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Charge Balance (charge + balance)
Selected AbstractsConstrained multivariate trend analysis applied to water quality variablesENVIRONMETRICS, Issue 1 2002D. M. Cooper Abstract Constrained multivariate regression analysis is used to model trends and seasonal effects in time series measurements of water quality variables. The constraint used ensures that when identifying trends the scientifically important charge balance of model-fitted concentrations is maintained, while accounting for between variable dependencies. The analysis is a special case of linear reduction of dimensionality which preserves the integrity of a subset of the original variables, while allowing the remainder to be identified as linear combinations of this subset. The technique is applied to water quality measurements made at the outflow from Loch Grannoch, an acid-sensitive loch in Scotland. A reduction in marine ion concentrations is observed in water samples collected four times a year over the period 1988,2000. This is identified with long term variability in the marine component in rainfall. Separation of the non-marine component of the solute load shows a reduction in non-marine sulphate and calcium concentrations, and an increase in the non-marine sodium concentration. There is no significant change in either alkalinity or acid neutralizing capacity over the period. The reduction in non-marine sulphate is consistent with reductions in atmospheric inputs of sulphate. However, the reduction in sulphate has not been accompanied by a reduction in the acidity of water samples from Loch Grannoch, but with a reduction in calcium concentration and an apparent increase in organic acids, as evidenced by increased dissolved organic carbon concentrations, with possible increases in nitrate and non-marine sodium concentrations. Copyright © 2002 John Wiley & Sons, Ltd. [source] The effect of surface,solute interactions on the transport of solutes through porous materialsEUROPEAN JOURNAL OF SOIL SCIENCE, Issue 3 2009D. A. Rose Summary We have investigated the effect of differences in surface charge, valency of ion, solute concentration, solution flux and physical structure on the leaching and uptake of individual ions from simple solutions flowing through porous materials. We studied the miscible displacement of solutions of four salts (KBr, K2SO4, CaBr2 and CaSO4) having different cation : anion ratios separately through three inert materials (ballotini, pumice and ceramic) and two sizes of a reactive material (sepiolite) over several ranges of concentration (c) and at many pore-water velocities (v) under steady vertical saturated flow. Breakthrough curves of individual effluent ions (K+, Br,, Ca2+ and SO42,) were analysed by CXTFIT 2.0 to optimize transport parameters (retardation factor, R; dispersion coefficient, K) assuming that transport was governed by the convective,dispersion equation. In the inert materials, R did not differ significantly from 1 irrespective of c. In sepiolite, R was < 1 for anions and > 1 for cations, and became more extreme as c decreased. R varied with the valency of the anions, as predicted by diffuse double layer theory, and with that of the cations by a simple charge balance. Freundlich isotherms, reconstructed from R values, described the sorption of the cations and exclusion of the anions. For the inert materials, K did not depend on the ion or c and increased monotonically with v. For sepiolite, K also increased with v and with small but non-significant differences between ions and concentrations. The K(v) functions were consistent with Passioura's theory of dispersion in aggregated media, and the transport was reversible as R and K values did not depend on whether the media were being leached or resalinized. The effective dispersion coefficient of an ion is K* = K/R so, although K(v) appears to be unaffected by ion or concentration of solute in sepiolite, K*(v) will be affected. Thus, the controlling factor of these surface,solute interactions is R. [source] Multifunctional Triphenylamine/Oxadiazole Hybrid as Host and Exciton-Blocking Material: High Efficiency Green Phosphorescent OLEDs Using Easily Available and Common MaterialsADVANCED FUNCTIONAL MATERIALS, Issue 17 2010Youtian Tao Abstract A new triphenylamine/oxadiazole hybrid, namely m -TPA- o -OXD, formed by connecting the meta -position of a phenyl ring in triphenylamine with the ortho -position of 2,5-biphenyl-1,3,4-oxadiazole, is designed and synthesized. The new bipolar compound is applicable in the phosphorescent organic light-emitting diodes (PHOLEDs) as both host and exciton-blocking material. By using the new material and the optimization of the device structures, very high efficiency green and yellow electrophosphorescence are achieved. For example, by introducing 1,3,5-tris(N -phenylbenzimidazol-2-yl)benzene (TPBI) to replace 2, 9-dimethyl-4,7-diphenyl-1, 10-phenanthroline (BCP)/tris(8-hydroxyquinoline)aluminium (Alq3) as hole blocking/electron transporting layer, followed by tuning the