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.

A comparative study of carbon gasification with O-2 and CO2 by density functional theory calculations

A comparative study of carbon gasification with O-2 and CO2 was conducted by using density functional theory calculations. It was found that the activation energy and the number of active sites in carbon gasification reactions are significantly affected by both the capacity and manner of gas chemisorption. O-2 has a strong adsorption capacity and the dissociative chemisorption of O-2 is thermodynamically favorable on either bare carbon surface or even isolated edge sites. As a result, a large number of semiquinone and o-quinone oxygen can be formed indicating a significant increase in the number of active sites. Moreover, the weaker o-quinone C-C bonds can also drive the reaction forward at (ca. 30%) lower activation energy. Epoxy oxygen forms under relatively high O-2 pressure, and it can only increase the number of active sites, not further reduce the activation energy. CO2 has a lower adsorption capacity. Dissociative chemisorption of CO2 can only occur on two consecutive edge sites and o-quinone oxygen formed from CO2 chemisorption is negligible, let alone epoxy oxygen. Therefore, CO2-carbon reaction needs (ca 30%) higher activation energy. Furthermore, the effective active sites are also reduced by the manner Of CO2 chemisorption. A combination of the higher activation energy and the fewer active sites leads to the much lower reaction rate Of CO2-carbon.

Testing landscape metrics as indicators of habitat loss and fragmentation in continuous eucalypt forests (Queensland, Australia)

Landscape metrics are widely applied in landscape ecology to quantify landscape structure. However, many are poorly tested and require rigorous validation if they are to serve as reliable indicators of habitat loss and fragmentation, such as Montreal Process Indicator 1.1e. We apply a landscape ecology theory, supported by exploratory and confirmatory statistical techniques, to empirically test landscape metrics for reporting Montreal Process Indicator 1.1e in continuous dry eucalypt forests of sub-tropical Queensland, Australia. Target biota examined included: the Yellow-bellied Glider (Petaurus australis); the diversity of nectar and sap feeding glider species including P. australis, the Sugar Glider P. breviceps, the Squirrel Glider P. norfolcensis, and the Feathertail Glider Acrobates pygmaeus; six diurnal forest birds species; total diurnal bird species diversity; and the density of nectar-feeding diurnal bird species. Two scales of influence were considered: the stand-scale (2 ha), and a series of radial landscape extents (500 m - 2 km; 78 - 1250 ha) surrounding each fauna transect. For all biota, stand-scale structural and compositional attributes were found to be more influential than landscape metrics. For the Yellow-bellied Glider, the proportion of trace habitats with a residual element of old spotted-gum/ironbark eucalypt trees was a significant landscape metric at the 2 km landscape extent. This is a measure of habitat loss rather than habitat fragmentation. For the diversity of nectar and sap feeding glider species, the proportion of trace habitats with a high coefficient of variation in patch size at the 750 m extent was a significant landscape metric. None of the landscape metrics tested was important for diurnal forest birds. We conclude that no single landscape metric adequately captures the response of the region's forest biota per se. This poses a major challenge to regional reporting of Montreal Process Indicator 1.1e, fragmentation of forest types.

Revisiting the question of limited genetic variation within Schistosoma japonicum

Recent electrophoretic data have indicated that Schistosoma japonicum in mainland China may be a species complex, with the existence of a cryptic species being predicted from the analysis of schistosome populations from Sichuan province. To investigate the Sichuan form of S. japonicum, 4.9 kbp of mitochondrial DNA from each of three samples of the parasite from China (two from Sichuan and one from Hunan) and one from Sorsogon in the Philippines were amplified, sequenced and characterized. The sequence data were compared with those from the related South-east Asian species of S. mekongi (Khong Island, Laos) and S. malayensis (Baling, Malaysia) and that from S. japonicum from Anhui (China). At both the nucleotide and amino-acid levels, the variation among the five S. japonicum samples was limited ( < 1%). This was consistent with the conclusions drawn from previous molecular studies, in which minimal variation among S. japonicum populations was also detected. In contrast, S. mekongi and S. malayensis, species recognized as separate but closely related, differ from each other by about 10%, and each differs by 25%-26% from S. japonicum. Phylogenetic trees provided a graphic representation of these differences, showing all S. japonicum sequences to be very tightly clustered and distant from S. mekongi and S. malayensis, the last two being clearly distinct from each other. The results thus indicate no significant intraspecific genetic variation among S. japonicum samples collected from different geographical areas and do not support the idea of a distinct form in Sichuan.

