Nature and strength of C-H center dot center dot center dot O interactions involving formyl hydrogen atoms: computational and experimental studies of small aldehydes

Structural and electronic properties of C-H center dot center dot center dot O contacts in compounds containing a formyl group are investigated from the perspective of both hydrogen bonding and dipole-dipole interactions, in a systematic and graded approach. The effects of a-substitution and self-association on the nature of the formyl H-atom are studied with the NBO and AIM methodologies. The relative dipole-dipole contributions in formyl C-H center dot center dot center dot O interactions are obtained for aldehyde dimers. The stabilities and energies of aldehyde clusters (dimer through octamer) have been examined computationally. Such studies have an implication in crystallization mechanisms. Experimental X-ray crystal structures of formaldehyde, acrolein and N-methylformamide have been determined in order to ascertain the role of C-H center dot center dot center dot O interactions in the crystal packing of formyl compounds.

Role of B2O3 on the phase stability and long phosphorescence of SrAl2O4 : Eu, Dy

The role of B2O3 addition on the long phosphorescence of SrAl2O4:Eu2+, Dy3+ has been investigated. B2O3 is just not an inert high temperature solvent (flux) to accelerate grain growth, according to SEM results. B2O3 has a substitutional effect, even at low concentrations. by way of incorporation of BO4 in the corner-shared AlO4 framework of the distorted 'stuffed' tridymite structure of SrAl2O4. which is discernible from the IR and solid-state MAS NMR spectral data. With increasing concentrations, B2O3 reacts with SrAl2O4 to form Sr4Al4O25 together with Sr-borate (SrB2O4) as the glassy phase, as evidenced by XRD and SEM studies. At high B2O3 contents, Sr4Al14O25 converts to SrAl2B2O7 (cubic and hexagonal), SrAl12O19 and Sr-borate (SrB4O7) glass. Sr4Al14O25:Eu2+, Dy3+ has also been independently synthesized to realize the blue emitting (lambda(em)approximate to490 nm) phosphor. The afterglow decay as well as thermoluminescence studies reveal that Sr4Al14O25:Eu, Dy exhibits equally long phosphorescence as that of SrAl2O4:Eu2+, Dy3+. In both cases, long phosphorescence is noticed only when BO4 is present along with Dy3+ and Eu2+. Here Dy3+ because of its higher charge density than Eu2+ prefers to occupy the Sr sites in the neighbourhood of BO4, as the effective charge on borate is more negative than that of AlO4. Thus. Dy3+ forms a substitutional defect complex with borate and acts as an acceptor-type defect center. These defects Eu2+ ions and the subsequent thermal release of hole at room temperature followed by the trap the hole generated by the excitation of recombination with electron resulting in the long persistent phosphorescence. (C) 2003 Elsevier Science B.V. All rights reserved.

Properties of the Ferrimagnetic Double-Perovskites A2FeReO6 (A=Ba and Ca)

We have synthesized ceramics of A2FeReO6 double-perovskites A2FeReO6 (A=Ba, Ca). Structural characterizations indicate a cubic structure with a=8.0854(1) Å for Ba2FeReO6 and a distorted monoclinic symmetry with a=5.396(1) Å, b=5.522(1) Å, c=7.688(2) Å and β=90.4° for Ca2FeReO6. The barium compound is metallic from 5K to 385K, i.e. no metal-insulator transition has been seen up to 385K, and the calcium compound is semiconducting from 5K to 385K. Magnetization measurements show a ferrimagnetic behavior for both materials, with Tc =315 K for Ba2FeReO6 and above 385K for Ca2FeReO6. At 5K we observed, only for Ba2FeReO6, a negative magnetoresistance of 10% in a magnetic field of 5T. Electrical, magnetic and thermal properties are discussed and compared to those of the analogous compounds Sr2Fe(Mo,Re)O6 recently studied.

