924 resultados para Gibbs energy of mixing


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The metal-to-metal charge transfer (MMCT) transitions of a series of Class II mixed valence dinuclear complexes bearing cyano bridging ligands may be varied systematically by variations to either the hexacyanometallate(II) donor or Co-III acceptor moieties. Specifically, the new dinuclear species trans-[(LCoNCFe)-Co-14S(CN)(5)](-) (L-14S = 6-methyl-1,11-diaza-4,8-dithia- cyclotetradecane-6-amine) and trans-[(LCoNCRu)-Co-14(CN)(5)]-(L-14 = 6-methyl-1,4,8,11-tetraazacyclotetradecane-6-amine) have been prepared and their spectroscopic and electrochemical properties are compared with the relative trans-[(LCoNCFe)-Co-14(CN)(5)](-). The crystal structures of Na{trans-[(LCoNCFe)-Co-14S(CN)(5)]}.51/2H(2)O.1/2EtOH, Na{trans-[(LCoNCRu)-Co-14(CN)(5)]}.3H(2)O and Na{trans-[(LCoNCRu)-Co-14(CN)(5)]}.8H(2)O are also reported. The ensuing changes to the MMCT energy have been examined within the framework of Hush theory, and it was found that the free energy change between the redox isomers was the dominant effect in altering the energy of the MMCT transition.

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Activated sludge basins (ASBs) are a key-step in wastewater treatment processes that are used to eliminate biodegradable pollution from the water discharged to the natural environment. Bacteria found in the activated sludge consume and assimilate nutrients such as carbon, nitrogen and phosphorous under specific environmental conditions. However, applying the appropriate agitation and aeration regimes to supply the environmental conditions to promote the growth of the bacteria is not easy. The agitation and aeration regimes that are applied to activated sludge basins have a strong influence on the efficacy of wastewater treatment processes. The major aims of agitation by submersible mixers are to improve the contact between biomass and wastewater and the prevention of biomass settling. They induce a horizontal flow in the oxidation ditch, which can be quantified by the mean horizontal velocity. Mean values of 0.3-0.35 m s-1 are recommended as a design criteria to ensure best conditions for mixing and aeration (Da Silva, 1994). To give circulation velocities of this order of magnitude, the positioning and types of mixers are chosen from the plant constructors' experience and the suppliers' data for the impellers. Some case studies of existing plants have shown that measured velocities were not in the range that was specified in the plant design. This illustrates that there is still a need for design and diagnosis approach to improve process reliability by eliminating or reducing the number of short circuits, dead zones, zones of inefficient mixing and poor aeration. The objective of the aeration is to facilitate the quick degradation of pollutants by bacterial growth. To achieve these objectives a wastewater treatment plant must be adequately aerated; thus resulting in 60-80% of all energetic consummation being dedicated to the aeration alone (Juspin and Vasel, 2000). An earlier study (Gillot et al., 1997) has illustrated the influence that hydrodynamics have on the aeration performance as measure by the oxygen transfer coefficient. Therefore, optimising the agitation and aeration systems can enhance the oxygen transfer coefficient and consequently reduce the operating costs of the wastewater treatment plant. It is critically important to correctly estimate the mass transfer coefficient as any errors could result in the simulations of biological activity not being physically representative. Therefore, the transfer process was rigorously examined in several different types of process equipment to determine the impact that different hydrodynamic regimes and liquid-side film transfer coefficients have on the gas phase and the mass transfer of oxygen. To model the biological activity occurring in ASBs, several generic biochemical reaction models have been developed to characterise different biochemical reaction processes that are known as Activated Sludge Models, ASM (Henze et al., 2000). The ASM1 protocol was selected to characterise the impact of aeration on the bacteria consuming and assimilating ammonia and nitrate in the wastewater. However, one drawback of ASM protocols is that the hydrodynamics are assumed to be uniform by the use of perfectly mixed, plug flow reactors or as a number of perfectly mixed reactors in series. This makes it very difficult to identify the influence of mixing and aeration on oxygen mass transfer and biological activity. Therefore, to account for the impact of local gas-liquid mixing regime on the biochemical activity Computational Fluid Dynamics (CFD) was used by applying the individual ASM1 reaction equations as the source terms to a number of scalar equations. Thus, the application of ASM1 to CFD (FLUENT) enabled the investigation of the oxygen transfer efficiency and the carbon & nitrogen biological removal in pilot (7.5 cubic metres) and plant scale (6000 cubic metres) ASBs. Both studies have been used to validate the effect that the hydrodynamic regime has on oxygen mass transfer (the circulation velocity and mass transfer coefficient) and the effect that this had on the biological activity on pollutants such as ammonia and nitrate (Cartland Glover et al., 2005). The work presented here is one part to of an overall approach for improving the understanding of ASBs and the impact that they have in terms of the hydraulic and biological performance on the overall wastewater treatment process. References CARTLAND GLOVER G., PRINTEMPS C., ESSEMIANI K., MEINHOLD J., (2005) Modelling of wastewater treatment plants ? How far shall we go with sophisticated modelling tools? 3rd IWA Leading-Edge Conference & Exhibition on Water and Wastewater Treatment Technologies, 6-8 June 2005, Sapporo, Japan DA SILVA G. (1994). Eléments d'optimisation du transfert d'oxygène par fines bulles et agitateur séparé en chenal d'oxydation. PhD Thesis. CEMAGREF Antony ? France. GILLOT S., DERONZIER G., HEDUIT A. (1997). Oxygen transfer under process conditions in an oxidation ditch equipped with fine bubble diffusers and slow speed mixers. WEFTEC, Chicago, USA. HENZE M., GUJER W., MINO T., van LOOSDRECHT M., (2000). Activated Sludge Models ASM1, ASM2, ASM2D and ASM3, Scientific and Technical Report No. 9. IWA Publishing, London, UK. JUSPIN H., VASEL J.-L. (2000). Influence of hydrodynamics on oxygen transfer in the activated sludge process. IWA, Paris - France.