thicknesses of hole-transport 1, 4-bis[(1-naphthylphenyl)amino]biphenyl (NPB) layer to manipulate the charge balance, a maximum external quantum efficiency (,EQE,max) of 23.0% and a maximum power efficiency (,p,max) of 94.3 lm W,1 are attained for (ppy)2Ir(acac) based green electrophosphorescence. Subsequently, by inserting a thin layer of m -TPA- o -OXD as self triplet exciton block layer between hole-transport and emissive layer to confine triplet excitons, a ,EQE,max of 23.7% and ,p,max of 105 lm W,1 are achieved. This is the highest efficiency ever reported for (ppy)2Ir(acac) based green PHOLEDs. Furthermore, the new host m -TPA- o -OXD is also applicable for other phosphorescent emitters, such as green-emissive Ir(ppy)3 and yellow-emissive (fbi)2Ir(acac). A yellow electrophosphorescent device with ,EQE,max of 20.6%, ,c,max of 62.1 cd A,1, and ,p,max of 61.7 lm W,1, is fabricated. To the author's knowledge, this is also the highest efficiency ever reported for yellow PHOLEDs. [source] Harvesting Excitons Via Two Parallel Channels for Efficient White Organic LEDs with Nearly 100% Internal Quantum Efficiency: Fabrication and Emission-Mechanism AnalysisADVANCED FUNCTIONAL MATERIALS, Issue 1 2009Qi Wang Abstract By incorporating two phosphorescent dyes, namely, iridium(III)[bis(4,6-difluorophenyl)-pyridinato-N,C2,]picolinate (FIrpic) for blue emission and bis(2-(9,9-diethyl-9H -fluoren-2-yl)-1-phenyl-1H -benzoimidazol-N,C3)iridium(acetylacetonate) ((fbi)2Ir(acac)) for orange emission, into a single-energy well-like emissive layer, an extremely high-efficiency white organic light-emitting diode (WOLED) with excellent color stability is demonstrated. This device can achieve a peak forward-viewing power efficiency of 42.5,lm,W,1, corresponding to an external quantum efficiency (EQE) of 19.3% and a current efficiency of 52.8,cd,A,1. Systematic studies of the dopants, host and dopant-doped host films in terms of photophysical properties (including absorption, photoluminescence, and excitation spectra), transient photoluminescence, current density,voltage characteristics, and temperature-dependent electroluminescence spectra are subsequently performed, from which it is concluded that the emission natures of FIrpic and (fbi)2Ir(acac) are, respectively, host,guest energy transfer and a direct exciton formation process. These two parallel pathways serve to channel the overall excitons to both dopants, greatly reducing unfavorable energy losses. It is noteworthy that the introduction of the multifunctional orange dopant (fbi)2Ir(acac) (serving as either hole-trapping site or electron-transporting channel) is essential to this concept as it can make an improved charge balance and broaden the recombination zone. Based on this unique working model, detailed studies of the slight color-shift in this WOLED are performed. It is quantitatively proven that the competition between hole trapping on orange-dopant sites and undisturbed hole transport across the emissive layer is the actual reason. Furthermore, a calculation of the fraction of trapped holes on (fbi)2Ir(acac) sites with voltage shows that the hole-trapping effect of the orange dopant is decreased with increasing drive voltage, leading to a reduction of orange emission. [source] Optimizing the formula of rare earth-bearing materials: A computational chemistry investigationINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 3 2007Marjorie Bertolus Abstract We present a computational investigation into the nature of bonds formed by rare earth elements (REE) in materials. This study focuses on the incorporation of neodymium in minerals called apatites, which are derived from fluorapatite: Ca10(PO4)6F2. These minerals, which allow many substitutions on all three Ca, P, and F sites, are considered as potential host phases for radioactive elements separated from nuclear waste. Nd and trivalent actinides have very similar physical and chemical properties, and Nd is not radioactive and much more easily handled. It is therefore very often used as a surrogate for actinides with oxidation degree three in experimental studies. Several formulas can be considered to substitute Nd3+ to Ca2+ and maintain charge balance of the apatite. Existing experimental and theoretical studies, however, mostly concern the Ca9Nd(PO4)5SiO4F2 formula, where the Nd incorporation is compensated by the replacement of one PO by a SiO group. Moreover, only the cation position has been studied, whereas the silicate position and its influence on stability are unknown. We present a more general investigation of possible charge compensations on the one hand, and of the various resulting configurations on the other. All possible configurations of the two formulas Ca9Nd(PO4)5 SiO4F2 and Ca8NdNa(PO4)6F2 have been considered. Calculations have been performed within the framework of density functional theory (DFT). A computation scheme that permits good accuracy in these systems within reasonable computation times is determined. The results obtained for cohesion energies, geometries, and electronic densities are discussed. As for the formulation, it is shown that the Ca8NdNa(PO4)6F2 formula is less stable than the fluorapatite, while Ca9Nd(PO4)5 SiO4F2 is more stable. For the structures, it is found that Nd substitutes preferably in the second cationic site. Moreover, the most stable structures exhibit the shortest Na,Nd or Nd,Si distances. Local charge balance therefore seems favorable. Then, it is shown that Nd forms covalent bonds both in apatite and in britholite, while Na forms ionic bonds. Finally, a first correlation between the material stability and the covalent character of the bonds formed is established. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 [source] Ternary fluorides BaMF4 (M = Zn, Mg and Mn) at low temperaturesACTA CRYSTALLOGRAPHICA SECTION B, Issue 5 2009Jose Maria Posse Ternary fluorides BaMF4 (M = Zn, Mg, Mn) have been studied in the temperature range from 300 to 10,K using synchrotron and laboratory powder and single-crystal diffraction. The first two compounds are stable down to 10,K, while the third one undergoes a phase transition to an incommensurately modulated structure at approximately 250,K. The modulated phase is stable down to 10,K. The magnetic anomalies at 45 and 27,K observed previously in BaMnF4 are exclusively reflected in the behavior of the , component of the q vector, which assumes an irrational value of approximately 0.395,Å,1 at the temperature corresponding to the onset of the magnetic ordering and then stays constant down to 10,K. Mn,Mn distances do not indicate any structural response to the magnetic ordering. The formation of the modulated phase can be explained on the basis of simple geometrical criteria. The incorporation of the large Mn cation in the octahedral sheets implies an increase of the cavity in which the Ba ion is incorporated. This leads to the formation of the modulated structure to adapt the coordination sphere around Ba in such a way that the bond-valence sums can be kept close to the ideal value of two. With further lowering of the temperature, the charge balance around the Ba ion requires an increasingly anharmonic character of the modulation function of Ba, until finally at 10,K a crenel-like shape is assumed for the modulation of this atom. [source] Structural derivation and crystal chemistry of apatitesACTA CRYSTALLOGRAPHICA SECTION B, Issue 1 2003T. J. White The crystal structures of the [A(1)2][A(2)3](BO4)3X apatites and the related compounds [A(1)2][A(2)3](BO5)3X and [A(1)2][A(2)3](BO3)3X are collated and reviewed. The structural aristotype for this family is Mn5Si3 (D88 type, P63/mcm symmetry), whose cation array approximates that of all derivatives and from which related structures arise through the systematic insertion of anions into tetrahedral, triangular or linear interstices. The construction of a hierarchy of space-groups leads to three apatite families whose high-symmetry members are P63/m, Cmcm and P63cm. Alternatively, systematic crystallographic changes in apatite solid-solution series may be practically described as deviations from regular anion nets, with particular focus on the O(1),A(1),O(2) twist angle , projected on (001) of the A(1)O6 metaprism. For apatites that contain the same A cation, it is shown that , decreases linearly as a function of increasing average ionic radius of the formula unit. Large deviations from this simple relationship may indicate departures from P63/m symmetry or cation ordering. The inclusion of A(1)O6 metaprisms in structure drawings is useful for comparing apatites and condensed-apatites such as Sr5(BO3)3Br. The most common symmetry for the 74 chemically distinct [A(1)2][A(2)3](BO4)3X apatites that were surveyed was P63/m (57%), with progressively more complex chemistries adopting P63 (21%), P (9%), P (4.3%), P21/m (4.3%) and P21 (4.3%). In chemically complex apatites, charge balance is usually maintained through charge-coupled cation substitutions, or through appropriate mixing of monovalent and divalent X anions or X -site vacancies. More rarely, charge compensation is achieved through insertion/removal of oxygen to produce BO5 square pyramidal units (as in ReO5) or BO3 triangular coordination (as in AsO3). Polysomatism arises through the ordered filling of [001] BO4 tetrahedral strings to generate the apatite,nasonite family of structures. [source] Coordination and hydrogen-bonding assemblies in hybrid reaction products between 5,10,15,20-tetra-4-pyridylporphyrin and dysprosium trinitrate hexahydrateACTA CRYSTALLOGRAPHICA SECTION C, Issue 8 2010Sophia Lipstman Reactions of the title free-base porphyrin compound (TPyP) with dysprosium trinitrate hexahydrate in different crystallization environments yielded two solid products, viz. [,-5,15-bis(pyridin-1-ium-4-yl)-10,20-di-4-pyridylporphyrin]bis[aquatetranitratodysprosium(III)] benzene solvate, [Dy2(NO3)8(C40H28N8)(H2O)2]·C6H6, (I), and 5,10,15,20-tetrakis(pyridin-1-ium-4-yl)porphyrin pentaaquadinitratodysprosate(III) pentanitrate diethanol solvate dihydrate, (C40H30N8)[Dy(NO3)2(H2O)5](NO3)5·2C2H6O·2H2O, (II). Compound (I) represents