CO adsorption on ionic Pt, Pd and Cu sites in Ce(1-x)M(x)O(2-delta) (M = Pt(2+), Pd(2+), Cu(2+))

Noble metal ion substituted CeO(2) in the form of Ce(0.98)M(0.02)O(2-delta) solid solution (where M = Pt, Pd, Cu) are the new generation catalysts with applications in three-way exhaust catalysis. While adsorption of CO on noble metals ions is well-known, adsorption of CO on noble metal ions has not been studied because creating exclusive ionic sites has been difficult. Using first-principles density functional theory (DFT) we have shown that CO gets adsorbed on the noble metal Pt(2+), Pd(2+), Cu(2+) ionic sites in the respective compounds, and the net energy of the overall system decreases. Adsorption of CO on metal ions is also confirmed by Fourier transform infrared spectroscopy (FTIR).

String-like propagation of the 5-coordinated defect state in supercooled water: molecular origin of dynamic and thermodynamic anomalies

We find that at low temperature water, large amplitude (similar to 60 degrees) rotational jumps propagate like a string, with the length of propagation increasing with lowering temperature. The strings are formed by mobile 5-coordinated water molecules which move like a Glarum defect (J. Chem. Phys., 1960, 33, 1371), causing water molecules on the path to change from 4-coordinated to 5-coordinated and again back to 4-coordinated water, and in the process cause the tagged water molecule to jump, by following essentially the Laage-Hynes mechanism (Science, 2006, 311, 832-835). The effects on relaxation of the propagating defect causing large amplitude jumps are manifested most dramatically in the mean square displacement (MSD) and also in the rotational time correlation function of the O-H bond of the molecule that is visited by the defect (transient transition to the 5-coordinated state). The MSD and the decay of rotational time correlation function, both remain quenched in the absence of any visit by the defect, as postulated by Glarum long time ago. We establish a direct connection between these propagating events and the known thermodynamic and dynamic anomalies in supercooled water. These strings are found largely in the regions that surround the relatively rigid domains of 4-coordinated water molecules. The propagating strings give rise to a noticeable dynamical heterogeneity, quantified here by a sharp rise in the peak of the four-point density response function, chi(4)(t). This dynamics heterogeneity is also responsible for the breakdown of the Stokes-Einstein relation.

Structural Variability in the Monofluoroethynylbenzenes Mediated through Interactions Involving ``Organic'' Fluorine

Competition among weak intermolecular interactions can lead to polymorphism, the appearance of various crystalline forms of a substance with comparable cohesive energies. The crystal structures of 2-fluorophenylacetylene (2FPA) and 3-fluorophenylacetylene (3FPA), both of which are liquids at ambient conditions, have been determined by in situ cryocrystallization. Both compounds exhibit dimorphs, with one of the forms observed in common, P2(1), Z = 2 and the other form being Pna2(1), Z = 4 for 2FPA and P2(1)/c, Z = 12 for 3FPA. Variations in the crystal structures of the dimorphs of each of these compounds arise from subtle differences in the way in which weak intermolecular interactions such as C-H center dot center dot center dot pi and C-H center dot center dot center dot F are manifested. The interactions involving ``organic'' fluorine, are entirely different from those in the known structure of 4-fluorophenylacetylene (4FPA), space group P2(1)/c, Z = 4. The commonalities and differences in these polymorphs of 2FPA and 3FPA have been analyzed in terms of supramolecular synthons and extended long-range synthon aufbau module (LSAM) patterns. These structures are compared with the three polymorphs of phenylacetylene, in terms of the T-shaped C-H center dot center dot center dot pi interaction, a feature common to all these structures.

