Measurement of Gibbs energy of formation of Ca2PbO4 using a solid-state cell with three electrodes

Phase relations in the system Ca-Pb-O at 1100 K have been determined by equilibrating 18 compositions in the ternary and identifying the phases present in quenched samples by X-ray diffraction and energy dispersive X-ray analysis (EDX). Only one ternary compound Ca2PbO4 was found to be present. The compound coexists with CaO and PbO. The intermetallic compounds Ca2Pb, Ca5Pb3 and CaPb and liquid alloys are in equilibrium with CaO. The standard Gibbs energies of formation of Ca2PbO4 (880 - 1100 K) and Pb3O4 (770 - 910 K) were determined using solid-state cells based on yttria-stabilized zirconia as the solid electrolyte. Pure oxygen gas at 0.1 MPa was used as the reference electrode. For measurements on Ca2PbO4, a novel cell design with three electrodes in series, separated by solid electrolyte membranes, was used to avoid polarization of the electrode containing three solid phases. Two three-phase electrodes were used. The first absorbs the electrochemical flux of oxygen from the reference electrode to the measuring electrode. The other three-phase electrode, which is unaffected by the oxygen flux through the solid electrolyte, is used for electromotive force (EMF) measurement. The results from EMF studies were cross-checked using thermogravimetry (TG) under controlled oxygen partial pressures. The stability of Pb3O4 was investigated using a conventional solid-state cell with RuO2 electrodes. The results can be summarized by the following equations: 2CaO + PbO +1/2O(2) --> Ca2PbO4 Delta(r)G degrees/J mol(-1) = (- 128340 + 93.21 T/K) +/- 200 3PbO + 1/2O(2) --> Pb3O4 Delta(r)G degrees/J mol(-1) = (- 70060 + 77.5 T/K) +/- 150

Stereospecific solid-state NaBH4-promoted reduction of 1-methylpentacyclo[5.4.0.0(2,6).0(3,10).0(5,9)]undecane-8,11-dione

NaBH4 reduction of a cage dione proceeds in a stereospecific fashion to give the endo,endo-diol. This reactivity is related to the crystal structure.

Structural and conformational study of peptides containing glycine and alanine residues by C-13 CPMAS NMR spectroscopy in solid state

The results of the structural and conformational studies carried out using C-13 CPMAS NMR technique on several glycine and alanine containing peptides in the solid state are reported. The study demonstrates the effects of variations in C-13 chemical shifts due to conformation and hydrogen bonding. The possibility of applying this technique to obtain insight into the conformational characteristics of peptides of unknown structures is discussed.

Electrocatalytic efficiency of polyaniline by cyclic voltammetry and electrochemical impedance spectroscopy studies

Electrochemical redox reactions of ferrous/ferric (Fe2+/Fe3+) and hydroquinone/quinone (H(2)Q/Q) were studied on Pt and polyaniline (PANI)-deposited Pt electrodes in 0.5 M H2SO4-supporting electrolyte by cyclic voltammetry and ac impedance spectroscopy. A comparison of the experimental data obtained with the Pt and PANI/Pt electrodes suggested that the reactions were catalyzed by the PANI. Based on a relative increase in peak currents of cyclic voltammograms, catalytic efficiency (gamma(cv)) of the PANI was defined. There was an increase in gamma(cv) with an increase of scan rate and a decrease of concentration of Fe2+/Fe3+ or H(2)Q. The complex plane impedance spectrum of the electrode consisted of a semicircle in high frequency range and a linear spike in low frequency range. The exchange current density (i(0)) calculated using the semicircle part of the impedance showed Butler-Volmer kinetics with respect to concentration dependence. From a relative increase of i(0) on the PANI/Pt electrode, catalytic efficiency (gamma(eis)) was evaluated. (C) 2002 Elsevier Science B.V. All rights reserved.

Electrochemical studies of polyaniline in a gel polymer electrolyte - High energy and high power characteristics of a solid-state redox supercapacitor

Studies on redox supercapacitors employing electronically conducting polymers are of great importance for hybrid power sources and pulse power applications. In the present study, polyaniline (PANI) has been potentiodynamically deposited on stainless steel substrate and characterized in a gel polymer electrolyte (GPE). Use of the GPE facilitates a voltage limit of the capacitor to 1 V, instead of 0.75 V in aqueous electrolytes. From charge-discharge studies of the solid-state PANI capacitors, a specific capacitance of 250 F g(-1) has been obtained at a specific power of 7.5 kW kg(-1) of PANI. The values of specific capacitance and specific power are considerably higher than those reported in the literature. High energy and high power characteristics of the PANI are presented. (C) 2002 The Electrochemical Society.

