Adsorption of argon and nitrogen in cylindrical pores of MCM-41 materials: application of density functional theory

Adsorption of argon and nitrogen at their respective boiling points in cylindrical pores of MCM-41 type silica-like adsorbents is studied by means of a non-local density functional theory (NLDFT), which is modified to deal with amorphous solids. By matching the theoretical results of the pore filling pressure versus pore diameter against the experimental data, we arrive at a conclusion that the adsorption branch (rather than desorption) corresponds to the true thermodynamic equilibrium. If this is accepted, we derive the optimal values for the solid–fluid molecular parameters for the system amorphous silica–Ar and amorphous silica–N2, and at the same time we could derive reliably the specific surface area of non-porous and mesoporous silica-like adsorbents, without a recourse to the BET method. This method is then logically extended to describe the local adsorption isotherms of argon and nitrogen in silica-like pores, which are then used as the bases (kernel) to determine the pore size distribution. We test this with a number of adsorption isotherms on the MCM-41 samples, and the results are quite realistic and in excellent agreement with the XRD results, justifying the approach adopted in this paper.

Selecting optimal instantiations of data models - Theory and validation of an ex ante approach

The schema of an information system can significantly impact the ability of end users to efficiently and effectively retrieve the information they need. Obtaining quickly the appropriate data increases the likelihood that an organization will make good decisions and respond adeptly to challenges. This research presents and validates a methodology for evaluating, ex ante, the relative desirability of alternative instantiations of a model of data. In contrast to prior research, each instantiation is based on a different formal theory. This research theorizes that the instantiation that yields the lowest weighted average query complexity for a representative sample of information requests is the most desirable instantiation for end-user queries. The theory was validated by an experiment that compared end-user performance using an instantiation of a data structure based on the relational model of data with performance using the corresponding instantiation of the data structure based on the object-relational model of data. Complexity was measured using three different Halstead metrics: program length, difficulty, and effort. For a representative sample of queries, the average complexity using each instantiation was calculated. As theorized, end users querying the instantiation with the lower average complexity made fewer semantic errors, i.e., were more effective at composing queries. (c) 2005 Elsevier B.V. All rights reserved.

Comparison of nitrogen adsorption at 77 K on non-porous silica and pore wall of MCM-41 materials by means of density functional theory

Nitrogen adsorption on a surface of a non-porous reference material is widely used in the characterization. Traditionally, the enhancement of solid-fluid potential in a porous solid is accounted for by incorporating the surface curvature into the solid-fluid Potential of the flat reference surface. However, this calculation procedure has not been justified experimentally. In this paper, we derive the solid-fluid potential of mesoporous MCM-41 solid by using solely the adsorption isotherm of that solid. This solid-fluid potential is then compared with that of the non-porous reference surface. In derivation of the solid-fluid potential for both reference surface and mesoporous MCM-41 silica (diameter ranging front 3 to 6.5 nm) we employ the nonlocal density functional theory developed for amorphous solids. It is found that, to out, surprise, the solid-fluid potential of a porous solid is practically the same as that for the reference surface, indicating that there is no enhancement due to Surface curvature. This requires further investigations to explain this unusual departure from our conventional wisdom of curvature-induced enhancement. Accepting the curvature-independent solid-fluid potential derived from the non-porous reference surface, we analyze the hysteresis features of a series of MCM-41 samples. (c) 2005 Elsevier Inc. All rights reserved.

Pore size distribution analysis of activated carbons: Application of density functional theory using nongraphitized carbon black as a reference system

The application of nonlocal density functional theory (NLDFT) to determine pore size distribution (PSD) of activated carbons using a nongraphitized carbon black, instead of graphitized thermal carbon black, as a reference system is explored. We show that in this case nitrogen and argon adsorption isotherms in activated carbons are precisely correlated by the theory, and such an excellent correlation would never be possible if the pore wall surface was assumed to be identical to that of graphitized carbon black. It suggests that pore wall surfaces of activated carbon are closer to that of amorphous solids because of defects of crystalline lattice, finite pore length, and the presence of active centers.. etc. Application of the NLDFT adapted to amorphous solids resulted in quantitative description of N-2 and Ar adsorption isotherms on nongraphitized carbon black BP280 at their respective boiling points. In the present paper we determined solid-fluid potentials from experimental adsorption isotherms on nongraphitized carbon black and subsequently used those potentials to model adsorption in slit pores and generate a corresponding set of local isotherms, which we used to determine the PSD functions of different activated carbons. (c) 2005 Elsevier Ltd. All rights reserved.