Synthesis, Structure, Negative Thermal Expansion, and Photocatalytic Property of Mo Doped ZrV(2)O(7)

A new series of compounds identified in the phase diagram of ZrO(2)-V(2)O(8)-MoO(3) have been synthesized via the solution combustion method. Single crystals of one of the compounds in the series, ZrV(1.50)Mo(0.50)O(7.25), were grown by the melt-cool technique from the starting materials with double the MoO(3) quantity. The room temperature average crystal structure of the grown crystals was solved using the single crystal X-ray diffraction technique. The crystals belong to the cubic crystal system, space group Pa (3) over bar (No. 205) with a = 8.8969 (4) angstrom, V = 704.24 (6) angstrom(3), and Z = 4. The final R(1) value of 0.0213 was achieved for 288 independent reflections during the structure refinement. The Zr(4+) occupies the special position (4a) whereas V(5+) and Mo(6+) occupy two unique (8c) Wyckoff positions. Two fully occupied O atoms, (24d) and (4b), one partially occupied 0 atom (8c) have been identified for this molybdovanadate, which is a unique feature for these crystals. The structure is related to both ZrV(2)O(7) and cubic ZrMo(2)O(8). The temperature dependent single crystal studies show negative thermal expansion above 370 K. The compounds have been characterized by powder X-ray diffraction, solid-state UV-vis diffuse reflectance spectra, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The photocatalytic activity of these compounds has been investigated for the degradation of various dyes, and these compounds show specificity toward the degradation of non-azoic dyes.

Activities and their relation to cation distribution in NiAl2O4 MgAl2O4 spinel solid solutions

The activity of NiAl2O4 in NiAl2O4MgAl2O4 solid solutions has been measured by using a solid oxide galvanic cell of the type, Pt, Ni + NiAl2O4 + Al2O3(α)/CaOZrO2/Ni + NixMg1−xAl2O4 + Al2O3(α). Pt, in the temperature range 750–1150°C. The activities in the spinel solid solutions show negative deviations from Raoult's law. The cation distribution in the solid solutions has been calculated using site preference energies independent of composition for Ni2+, Mg2+, and Al3+ ions obtained from crystal field theory and measured cation disorder in pure NiAl2O4 and MgAl2O4, and assumi g ideal mixing of cations on the tetrahedral and octahedral positions. The calculated values correctly predict the decrease in the fraction, α, of Ni2+ ions on tetrahedral sites for 1>x>0.25, observed by Porta et al. [J. Solid State Chem.11, 135 (1974)] but do not support their tentative evidence for an increase in α for x < 0.25. The measured excess free energy of mixing can be completely accounted for by using either the calculated or the measured cation distributions. This suggests that the Madelung energy is approximately a linear function of composition in the solid solutions. The composition of NiOMgO solid solutions in equilibrium with NiAl2O4MgAl2O4 solid solutions has been calculated from the results and information available in literature.

Highly efficient dialkylphosphate-mediated syntheses of hydantoins and a bicyclohydantoin under solvent-free conditions

Diversely substituted hydantoins have been synthesized by new strategy from cyanamide based precursor, that is, methyl N-cyano-N-alkyl/arylaminoacetate. Dialkylphosphates were employed as the mild reagent to hydrolyze and cyclize the substrate in one step to give quantitative yields of the desired products. Syntheses of multivalent hydantoins viz bis-hydantoin, bicyclohydantoin have potentially widened the scope and applicability of the present method. Solvent-free conditions and very easy work-up procedure make the reaction convenient and eco-friendly. Single crystal structures of some of the representative compounds are also reported. (C) 2011 Elsevier Ltd. All rights reserved.