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We obtain new combinatorial upper and lower bounds for the potential energy of designs in q-ary Hamming space. Combined with results on reducing the number of all feasible distance distributions of such designs this gives reasonable good bounds. We compute and compare our lower bounds to recently obtained universal lower bounds. Some examples in the binary case are considered.

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The nonlinear properties of small amplitude electron-acoustic solitary waves (EAWs) in a homogeneous system of unmagnetized collisionless plasma consisted of a cold electron fluid and isothermal ions with two different temperatures obeying Boltzmann type distributions have been investigated. A reductive perturbation method was employed to obtain the Kadomstev-Petviashvili (KP) equation. At the critical ion density, the KP equation is not appropriate for describing the system. Hence, a new set of stretched coordinates
is considered to derive the modified KP equation. Moreover, the solitary solution, soliton energy and the associated electric field at the critical ion density were computed. The present investigation can be of relevance to the electrostatic solitary structures observed in various space plasma environments, such as Earth’s magnetotail region.

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The energy of a symmetric matrix is the sum of the absolute values of its eigenvalues. We introduce a lower bound for the energy of a symmetric partitioned matrix into blocks. This bound is related to the spectrum of its quotient matrix. Furthermore, we study necessary conditions for the equality. Applications to the energy of the generalized composition of a family of arbitrary graphs are obtained. A lower bound for the energy of a graph with a bridge is given. Some computational experiments are presented in order to show that, in some cases, the obtained lower bound is incomparable with the well known lower bound $2\sqrt{m}$, where $m$ is the number of edges of the graph.

