Effects of Total Thermal Balance on the Thermal Energy Absorbed or Released by a High-Temperature Phase Change Material

Front tracking and enthalpy methods used to study phase change processes are based on a local thermal energy balance at the liquid–solid interface where mass accommodation methods are also used to account for the density change during the phase transition. Recently, it has been shown that a local thermal balance at the interface does not reproduce the thermodynamic equilibrium in adiabatic systems. Total thermal balance through the entire liquid–solid system can predict the correct thermodynamic equilibrium values of melted (solidified) mass, system size, and interface position. In this work, total thermal balance is applied to systems with isothermal–adiabatic boundary conditions to estimate the sensible and latent heat stored (released) by KNO3 and KNO3/NaNO3 salts which are used as high-temperature phase change materials. Relative percent differences between the solutions obtained with a local thermal balance at the interface and a total thermal balance for the thermal energy absorbed or released by high-temperature phase change materials are obtained. According to the total thermal balance proposed, a correction to the liquid–solid interface dynamics is introduced, which accounts for an extra amount of energy absorbed or released during the phase transition. It is shown that melting or solidification rates are modified by using a total thermal balance through the entire system. Finally, the numerical and semi-analytical methods illustrate that volume changes and the fraction of melted (solidified) solid (liquid) estimated through a local thermal balance at the interface are not invariant in adiabatic systems. The invariance of numerical and semi-analytical solutions in adiabatic systems is significantly improved through the proposed model.     

On the population monotonicity of independent set games

An independent set game is a cooperative game dealing with profit sharing in the maximum independent set problem. A population monotonic allocation scheme is a rule specifying how to share the profit of each coalition among its participants such that every participant is better off when the coalition expands. In this paper, we provide a necessary and sufficient characterization for independent set games admitting population monotonic allocation schemes. Moreover, our characterization can be verified efficiently.     

Algebraic spatial correlations in lattice gas automata violating detailed balance

In this paper we discuss the existence of generic long-range correlations in spatially homogeneous and stable equilibrium states of closed lattice gas automata whose stochastic collision rules violate the symmetry conditions of detailed balance and in addition satisfy local conservation laws. Such correlations occur even though the collision rules are strictly local and invariant under all symmetries of the lattice. First a phenomenological (Langevin equation) approach is discussed. Next we present a theoretical analysis on the basis of an approximate microscopic (ring kinetic) theory. This theory is used to calculate the amplitude ofr ^– tails in the spatial correlations, and the result is compared with computer simulations.     

Interactions between naproxen and maltoheptaose,the non-cyclic analog ofβ-cyclodextrin

The crystallinity of naproxen in solid combinations with amorphous maltoheptaose, the non-cyclic analog of -cyclodextrin, was assessed using differential scanning calorimetry supported by X-ray powder diffractometry. Cogrinding induced a decrease in drug crystalinity to an extent which depended on the grinding time, and was most pronounced for the combination of equimolecular composition. Thermal analysis showed that the mechanism behind the conversion of crystalline naproxen into the amorphous state by cogrinding with maltoheptaose differed from that with randomly substituted, amorphous -cyclodextrins. Interactions of naproxen with maltoheptaose in aqueous solution were studied by means of fluorescence spectroscopy, phase-solubility analysis, and computeraided molecular modelling. Maltoheptaose can wrap up naproxen, taking on a cyclic conformation and forming a pseudo inclusion complex (apparent binding constant K_{1: 1} = 1.0 × 10³ (–20%) L mol^–1 at 25 °C) which is about as stable as the true inclusion complex with -cyclodextrin in the lowest temperature range (0-100 K). A better complexing ability for naproxen in terms of binding constant values, however, was displayed by both native and derivatized -cyclodextrins, the hosts with covalently-bound cyclic structures.     

Influence of the heating conditions on the thermal and chemical behaviour of solid particles undergoing a fast endothermic decomposition

This paper deals with models describing the thermal and chemical behaviour of solid particles undergoing fast endothermic reactions under the influence of an external heat flux. The heat source temperature is supposed to be constant, to increase with time, or to deliver a simple thermal flash. It is shown that the pyrolysis conditions (reaction temperature, conversion, etc.) depend on the chemical characteristics of the reaction and also to a large extent on the external heating conditions. Relationships are proposed to take into account these parameters. The results are applied to the thermal decomposition of NaHCO₃. The pyrolysis of cellulose is finally chosen in order to show how these operating parameters can also affect the selectivity of a more complex reaction.     