Social rules for managing attempted interpersonal domination in the workplace: Influence of status and gender.

The present study utilized a social rules approach to investigate the relative influence of gender and status on managers' self-evaluations of their effectiveness in handling a dominating subordinate. In the first study 84 White middle-class participants identified the prescriptive and proscriptive rules for socially appropriate responding to a stimulus situation involving a pushy subordinate. Four rule sets were identified for female and male managers and subordinates, respectively. Rule-sets shared a number of common rules and showed some variation according to gender roles. In the second study, 91 White middle-class participants rated the individual rules for importance and also rated their personal and managerial effectiveness when responding to the stimulus situation using gender- and status-consistent and gender-and status-inconsistent response strategies. Both men and women rated the female gender and status- consistent strategy as most effective, and rated the status-inconsistent strategy as less effective than a gender-inconsistent response. Results were interpreted as providing more support for a situational gender-related theory of workplace behavior, rather than a traditional gender role perspective.

The pyramidal cell of the sensorimotor cortex of the macaque monkey: Phenotypic variation

Recent studies have revealed striking differences in pyramidal cell structure among cortical regions involved in the processing of different functional modalities. For example, cells involved in visual processing show systematic variation, increasing in morphological complexity with rostral progression from V1 through extrastriate areas. Differences have also been identified between pyramidal cells in somatosensory, motor and prefrontal cortex, but the extent to which the pyramidal cell phenotype may vary between these functionally related cortical regions remains unknown. In the present study we investigated the structure of layer III pyramidal cells in somatosensory and motor areas 3b, 4, 5, 6 and 7b of the macaque monkey. Cells were intracellularly injected in fixed, flat-mounted cortical slices and analysed for morphometric parameters. The size of the basal dendritic arbours, the number of their branches and their spine density were found to vary systematically between areas. Namely, we found a trend for increasing complexity in dendritic arbour structure through areas 3b, 5 and 7b. A similar trend occurred through areas 4 and 6. The differences in arbour structure may determine the number of inputs received by neurons and may thus be an important factor in determining function at the cellular and systems level.

Application of fairness theory to service failures and service recovery

This article presents a fairness theory-based conceptual framework for studying and managing consumers’ emotions during service recovery attempts. The conceptual framework highlights the central role played by counterfactual thinking and accountability. Findings from five focus groups are also presented to lend further support to the conceptual framework. Essentially, the article argues that a service failure event triggers an emotional response in the consumer, and from here the consumer commences an assessment of the situation, considering procedural justice, interactional justice, and distributive justice elements, while engaging in counterfactual thinking and apportioning accountability. More specifically, the customer assesses whether the service provider could and should have done something more to remedy the problem and how the customer would have felt had these actions been taken. The authors argue that during this process situational effort is taken into account when assessing accountability. When service providers do not appear to exhibit an appropriate level of effort, consumers attribute this to the service provider not caring. This in turn leads to the customer feeling more negative emotions, such as anger and frustration. Managerial implications of the study are discussed.

Comparative genetic study confirms exceptionally low genetic variation in the ancient and endangered relictual conifer, Wollemia nobilis (Araucariaceae)

The Wollemi pine, Wollemia nobilis (Araucariaceae), was discovered in 1994 as the only extant member of the genus, previously known only from the fossil record. With fewer than 100 trees known from an inaccessible canyon in southeastern Australia, it is one of the most endangered tree species in the world. We conducted a comparative population genetic survey at allozyme, amplified fragment length polymorphism (AFLP) and simple sequence repeat (SSR) loci in W. nobilis, Araucaria cunninghatnii and Agathis robusta - representatives of the two sister genera. No polymorphism was detected at 13 allozyme loci, more than 800 AFLP loci or the 20 SSR loci screened in W. nobilis. In Ag. robusta only one of 12 allozyme loci, five of 800 AFLP loci and none of the 15 SSR loci were variable. For A. cunninghamii, 10 of > 800 AFLP loci and five of 20 SSR loci were variable. Thus low genetic diversity characterizes all three species. While not ruling out the existence of genetic variation, we conclude that genetic diversity is exceptionally low in the Wollemi pine. To our knowledge this is the most extreme case known in plants. We conclude that the combination of small population effects, clonality and below-average genetic variation in the family are probable contributing factors to the low diversity. The exceptionally low genetic diversity of the Wollemi pine, combined with its known susceptibility to exotic fungal pathogens, reinforces current management policies of strict control of access to the pines and secrecy of the pine locations.