Reaction of La2CuO4 with binary metal oxides in the solid state: Metathesis, addition, and redox metathesis pathways

Investigation of the reaction of La2CuO4 with several binary metal oxides in the solid state at elevated temperatures has revealed three different reaction pathways. Reaction of La2CuO4 with strongly acidic oxides such as Re2O7, MoO3, and V2O5 follows a metathesis route, yielding a mixture of products: La3ReO8/La2MoO6/LaVO4 and CuO. Oxides such as TiO2, MnO2, and RuO2 which are not so acidic yield addition products: La2CuMO6 (M = Ti, Mn, Ru). SnO2 is a special case which appears to follow a metathesis route, giving La2Sn2O7 pyrochlore and CuO, which on prolonged reaction transform to the layered perovskite La2CuSnO6. The reaction of La2CuO4 with lower valence oxides VO2 and MoO2, on the other hand, follows a novel redox metathesis route, yielding a mixture of LaVO4/LaCuO2 and La2MoO6/Cu, respectively. This result indicates that it is the redox reactivity involving V-IV + Cu-II --> V-V + Cu-I and Mo-IV + Cu-II --> Mo-VI + Cu-0, and not the acidity of the binary oxide, that controls the nature of the products formed in these cases. The general significance of these results toward the synthesis of complex metal oxides containing several metal atoms is discussed.

Solid state structural and solution studies on the formation of a flexible cavity for anions by copper(I) and 1,2-bis(diphenylphosphino)ethane

Copper(l) complexes of 1,2-bis(diphenylphosphino)ethane (dppe) with a stoichiometry Cu-2(dppe)(3)(X)(2) [X- = CN- (1), SCN- (2), NO3- (3)] are obtained from direct reactions of CuX and dppe. The complexes are structurally and spectroscopically (NMR and IR) characterized. The structure of the [Cu-2(dPPe)(3)](2+) dication is similar to the structural motif observed in many other complexes with a chelating dppe and a bridging dppe connecting two copper centers. In complexes 1 -3, the anions are confined to the cavity formed by the phosphines which force a monodentate coordination mode despite the predominant bidentate/bridging character of the anions. The coordination angles rather than the thermochemical radii dictate the steric requirement of anions. While the solution behavior of 3, with nitrate, is similar to complexes studied earlier, complexes with pseudohalides exhibit new solution behavior. (C) 2002 Elsevier Science Ltd. All rights reserved.

System Dy-Fe-O: thermodynamic properties of ternary oxides using Calvet calorimetry and solid-state electrochemical cell

The enthalpy increments and the standard molar Gibbs energies of formation-of DyFeO3(s) and Dy3Fe5O12(s) have been measured using a Calvet micro-calorimeter and a solid oxide galvanic cell, respectively. A co-operative phase transition, related to anti-ferromagnetic to paramagnetic transformation, is apparent. from the heat capacity data for DyFeO3 at similar to 648 K. A similar type of phase transition has been observed for Dy3Fe5O12 at similar to 560 K which is related to ferrimagnetic to paramagnetic transformation. Enthalpy increment data for DyFeO3(s) and Dy3Fe5O12(s), except in the vicinity of the second-order transition, can be represented by the following polynomial expressions:{H(0)m(T) - H(0)m(298.15 K)) (Jmol(-1)) (+/-1.1%) = -52754 + 142.9 x (T (K)) + 2.48 x 10(-3) x (T (K))(2) + 2.951 x 10(6) x (T (K))(-1); (298.15 less than or equal to T (K) less than or equal to 1000) for DyFeO3(s), and {H(0)m(T) - H(0)m(298.15 K)} (Jmol(-1)) (+/-1.2%) = -191048 + 545.0 x (T - (K)) + 2.0 x 10(-5) x (T (K))(2) + 8.513 x 10(6) x (T (K))(-1); (208.15 less than or equal to T (K) less than or equal to 1000)for Dy3Fe5O12(s). The reversible emfs of the solid-state electrochemical cells: (-)Pt/{DyFeO3(s) + Dy2O3(s) + Fe(s)}/YDT/CSZ//{Fe(s) + Fe0.95O(s)}/Pt(+) and (-)Pt/{Fe(s) + Fe0.95O(s)}//CSZ//{DyFeO3(s) + Dy3Fe5O12(s) + Fe3O4(s)}/Pt(+), were measured in the temperature range from 1021 to 1250 K and 1035 to 1250 K, respectively. The standard Gibbs energies of formation of solid DyFeO3 and Dy3Fe5O12 calculated by the least squares regression analysis of the data obtained in the present study, and data for Fe0.95O and Dy2O3 from the literature, are given by Delta(f)G(0)m(DyFeO3,s)(kJmol(-1))(+/-3.2)= -1339.9 + 0.2473 x (T(K)); (1021 less than or equal to T (K) less than or equal to 1548)and D(f)G(0)m(Dy3Fe5O12,s) (kJmol(-1)) (+/-3.5) = -4850.4 + 0.9846 x (T (K)); (1035 less than or equal to T (K) less than or equal to 1250) The uncertainty estimates for Delta(f)G(0)m include the standard deviation in the emf and uncertainty in the data taken from the literature. Based on the thermodynamic information, oxygen potential diagram and chemical potential diagrams for the system Dy-Fe-O were developed at 1250 K. (C) 2002 Editions scientifiques et medicales Elsevier SAS. All rights reserved.

