Gibbs energies of formation of UMoC1.7 and UMoC2

The chemical potentials oi carbon associated with two three-phase fields in the system U-Mo-C were measured by using the methane-hydrogen gas equilibration technique in the temperature range 973 to 1173K. The technique was validated by measuring the standard Gibbs energy of formation of Mo2C. From the experimentally measured values of the chemical potential of carbon in the ternary phase fields UC+Mo+UMoC1.7 and UC+UMoC1.7+UMoC2 and data for UC from the literature, the Gibbs energies of formation of the two ternary carbides were derived:

meso-substituted octabromoporphyrins: Synthesis, spectroscopy, electrochemistry and electronic structure

The free-base, copper(II) and zinc(II) derivatives of 5,10,15,20-tetraarylporphyrin (aryl = phenyl, 4-methylphenyl or 4-chlorophenyl) and the corresponding brominated 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraarylporphyrin derivatives have been synthesized and their spectral and redox properties compared by UV/VIS, H-1 NMR, ESR and cyclic voltammetric methods. Substitution with the electron-withdrawing bromine groups at the pyrrole carbons has a profound influence on the UV/VIS and H-1 NMR spectral features and also on the redox potentials of these systems. On the other hand, electron-withdrawing chloro or electron-donating methyl groups at the para positions of the four phenyl rings have only a marginal effect on the spectra and redox potentials of both the brominated and the non-brominated derivatives. The ESR data for the copper(II) derivatives of ail these systems reveal that substitution at either the beta-pyrrole carbons and/or the para positions of the meso-phenyl groups does not significantly affect the spin-Hamiltonian parameters that describe the metal centre in each case. Collectively, these observations suggest that the highest-occupied (HOMO) and lowest-unoccupied molecular orbitals (LUMO) of the octabromoporphyrins involve the porphyrin pi-ring system as is the case with the non-brominated derivatives.-Investigations have been carried out to probe the electronic structures of these systems by three different approaches involving spectral and redox potential data as well as AMI calculations. The results obtained suggest that the electron-withdrawing beta-bromine substituents stabilize the LUMOs and, to a lesser degree, the HOMOs and that the extent of these changes can be fine-tuned, in a subtle way, by substituting at the meso-aryl rings of a given porphyrin.

Phase equilibria in the system CaO-CoO-SiO2 and Gibbs energies of formation of the quaternary oxides CaCoSi2O6, Ca2CoSi2O7, and CaCoSiO4

Phase relations in the pseudoternary system CaO-CoO-SiO2 have been established at 1323 K. Three quaternary oxides were found to be stable: CaCoSi2O6 with clinopyroxene (Cpx), Ca2CoSi2O7 with melilite (Mel), and CaCoSiO4 with olivine (Ol) structures. The Gibbs energies of formation of the quaternary oxides from their component binary oxides were measured using solid-state galvanic cells incorporating yttria-stabilized zirconia as the solid electrolyte in the temperature range of 1000-1324 K. The results can be summarized as follows: CoO (rs) + CaO (rs) + 2SiO(2) (Qtz) --> CaCoSi2O6 (Cpx), Delta G(f)(0) = -117920 + 11.26T (+/-150) J/mol CoO (rs) + 2CaO (rs) + 2SiO(2) (Qtz) --> Ca2CoSi2O7 (Mel), Delta G(f)(0) = -192690 + 2.38T (+/-130) J/mol CoO (rs) + CaO (rs) + SiO2 (Qtz) --> CaCoSiO2 (Ol), Delta G(f)(0) = -100325 + 2.55T (+/-100) J/mol where rs = rock salt (NaCl) structure and Qtz = quartz. The uncertainty limits correspond to twice the standard error estimate. The experimentally observed miscibility gaps along the joins CaO-CoO and CaCoSiO4-Co2SiO4 were used to calculate the excess free energies of mixing for the solid solutions CaxCo1-xO and (CayCo1-y)CoSiO4:Delta G(E) = X(1 - X)[31975X + 26736 (1 - X)] J/mol and Delta G(E) = 23100 (+/-250) Y(1 - Y) J/mol. A T-X phase diagram for the binary CaO-CoO was computed from the thermodynamic information; the diagram agrees with information available in the literature. The computed miscibility gap along the CaCoSiO4-Co2SiO4 join is associated with a critical temperature of 1389 (+/-15) K. Stability fields for the various solid solutions and the quaternary compounds are depicted on chemical-potential diagrams for SiO2, CaO, and CoO at 1323 K.

