of feed. The system is flexible and can be constructed in such a way that the various needs of a flock of different breeds, including village chickens, under different climates can be met. The system also offers a more effective way to use home-produced grain, such as maize, and by-products, such as rice bran, in developing countries. Because oyster-shell grit is readily available in developing countries at lower cost than limestone, the use of cheaper oyster-shell grit can further benefit small-holders in these countries. These benefits apart, simpler equipment suffices when designing and building a feed mixer on the farm, and transport costs are lower. If whole (unground) grain is used, the intake of which is accompanied by increased efficiency of feed utilisation, the costs of grinding, mixing and many of the handling procedures associated with mash and pellet preparation are eliminated. The choice feedstuffs can all be offered in the current feed distribution systems, either by mixing the ingredients first or by using a bulk bin divided into three compartments.

An investigation into commitment in non-Western industrial marketing relationships

This paper reports an investigation into the antecedents of commitment in non-Western industrial marketing relationships. The authors draw the antecedents from extant literature and posit that commitment is related to trust (integrity and reliability), communication quality, conflict, and similarity (social, ethnic, and economic). It is further argued that trust mediates the effects of communication, conflict, and similarity on commitment. As an extension, the authors examine the moderating effects of normative contracts (an implicit understanding of roles and responsibilities) on the construct interrelationships. The hypotheses are tested using data collected from approximately 150 industrial marketing relationships sampled from overseas Chinese firms. The results generally support the authors' framework; however, the mediating hypotheses are not supported. There is evidence of systematic differences in the effects of the studied antecedents on commitment and trust. Furthermore, a multigroup analysis provides evidence of significant moderating effects due to contracting mode. The study provides new insights into the theory and practice of industrial marketing. (C) 2003 Elsevier Science Inc. All rights reserved.

Impulse-response function of splanchnic circulation with model-independent constraints: theory and experimental validation

Modeling physiological processes using tracer kinetic methods requires knowledge of the time course of the tracer concentration in blood supplying the organ. For liver studies, however, inaccessibility of the portal vein makes direct measurement of the hepatic dual-input function impossible in humans. We want to develop a method to predict the portal venous time-activity curve from measurements of an arterial time-activity curve. An impulse-response function based on a continuous distribution of washout constants is developed and validated for the gut. Experiments with simultaneous blood sampling in aorta and portal vein were made in 13 anesthetized pigs following inhalation of intravascular [O-15] CO or injections of diffusible 3-O[ C-11] methylglucose (MG). The parameters of the impulse-response function have a physiological interpretation in terms of the distribution of washout constants and are mathematically equivalent to the mean transit time ( T) and standard deviation of transit times. The results include estimates of mean transit times from the aorta to the portal vein in pigs: (T) over bar = 0.35 +/- 0.05 min for CO and 1.7 +/- 0.1 min for MG. The prediction of the portal venous time-activity curve benefits from constraining the regression fits by parameters estimated independently. This is strong evidence for the physiological relevance of the impulse-response function, which includes asymptotically, and thereby justifies kinetically, a useful and simple power law. Similarity between our parameter estimates in pigs and parameter estimates in normal humans suggests that the proposed model can be adapted for use in humans.