Intensive case management: A critical re-appraisal of the scientific evidence for effectiveness

Intensive Case Management (ICM) is widely claimed to be an evidence-based and cost effective program for people with high levels of disability as a result of mental illness. However, the findings of recent randomized controlled trials comparing ICM with 'usual services' suggest that both clinical and cost effectiveness of ICM may be weakening. Possible reasons for this, including fidelity of implementation, researcher allegiance effects and changes in the wider service environment within which ICM is provided, are considered. The implications for service delivery and research are discussed.

Charitable giving: A test of a revised Theory of Planned Behaviour model

Recent world events aside, downward trends in donating behaviour in Australia have increased the need for research into the factors that inhibit and encourage charitable giving. A revised Theory of Planned Behaviour (TPB) model was used to determine the influence of attitudes, norms (injunctive, descriptive, and moral norms), perceived behavioural control (PBC), and past behaviour (PB) on intentions to donate money to charities and community service organisations. Respondents (N=186) completed a questionnaire assessing the constructs of the revised TPB model. Four weeks later, self-reported donating behaviour was assessed (n=65). Results showed support for the revised TPB model. Attitudes, PBC, injunctive norms, moral norms, and PB all predicted donating intentions. Descriptive norms did not predict intentions. Intention was the only significant predictor of selfreported behaviour four weeks later, with neither PBC nor PB having a direct effect on behaviour. Theoretical and applied implications of the results are discussed.

A test of basic assumptions of Affective Events Theory (AET) in call centre work

Based on data from 2091 call centre representatives working in 85 call centres in the UK, central assumptions of affective events theory (AET) are tested. AET predicts that specific features of work (e.g. autonomy) have an impact on the arousal of emotions and moods at work that, in turn, co-determine job satisfaction of employees. AET further proposes that job satisfaction is an evaluative judgement that mainly explains cognitive-based behaviour, whereas emotions and moods better predict affective-based behaviour. The results support these assumptions. A clear separation of key constructs (job satisfaction, positive and negative emotions) was possible. Moreover, correlations between several work features (e.g. supervisory support) and job satisfaction were, in part, mediated by work emotions, even when controlling for gender, age, call centre type (in-house versus outsourced centres) and call centre size. Predictions regarding consequences of satisfaction and affect were partly corroborated as continuance commitment was more strongly related to job satisfaction than to positive emotions. In addition, affective commitment and health complaints were related to both emotions and job satisfaction to the same extent. Thus, AET is a fruitful framework for explaining why and how specific management strategies used for designing work features influence important organizational attitudes and well-being of employees. © 2006 British Academy of Management.

An application of strategic group theory to the UK pharmaceuticals industry

Conducts a strategic group mapping exercise by analysing R&D investment, sales/marketing cost and leadership information pertaining to the pharmaceuticals industry. Explains that strategic group mapping assists companies in identifying their principal competitors, and hence supports strategic decision-making, and shows that, in the pharmaceutical industry, R&D spending, the cost of sales and marketing, i.e. detailing, and technological leadership are mobility barriers to companies moving between sectors. Illustrates, in bubble-chart format, strategic groups in the pharmaceutical industry, plotting detailing-costs against the scale of activity in therapeutic areas. Places companies into 12 groups, and profiles the strategy and market-position similarities of the companies in each group. Concludes with three questions for companies to ask when evaluating their own, and their competitors, strategies and returns, and suggests that strategy mapping can be carried out in other industries, provided mobility barriers are identified.