Variation of Cu-O charge-transfer energies in YBa2Cu3O7-x thin films studied by photoemission spectroscopy

It is pointed out that the change in the oxidation state of Cu in YBa2CU3O7-x with increasing x vitiates the trend in the Cu(2p) satellite intensity and hence the Cu-O charge-transfer energy. When Y is partly replaced by Ca, however, the satellite intensity and T(c) decrease with the increase in Ca content or hole concentration, just as in other cuprates.

Potentiometric determination of the gibbs energies of formation of SrZrO3 and BaZrO3

The Gibbs free energies of formation of strontium and barium zirconates have been determined in the temperature range 960 to 1210 K using electrochemical cells incorporating the respective alkaline-earth fluoride single crystals as solid electrolytes. Pure strontium and barium monoxides were used in the reference electrodes. During measurements on barium zirconate, the oxygen partial pressure in the gas phase over the electrodes was maintained at a low value of 18.7 Pa to minimize the solubility of barium peroxide in the monoxide phase. Strontium zirconate was found to undergo a phase transition from orthorhombic perovskite to) with space group Cmcm; D-2h(17) to tetragonal perovskite (t) having the space group 14/mcm; D-4h(18) at 1123 (+/- 10) K. Barium zirconate does not appear to undergo a phase transition in the temperature range of measurement. It has the cubic perovskite (c) structure. The standard free energies of formation of the zirconates from their component binary oxides AO (A = Sr, Ba) with rock salt (rs) and ZrO2 with monoclinic (m) structures can be expressed by the following relations:SrO (rs) + ZrO2 (m) --> SrZrO3 (o) Delta G degrees = -74,880 - 14.2T (+/-200) J mol(-1) SrO (rs) + ZrO2 (m) --> SrZrO3 (t) Delta G degrees = -73,645 - 15.3T (+/-200) J mol(-1) BaO (rs) + ZrO2 (m) --> BaZrO4 (c) Delta G degrees = -127,760 - 1.79T (+/-250) J mol(-1) The results of this study are in reasonable agreement with calorimetric measurements reported in the literature. Systematic trends in the stability of alkaline-earth zirconates having the stoichiometry AZrO(3) are discussed.

Role of Hetero-Halogen (F center dot center dot center dot X, X = Cl, Br, and I) or Homo-Halogen (X center dot center dot center dot X, X = F, Cl, Br, and I) Interactions in Substituted Benzanilides

A series of halogen-substituted benzanilides have been synthesized and characterized, and crystallization studies directed toward generation of polymorphs have been performed to delineate the importance of interactions involving halogens. The effect of halogen substitution on the molecular conformation and supramolecular packing has been investigated. The N-H center dot center dot center dot O H-bond is a key structure-directing element acting in conjunction with C-H center dot center dot center dot O and C-H center dot center dot center dot pi interactions. In addition, it is of importance to note that organic fluorine prefers Type I F center dot center dot center dot F contacts, whereas Cl, Br, and I prefer Type II contacts. Hetero-halogen center dot center dot center dot halogen interactions on the other hand are predominately of Type II geometry, and this is due to the greater polarizability of the electron density associated with the heavier halogens. It is of importance to evaluate the contributing role of these interactions in crystal structure packing and the co-operativity associated with such interactions in the solid state.

Thermal analysis studies on hydroxobridged homo and hetero trinuclear cobalt(III) complexes

The synthesis and thermal analysis studies of several hydroxobridged homo and hetero trinuclear cobalt(III) complexes are reported. The complexes are of the type [M(H2O)(x) {(OH)(2)Co(en)(2)}(2)](SO4)(2). nH(2)O and [M(H2O)(x){(OH)(2)Co(NH3)(4)}(2)] (SO4)(2). nH(2)O where en denotes ethylenediamine and M =Co(II), Ni(II), Cu(II) and Zn(II) with x=0 for Cu(II), and 2 for other metal ions, and n =3, 4 or 5. The TG and DTA studies of these compounds show that one or more intermediate compounds are formed in each case before the metal oxides are produced.