a 2:1 metal,porphyrin coordinated complex, which lies across a centre of inversion. Two trans -related pyridyl groups are involved in Dy coordination. The two other pyridyl substituents are protonated and involved in intermolecular hydrogen bonding along with the metal-coordinated water and nitrate ligands. Compound (II) represents an extended hydrogen-bonded assembly between the tetrakis(pyridin-1-ium-4-yl)porphyrin tetracation, the [Dy(NO3)2(H2O)5]+ cation and the free nitrate ions, as well as the ethanol and water solvent molecules. This report provides the first structural characterization of the exocyclic dysprosium complex with tetrapyridylporphyrin. It also demonstrates that charge balance can be readily achieved by protonation of the peripheral pyridyl functions, which then enhances their capacity in hydrogen bonding as H-atom donors rather than H-atom acceptors. [source] Two oxo complexes with tetranuclear [Fe4(,3 -O)2]8+ and trinuclear [Fe3(,3 -O)]7+ unitsACTA CRYSTALLOGRAPHICA SECTION C, Issue 7 2006Ana María Atria Two new oxo complexes, namely hexa-,2 -acetato-acetatoaquabis(di-3-pyridylamine)di-,3 -oxo-tetrairon(III) chloride monohydrate ethanol 1.25-solvate, [Fe4(C2H3O2)7O2(C10H9N3)2(H2O)]Cl·1.25C2H6O·H2O, (I), containing a tetranuclear [Fe4(,3 -O)2]8+ unit, and 2-methylimidazolium hexa-,2 -acetato-acetatodiaqua-,3 -oxo-triiron(III) chloride dihydrate, (C4H7N2)[Fe3(C2H3O2)7O(H2O)2]Cl·2H2O, (II), with a trinuclear [Fe3(,3 -O)]7+ unit, are presented. Both structures are formed by two well differentiated entities, viz. a compact isolated cluster composed of FeIII ions coordinated to O2, and CH3CO2, anions, and an external group formed by a central Cl, ion surrounded by different solvent groups to which the anion is bound through hydrogen bonding. In the case of (I), charge balance cannot be achieved within the groups, so the structure is macroscopically ionic; in the case of (II), in contrast, each group is locally neutral owing to the internal compensation of charges. The trinuclear complex crystallizes with the metal cluster, chloride anion and 2-methylimidazolium cation bisected by a crystallographic mirror plane. [source] A neutron crystallographic analysis of T6 porcine insulin at 2.1,Å resolutionACTA CRYSTALLOGRAPHICA SECTION D, Issue 10 2009Wakari Iwai Neutron diffraction data for T6 porcine insulin were collected to 2.1,Å resolution from a single crystal partly deuterated by exchange of mother liquor. A maximum-likelihood structure refinement was undertaken using the neutron data and the structure was refined to a residual of 0.179. The hydrogen-bonding network of the central core of the hexamer was observed and the charge balance between positively charged Zn ions and their surrounding structure was interpreted by considering the protonation and/or deprotonation states and interactions of HisB10, water and GluB13. The observed double conformation of GluB13 was essential to interpreting the charge balance and could be compared with the structure of a dried crystal of T6 human insulin at 100,K. Differences in the dynamic behaviour of the water molecules coordinating the upper and lower Zn ions were observed and interpreted. The hydrogen bonds in the insulin molecules, as well as those involving HisB10 and GluB13, are discussed. The hydrogen/deuterium (H/D) exchange ratios of the amide H atoms of T6 porcine insulin in crystals were obtained and showed that regions highly protected from H/D exchange are concentrated in the centre of a helical region of the B chains. From the viewpoint of soaking time versus H/D-exchange ratios, the amide H atoms can be classified into three categories. [source] Selective Lanthanides Sequestration Based on a Self-Assembled OrganosilicaCHEMISTRY - A EUROPEAN JOURNAL, Issue 33 2010Eric Besson Dr. Abstract In this paper, we investigate the cation-exchange properties of a self-assembled hybrid material towards trivalent ions, lanthanides (La3+, Eu3+, Gd3+, Yb3+) and Fe3+. The bis-zwitterionic lamellar material was prepared by sol,gel process from only 3-aminopropyltriethoxysilane (APTES), succinic anhydride, and ethylenediamine. In ethanol heated under reflux, the exchange ethylenediammonium versus Ln3+ proved to be complete by complexometry measurements and elemental analyses, one Cl, ion per one LnIII remaining as expected for charge balance. In aqueous solution at 20,°C, the material was found to be selective towards lanthanide in spite of the similarity of their ionic radii. The cation uptake depends on the nature of the salt, the difference between two lanthanides reaching up to 20,% in some cases. Finally, ion-exchange reaction with FeCl3 was chosen as a probe to get more information on the material after incorporation of trivalent ions. Based on Mössbauer spectroscopic investigations on the resulting material in conjunction with the XRD analysis of materials containing trivalent ions, a structural model was proposed to describe the incorporation of trivalent ions by exchange reaction within the original zwitterionic material. [source] | ||||||||||