Gibbs energy formation of lead titanate

The Gibbs energy of formation of titania-saturated lead titanate has been determined by e.m.f. measurements on the solid state cell;Pt,Ir,Pb + Pb1−xTiO3−x + TiO2(rutile)/CaO-ZrO2/Ni + NiO,Pt in the temperature range 1075–1350 K. The results obtained are significantly different from those reported in the literature based upon vapour pressure measurements, employing Knudsen effusion and transportation techniques, and assuming that the vapor phase consisted entirely of monomeric PbO molecules. A reanalysis of the data obtained in the earlier vapor pressure studies using mass spectrometric measurements on polymeric PbO species in the gas phase, gives Gibbs energies of formation of lead titanate which are in better agreement with those obtained in this study. Earlier electrochemical measurements by Mehrotra et al. and more recent electrochemical measurements by Schmahl et al. both employing CaO-ZrO2 solid electrolytes are in good agreement with the present study. The electro-chemical measurements by Schmahl et al. using PbF 2 solid electrolyte give a slightly more positive Gibbs energy of formation. There was no evidence supporting the formation of compounds other than Pb1−xTiO3−x from yellow PbO and rutile form of TiO2 in the temperature range covered in this study.Résumé L'enthalpie libre de formation du titanate de plomb saturé en oxyde de titane a été déterminée par des mesures de FEM de la pile: Pt,Ir,Pb + Pb1−xTiO3−x + TiO2(rutile)/CaO-ZrO2/Ni + NiO,Pt dans le domaine de températures 1075–1350 K. Les résultats obtenus, different appréciablement de ceux publiés, déterminés par mesures de tensions de vapeur (techniques de transport et d'effusion de Knudsen) en supposant que la phase gazeuse etait uniquement constituée de molécules monomériques de PbO. Une réanalyse des résultats de la littérature, à partir de mesures par spectrométrie de masse sur les polymères de PbO gazeux, donne des enthalpies libres de formation du titanate de plomb se rapprochant de celles obtenues dans cette étude. Les mesures de Mehrotra et al. et plus récemment de Schmahl et al. utilisant toutes deux l'électrolyte CaO-ZrO2 concordent bien avec celles de la présente étude. Les mesures de Schmahl et al., à l'aide de l' électrolyte solide PbF2, donnent une enthalpie de formation légèrement plus positive. Pour la gammede températures étudiée, rien ne permet de supposer que des composés autres que Pb1−x TiO3−x puissent se former à partir du PbO Gaune) et du rutile (TiO2).

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.

Thermodynamic properties of Cr Mo solid alloys

The activity of Cr in solid Cr-Mo alloys has been measured at 1873 K using a metal-oxide-gas equilibrium technique. Thin foils of Mo were equilibrated with solid Cr203 under flowing gas mixtures of argon, hydrogen and watervapourof known composition. The equilibrium concentration of Cr in Mo was determined by chemical analysis. These measurements indicate positive deviations from Raoult's law. The activity data obtained in the study at 1873 K are combined with free energy of mixing at 1471 K, calorimetric enthalpy of mixing at 1673 K, and experimental evidence of phase separation at lower temperatures, reported in the literature, to obtain an optimised set of thermodynamic parameters for the Cr-Mosystem in the solid state.

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.”

Thermodynamic properties of Pt5La, Pt5Ce, Pt5Pr, Pt5Tb and Pt5Tm intermetallics

The Gibbs’ energies of formation of Pt5La, Pt5Ce, Pt5Pr, Pt5Tb and Pt5 Tm intermetallic compounds have been determined in the temperature range 870–1100 K using the solid state cell:Ta,M + MF3 /CaF2 /Pt5 M + Pt + MF3 ,TaTaM+MF3CaF2Pt5M+Pt+MF3Ta.The reversible emf of the cell is directly related to the Gibbs’ energy of formation of the Pt5M compound. The results can be summarized by the equations:DGf° á Pt5 La ñ = - 373,150 + 6 ·60 T( ±300 )J mol - 1 DGf° á Pt5 Ce ñ = - 367,070 + 5 ·79 T( ±300 )J mol - 1 DGf° á Pt5 Pr ñ = - 370,540 + 4 ·69 T( ±300 )J mol - 1 DGf° á Pt5 Tb ñ = - 372,280 + 4 ·11 T( ±300 )J mol - 1 DGf° á Pt5 Tm ñ = - 368,230 + 4 ·89 T( ±300 )J mol - 1 Unknown control sequence '\hfill'relative to the low temperature allotropic form of the lanthanide element and solid platinum as standard states The enthalpies of formation of all the Pt5M intermetallic compounds obtained in this study are in good agreement with Miedema’s model. The experimental values are more negative than those calculated using the model. The variation of the thermodynamic properties of Pt5M compounds with atomic number of the lanthanide element is discussed in relation to valence state and molar volume.