Calcium ruthenates: Determination of Gibbs energies of formation using electrochemical cells

Metallic Ru has been found to coexist separately with CaO, RuO2, and the interoxide phases, Ca2RuO4, Ca3Ru2O7, and CaRuO3, present along the pseudobinary system CaO-RuO2. The standard Gibbs energies of formation (Df((ox))G(o)) of the three calcium ruthenates from their component oxides have been measured in the temperature range 925-1350 K using solid-state cells with yttria-stabilized zirconia as the electrolyte and Ru+RuO2 as the reference electrode. The standard Gibbs energies of formation (Deltaf((ox))G(o)) of the compounds can be represented by Ca2RuO4:Deltaf((ox))G(o)/J mol(-1)=-38,340-6.611 T (+/-120), Ca3Ru2O7 : Df((ox))G(o)/J mol(-1)=-75,910-11.26 T (+/-180), and CaRuO3 : Deltaf((ox))G(o)/J mol(-1)=-35,480-3.844 T(+/-70). The data for Ca2RuO4 corresponds to the stoichiometric composition, which has an orthorhombic structure, space group Pbca, with short c axis ("S'' form). The structural features of the ternary oxides responsible for their mild entropy stabilization are discussed. A three-dimensional oxygen potential diagram for the system Ca-Ru-O is developed as a function of composition and temperature from the results obtained. Using the Neumann-Kopp rule to estimate the heat capacity of the ternary oxides relative to their constituent binary oxides, the standard enthalpies of formation of the three calcium ruthenates from the elements and their standard entropies at 298.15 K are evaluated. (C) 2003 The Electrochemical Society.

Electrochemical copolymerization of thiophene derivatives; a precursor to photovoltaic devices

This work presents an electrochemical technique for the polymerization and copolymerization of thiophene derivatives like 7,9-dithiophene-2yl-8H-cyclopenta[a]acenaphthalene-8-one and 3-hexylthiophene. The structural characterization of chemically synthesized monomers and electro-chemically synthesized polymers was carried out by nuclear magnetic resonance and Fourier transform infrared spectroscopy. Thermal characterizations indicate that copolymer has increased thermal stability than that of homopolymer. Morphological studies of the polymerized films carried out by scanning electron microscopy shows network structure of copolymer. Optical properties of the homopolymers and copolymer were studied by UV-visible spectrometer and it was observed that band gap of copolymer is less than the homopolymers. HOMO and LUMO levels, band gap values of the respective polymers were also calculated from the cyclic voltammetry technique with various scan rates. By the peak current obtained from various scan rates shows that all polymerization reactions are diffusion controlled process. Charge transfer resistances of polymers were determined using Nyquist plots. Conductivity of synthesized polymers shows higher conductivity for copolymer than homopolymers. (C) 2011 Elsevier Ltd. All rights reserved.

Gibbs free energies of formation of ZnAl2O4 and ZnCr2O4

The standard free energies of formation of zinc aluminate and chromite were determined by measuring the oxygen potential over a solid CuZn alloy, containing 10 at.−% Zn, in equilibrium with ZnO, ZnAl2O4+Al2O3(χ) and ZnCr2O4+Cr2O3, in the temperature range 700–900°C. The oxygen potential was monitored by means of a solid oxide galvanic cell in which a Y2O3 ThO2 pellet was sandwiched between a CaOZrO2 crucible and tube. The temperature dependence of the free energies of formation of the interoxidic compounds can be represented by the equations, The heat of formation of the spinels calculated from the measurements by the “Second Law method” is found to be in good agreement with calorimetrically determined values. Using an empirical correlation for the entropy of formation of cubic spinel phases from oxides with rock-salt and corundum structures and the measured high temperature cation distribution in ZnAl2O4, the entropy of transformation of ZnO from wurtzite to rock-salt structure is evaluated.

Gibbs free energies of formation of indium (III) oxide and sulphate

Emf measurements on the galvanic cell Pt, Ta, In + In,O, / Tho,-Y,03 / Cu + C+O, Pt were used to obtain the standard free energy of formation of 1%03fr om 600 to 900°C. Differential thermal analysis was used to detect the decomposition of In2(S0,), under controlled SO2 + O2 + Ar mixtures in thqtemperature range 640-8wC. X-ray diffraction analysis indicated that the decomposition product was 1%03 without an oxywlphate intermediate. The following equations were obtained for the variation of the standard free-energy change(Jlmole) with temperature:

Potentiometric determination of the Gibbs energies of formation of lead aluminates