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Given a transitive Anosov diffeomorphism on a closed manifold it is known that, for smooth enough observables, the system is mixing w.r.t. the measure of maximal entropy. Therefore, it makes sense to investigate the speed of decay of correlations and to look for the so-called Ruelle-Pollicott resonances, in order to determine a complete asymptotics for the decay of correlations. In this thesis we are able to find the first terms of that asymptotics and to prove an estimate for the speed of decaying of correlations. The proof is based on a surprising connection between the action of a transfer operator on suitable anisotropic Banach spaces of currents and the action induced by the Anosov map on the de Rham cohomology.

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Short fiber reinforced thermoplastics have generated much interest these days since fibrous materials tend to increase both mechanical and thermal properties, such as tensile strength, flexural strength, flexural modulus, heat deflection temperature, creep resistance, and some times impact strength of thermoplastics. If the matrix and reinforcement are both based on polymers the composite are recyclable. The rheological behavior of recyclable composites based on nylon fiber reinforced polypropylene (PP) is reported in this paper. The rheological behavior was evaluated both using a capillary rheometer and a torque rheometer. The study showed that the composite became pseudoplastic with fiber content and hence fiber addition did not affect processing adversely at higher shear rates. The torque rheometer data resembled that obtained from the capillary rheometer. The energy of mixing and activation energy of mixing also did not show much variation from that of PP alone.

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A thermodynamic study involving 7-nitro-1,3,5-triaza adamantane, 1, and its interaction with metal cations in nonaqueous media is first reported. Solubility data of 1 in various solvents were used to derive the standard Gibbs energies of solution, Delta G(s)degrees in these solvents. The effect of solvation in the different media was assessed from the Gibbs energy of transfer taking acetonitrile as a reference solvent. (1)H NMR studies of the interaction of 1 and metal cations were carried out in CD(3)CN and CD(3)OD and the data are reported. Conductance measurements revealed that this ligand forms lead(II) or zinc complexes of 1: 1 stoichiometry in acetonitrile. It also revealed a stoichiometry of two molecules of 1 per mercury(II) and two cadmiu (II) ions per molecule of 1. The addition of silver salt to 1 led to the precipitation of the silver-1 complex which was isolated and characterized by X-ray crystallography. At variance with conductance measurements in solution, in the solid state the X-ray structure show`s a 1:1 stoichiometry in the Hg(II) complex. The themiodynamics of complexation of 1 and these cations provide a quantitative assessment of the selective behavior of this ligand for ions of environmental relevance.

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The cytosolic phosphorylation ratio ([ATP]/[ADP][P(i)]) in the mammalian heart was found to be inversely related to body mass with an exponent of -0.30 (r = 0.999). This exponent is similar to -0.25 calculated for the mass-specific O2 consumption. The inverse of cytosolic free [ADP], the Gibbs energy of ATP hydrolysis (delta G'ATP), and the efficiency of ATP production (energy captured in forming 3 mol of ATP per cycle along the mitochondrial respiratory chain from NADH to 1/2 O2) were all found to scale with body mass with a negative exponent. On the basis of scaling of the phosphorylation ratio and free cytosolic [ADP], we propose that the myocardium and other tissues of small mammals represent a metabolic system with a higher driving potential (a higher delta G'ATP from the higher [ATP]/[ADP][P(i)]) and a higher kinetic gain [(delta V/Vmax)/delta [ADP]] where small changes in free [ADP] produce large changes in steady-state rates of O2 consumption. From the inverse relationship between mitochondrial efficiency and body size we calculate that tissues of small mammals are more efficient than those of large mammals in converting energy from the oxidation of foodstuffs to the bond energy of ATP. A higher efficiency also indicates that mitochondrial electron transport is not the major site for higher heat production in small mammals. We further propose that the lower limit of about 2 g for adult endotherm body size (bumblebee-bat, Estrucan shrew, and hummingbird) may be set by the thermodynamics of the electron transport chain. The upper limit for body size (100,000-kg adult blue whale) may relate to a minimum delta G'ATP of approximately 55 kJ/mol for a cytoplasmic phosphorylation ratio of 12,000 M-1.