Twisted aromatics, 9-anthryl and 1-pyrenyl terpyridines organize into novel multi-directional 'ladder-like' motifs in the solid state

9-Anthryl and 1-pyrenyl terpyridines (1 and 2, respectively), key precursors for the design of novel fluorescent sensors have been synthesized and characterized by H-1 NMR, mass spectroscopy and X-ray crystallography. Twisted molecular conformations for each 1 and 2 were observed in their single crystal structures. Energy minimization calculations for the 1 and 2 using the semi-empirical AM1 method show that the 'twisted' conformation is intrinsic to these systems. We observe interconnected networks of edge-to-face CH...pi interactions, which appear to be cooperative in nature, in each of the crystal structures. The two twisted molecules, although having differently shaped polyaromatic hydrocarbon substituents, show similar patterns of edge-to-face CH...pi interactions.The presently described systems comprise of two aromatic surfaces that are almost orthogonal to each other. This twisted or orthogonal nature of the molecules leads to the formation of interesting multi-directional ladder like supramolecular organizations. A combination of edge-to-face and face-to-face packing modes helps to stabilize these motifs. The ladder like architecture in 1 is helical in nature. (C) 2002 Published by Elsevier Science B.V.

Supramolecular polymer for explosives sensing: role of H-bonding in enhancement of sensitivity in the solid state

A pi-electron rich supramolecular polymer as an efficient fluorescent sensor for electron deficient nitroaromatic explosives has been synthesized, and the role of H-bonding in dramatic amplification of sensitivity/fluorescence quenching efficiency in the solid state has been established.

Nanostructuration via solid state transformation as a strategy for improving the thermoelectric efficiency of PbTe alloys

The approach taken in this paper in order to modify the scattering features of electrons and phonons and improve the figure of merit (ZT) of thermoelectric PbTe is to alter the microstructure at constant chemistry. A lamellar pattern of PbTe/GeTe at the nano- and microscale was produced in Pb(0.36)Ge(0.64)Te alloy by the diffusional decomposition of a supersaturated solid solution. The mechanism of nanostructuration is most likely a discontinuous spinodal decomposition. A simple model relating the interface velocity to the observed lamellar spacing is proposed. The effects of nanostructuration in Pb(0.36)Ge(0.64)Te alloy on the electrical and thermal conductivity, thermopower and ZT were investigated. It was shown that nanostructuration through the formation of a lamellar pattern of PbTe/GeTe is unlikely to provide a significant improvement due to the occurrence of discontinuous coarsening. However, the present study allows an analysis of possible strategies to improve thermoelectric materials via optimal design of the microstructure and optimized heat treatment. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Some studies on a solid state sulphur probe for coal gasification system

Measurements on the solid electrolyte cell(Ar -b H2 ~ H2S/CaS + CaF2 ~- ( P t ) / / C a F 2 / / ( P t )-~- CaF2 ~ CaS/H2S ~- H2 ~- At) show that the emf of the cell is directly related through the Nernst equation to the difference in sulfur potentials established at the two Ar ~- H2 ~ H2S/electrode interfaces. The electrodes are designed to convert the sulfur potential gradient across the calcium fluoride electrolyte into an equivalent fluorine potential gradient with the aid of the reaction, CaF2(s) ~ 1~ S2(g)-e CaS(s) ~- F2(g). The response time of the probe varies from approximately 9 hr at 990~ to 2.5 hr at 1225~ The conversion of calcium sulfide and/or calcium fluoride into calcium oxide should not be a problem in anticipated commercial coal gasification systems. Suggestions are presented for improving the cell for such commercial applications.