The Gibbs energies of formation of three compounds in the PbO-Al2O3 system—2PbO · Al2O3, PbO · Al2O3, andPbO· 6Al2O3—have been determined from potentiometric measurements on reversible solid-state galvanic cells [dformula Pt, Ir | Pb, alpha-Al[sub 2]O[sub 3], PbO [center-dot] 6Al[sub 2]O[sub 3] | ZrO[sub 2]-CaO | NiO, Ni | Pt] [dformula Pt | NiO, Ni | ZrO[sub 2]-CaO | Pb, PbO [center-dot] 6Al[sub 2]O[sub 3], PbO [center-dot] Al[sub 2]O[sub 3] | Ir, Pt] and [dformula Pt | NiO, Ni | ZrO[sub 2]-CaO | Pb, PbO [center-dot] Al[sub 2]O[sub 3], 2PbO [center-dot] Al[sub 2]O[sub 3] | Ir, Pt] in the temperature range 850–1375 K. The results are discussed in the light of reported phase diagrams for the PbO-Al2O3system. The partial pressures of different lead oxide species, PbnOn, n = 1–6, in the gas phase in equilibrium withthe aluminates are calculated by combining the results of this study with the mass-spectrometric data of Drowart et al.(1) for polymerization equilibria in the gas phase. The concentration of oxygen in lead in equilibrium with the aluminatesare also derived from the results and the literature data on the Gibbs energy of solution of oxygen in liquid lead.

Measurement of Gibbs energies of formation of CoF2 and MnF2 using a new composite dispersed solid electrolyte

Gibbs energies of formation of CoF2 and MnF2 have been measured in the temperature range from 700 to 1100 K using Al2O3-dispersed CaF2 solid electrolyte and Ni+NiF2 as the reference electrode. The dispersed solid electrolyte has higher conductivity than pure CaF2 thus permitting accurate measurements at lower temperatures. However, to prevent reaction between Al2O3 in the solid electrolyte and NiF2 (or CoF2) at the electrode, the dispersed solid electrolyte was coated with pure CaF2, thus creating a composite structure. The free energies of formation of CoF2 and MnF2 are (± 1700) J mol−1; {fx37-1} The third law analysis gives the enthalpy of formation of solid CoF2 as ΔH° (298·15 K) = −672·69 (± 0·1) kJ mol−1, which compares with a value of −671·5 (± 4) kJ mol−1 given in Janaf tables. For solid MnF2, ΔH°(298·15 K) = − 854·97 (± 0·13) kJ mol−1, which is significantly different from a value of −803·3 kJ mol−1 given in the compilation by Barinet al.

Gibbs energies of formation of intermetallic phases in the systems Pt Mg, Pt Ca and Pt Ba and some applications

The standard Gibbs energies of formation of platinum-rich intermetallic compounds in the systems Pt-Mg, Pt-Ca, and Pt-Ba have been measured in the temperature range of 950 to 1200 K using solid-state galvanic cells based on MgF2, CaF2, and BaF2 as solid electrolytes. The results are summarized by the following equations: ΔG° (MgPt7) = −256,100 + 16.5T (±2000) J/mol ΔG° (MgPt3) = −217,400 + 10.7T (±2000) J/mol ΔG° (CaPt5) = −297,500 + 13.0T (±5000) J/mol ΔG° (Ca2Pt7) = −551,800 + 22.3T (±5000) J/mol ΔG° (CaPt2) = −245,400 + 9.3T (±5000) J/mol ΔG° (BaPt5) = −238,700 + 8.1T (±4000) J/mol ΔG° (BaPt2) = −197,300 + 4.0T (±4000) J/mol where solid platinum and liquid alkaline earth metals are selected as the standard states. The relatively large error estimates reflect the uncertainties in the auxiliary thermodynamic data used in the calculation. Because of the strong interaction between platinum and alkaline earth metals, it is possible to reduce oxides of Group ILA metals by hydrogen at high temperature in the presence of platinum. The alkaline earth metals can be recovered from the resulting intermetallic compounds by distillation, regenerating platinum for recycling. The platinum-slag-gas equilibration technique for the study of the activities of FeO, MnO, or Cr2O3 in slags containing MgO, CaO, or BaO is feasible provided oxygen partial pressure in the gas is maintained above that corresponding to the coexistence of Fe and “FeO.”