Predicting the performance of molecularly imprinted polymers: Selective extraction of caffeine by molecularly imprinted solid phase extraction

A rational design approach was taken to the planning and synthesis of a molecularly imprinted polymer capable of extracting caffeine (the template molecule) from a standard solution of caffeine and further from a food sample containing caffeine. Data from NMR titration experiments in conjunction with a molecular modelling approach was used in predicting the relative ratios of template to functional monomer and furthermore determined both the choice of solvent (porogen) and the amount used for the study. In addition the molecular modelling program yielded information regarding the thermodynamic stability of the pre-polymerisation complex. Post-polymerisation analysis of the polymer itself by analysis of the pore size distribution by BET yielded significant information regarding the nature of the size and distribution of the pores within the polymer matrix. Here is proposed a stepwise procedure for the development and testing of a molecularly imprinted polymer using a well-studied compound—caffeine as a model system. It is shown that both the physical characteristics of a molecularly imprinted polymer (MIP) and the analysis of the pre-polymerisation complex can yield vital information, which can predict how well a given MIP will perform.     

Pervaporative transport modelling in a ternary system: ethyltertiarybutylether/ethanol/polyurethaneimide

The study deals with the analysis of diffusion and mass transfer modelling during pervaporation in a true ternary system involving a polar liquid mixture (ETBE/EtOH) and a polar block copolymer (polyurethaneimide or PUI). A survey of methods of pervaporative transfer modelling in ternary systems is first developed. From differential permeation experiments carried out with both pure liquids, it appears that both permeants obey a Fickian law. Moreover, the diffusional behaviour is consistent with Long's model, which has thus been assumed for the related ternary system. An extension of the Brun's model is then derived, which takes into account the diffusion coupling as well the significant deviation from sorption ideality. From a practical point of view, the calculated values of fluxes show generally good agreement with the experimental results, although a small deviation occurs for mixtures of low ethanol content. Diffusion coefficients of both pure solvents corresponding to transient or steady state are compared. A very good agreement is found for the aprotic permeant (ETBE). whereas the diffusion coefficient of ethanol in transient state is only the quarter of the value corresponding to steady state. The results are discussed in comparison with related investigations in the literature, involving specific liquid-polymer interactions.     

Synthesis and conformational analysis of naphth[1′,2′:5,6][1,3]oxazino[3,2-c][1,3]benzoxazine and naphth[1′,2′:5,6][1,3]oxazino[3,4-c][1,3]benzoxazine derivatives

A new functional group, the hydroxy group, was inserted into a Betti base by reaction with salicylaldehyde, and the naphthoxazine derivatives thus obtained were converted by ring-closure reactions with formaldehyde, acetaldehyde, propionaldehyde or phosgene to the corresponding naphth[1′2′:5,6][1,3]oxazino[3,2-c][1,3]benzoxazine derivatives. Further, the conformational analysis of these polycyclic compounds by NMR spectroscopy and an accompanying molecular modelling are reported; especially, both quantitative anisotropic ring current effects of the aromatic moieties in these compounds and steric substituent effects were employed to determine the stereochemistry of the naphthoxazinobenzoxazine derivatives.     

Kinetic modelling of cadmium removal from phosphoric acid by non-dispersive solvent extraction

In this work it is reported that the kinetic modelling of the separation of cadmium from phosphoric acid by non-dispersive solvent extraction. Using Cyanex 302 as selective extractant, the extraction step was carried out in a hollow fibre module containing polypropylene fibres, whereas the concentration step required a ceramic module with tubular channels due to the high acidity of the backextraction agent. Application of the methodology previously reported by the authors led to the development of a kinetic model with three design parameters, i.e., equilibrium constant of the extraction reaction (K'_e = 6 × 10³ mol⁻²/l⁻²), membrane mass transport coefficient of the extraction module K_me=8.33×10⁻⁸ m/s) and of the backextraction module (K_ms=3.33×10⁻⁸ m/s), that described satisfactorily the behaviour of the separation-concentration system. Thus, in this work a new application of the non-dispersive solvent extraction technology is presented, characterising at the same time the behaviour and parameters of a new type of contactor, i.e., a tubular ceramic module.     

Shortcut method for evaluation and design of a hybrid process for enantioseparations

Hybrid processes for enantioseparations have a considerable potential for reducing investment and operational costs. An example is the combination of simulated moving bed (SMB) chromatography and selective crystallisation. However, the design of integrated processes is a difficult task. A shortcut method is presented that can serve as a tool for design and estimation of the potential of such processes. The approach requires only limited experimental data and thus allows for systematic parameter studies. The method is based on the determination of the purity-performance characteristic of the SMB process and rigorous application of mass balances. The use of relative mass fluxes allows derivation of simple algebraic expressions for essential process parameters. The significant potential of combining SMB and crystallisation is demonstrated for the example of the separation of mandelic acid enantiomers.