Thermal behaviour of complexes of antipyrine derivatives II

Parent and mixed ligand complexes of cobalt(II) and copper(II) ions with N,N-bis-(4-antipyrylmethyl)piperazine or N,N-tetra(4-antipyryl-methyl)-1,2-diaminoethane or/and imidazole as ligand and ClO ₄ ^– or SCN^– as counterion were synthesised and their thermal behaviour was investigated.This work was performed in the framework of cooperation between the Hungarian Academy of Sciences and Romanian Academy and was supported financially, in part, by the Hungarian Scientific Research Foundation (OTKA T 029554).     

Cellulose-precursor synthesis of nanocrystalline Ce<Subscript>0.8</Subscript>Gd<Subscript>0.2</Subscript>O<Subscript>2−δ</Subscript> for SOFC anodes

Developments of intermediate-temperature solid oxide fuel cells (IT SOFCs) require novel anode materials with a high electrochemical activity at 800–1070 K. The polarization of cermet anodes, made of nickel, ceria and yttria-stabilized zirconia (YSZ) and applied onto a YSZ solid electrolyte, can be significantly reduced by catalytically active ceria additions, the relative role of which increases with decreasing temperature. Further improvement is observed when using Ce_0.8Gd_0.2O_2– (CGO) having a high oxygen ionic conductivity instead of undoped ceria, owing to enlargement of the electrochemical reaction zone. Nanocrystalline CGO powders with grain sizes of 8–35 nm were thus synthesized via the cellulose-precursor technique and introduced into Ni–CGO–YSZ cermets, and tested in contact with a (La_0.9Sr_0.1)_0.98Ga_0.8Mg_0.2O_3– (LSGM) electrolyte at 873–1073 K. The results showed that the anode performance can be enhanced by additional surface activation, in particular by impregnation with a Ce-containing solution, and also by incorporation of YSZ, which probably acts as a cermet-stabilizing component. The overpotential of the surface-modified Ni–CGO (25 wt%–75 wt%) anode in a 10% H₂/90% N₂ atmosphere was approximately 110 mV at 1073 K with a current density of 200 mA/cm².Presented at the OSSEP Workshop Ionic and Mixed Conductors: Methods and Processes, Aveiro, Portugal, 10–12 April 2003     

Vesicle formation in oleyldimethylamine oxide/sodium oleate mixtures

Vesicle formation in a mixture of oleyldimethylamine oxide (OleylDMAO) and sodium oleate (NaOl) was investigated by viscoelastic measurements and cryoscopic transmission electron micrograph (cryo-TEM) observations. The viscoelastic properties changed with increasing mole fraction of NaOl (X _NaOl) from the Maxwell behavior of OleylDMAO solutions (X _NaOl=0) suggesting a transient network of long flexible chains. For X _NaOl=0.2 and 0.4 mixtures, both the shear storage modulus G and the shear loss modulus G showed weak dependences on angular frequency with a relation G>G. From cryo-TEM observations, vesicles coexisted with threadlike micelles in mixtures of X _NaOl=0.2 and 0.3. As X _NaOl increased further (X _NaOl=0.5 and 0.6), threadlike micelles disappeared and the coexistence of vesicles and globular micelles was observed. At X _NaOl=0.5, the viscosity decreased remarkably, which was consistent with the disappearance of threadlike micelles. The results indicated that vesicles were formed by the addition of NaOl to OleylDMAO solutions, contrary to the expectation of a decrease of the packing parameter with the introduction of electric charges.     

Gap Space Optimization for NO Removal in a Non‐thermal Plasma Discharge

Given the operational constraints of aerospace ground equipments (AGE), the nonthermal plasma discharge (NTPD) has been identified as a promising technology for their NO_x removal. As part of a program to optimize an NTPD system for this particular application, an investigation of the effect of discharge gap spacing on the electrical and chemical processes that occur in NTPDs was initiated. A number of experiments were performed to examine how the gap spacing affects the NO removal efficiency, discharge characteristics, and chemical reactions in a NTPD device. Gap spacings ranging from 0.8 to 4.0 mm were investigated in this study. An optimum gap spacing for NO removal was observed at approximately 2 mm and, based on the experimental data, a physical explanation for the optimum was developed. The experiments, results and conclusions are discusssed in detail in this paper.     

Ligand-ligand redox interaction through some metal-cluster units

The ligand-ligand redox interaction separated by di-, tri-, and hexanuclear cluster units is discussed in terms of the splitting of the redox waves (DeltaE(L)) and the comproportionation constants (Kcom(L)) of the ligand-based mixed valence state. Although two redox-active monodentate ligands in the mononuclear ruthenium(II) complexes (either cis or trans configurations) do not show appreciable splitting in their reduction waves, interestingly those separated by giant triruthenium and hexarhenium cluster units clearly show splitting. The molecular orbital considerations in the literature suggest that these units possess some pi-type molecular orbitals composed of metal dpi and possibly ligand ppi orbitals. Absence of the redox interactions in oxo-bridged diruthenium(II) and oxo-centered trirhodium(III) complexes where such pi molecular orbitals (including an antibonding one) are fully occupied, indicates the importance of empty pi* orbitals for the ligand redox communication.     

Quad quantum cascade laser spectrometer with dual gas cells for the simultaneous analysis of mainstream and sidestream cigarette smoke

A compact, fast response, infrared spectrometer using four pulsed quantum cascade (QC) lasers has been applied to the analysis of gases in mainstream (MS) and sidestream (SS) cigarette smoke. QC lasers have many advantages over the traditional lead-salt tunable diode lasers, including near room temperature operation with thermoelectric cooling and single mode operation with improved long-term stability. The new instrument uses two 36 m, 0.3 l multiple pass absorption gas cells to obtain a time response of 0.1s for the MS smoke system and 0.4s for the SS smoke system. The concentrations of ammonia, ethylene, nitric oxide, and carbon dioxide for three different reference cigarettes were measured simultaneously in MS and SS smoke. A data rate of 20Hz provides sufficient resolution to determine the concentration profiles during each 2s puff in the MS smoke. Concentration profiles before, during and after the puffs also have been observed for these smoke constituents in SS smoke. Also, simultaneous measurements of CO(2) from a non-dispersive infrared (NDIR) analyzer are obtained for both MS and SS smoke. In addition, during this work, nitrous oxide was detected in both the MS and SS smoke for all reference cigarettes studied.     

Structural and magnetic investigations of the mixed-valence Fe(II,III) two-dimensional layer complex, [Fe2(II) Fe2(III)(HCOO)10(C6H7N)6]n.

The structure of the complex, [Fe2(II)Fe2(III)(HCOO)10(C6H7N6)n, (1) exhibits a neutral two-dimensional layer network of alternating iron(II) and iron(III) ions, bridged equatorially by formate groups. All iron atoms are octahedrally coordinated, with iron(III) coordinating axially to one gamma-picoline and one formate group, while the iron(II) centers interact axially with two gamma-picoline groups, above and below the layer plane. The complex crystallizes in the triclinic space group P1 at all studied temperatures [at 120 K, the cell dimensions are: a = 10.228(1), b = 12.071(1), c = 12.072(1) A, alpha = 89.801(2), beta = 71.149(2), gamma = 73.371(2) degrees]. An intralayer antiferromagnetic exchange interaction of J = -2.8 cm(-1) between iron(II) and iron(III) was observed in the magnetic studies. Decreasing the temperature to close to 20 K causes a magnetic-ordering phenomenon to occur and a low-temperature phase with a long-range antiferromagnetic spin orientation appears. The magnetic phase transition was confirmed by M?ssbauer spectroscopic studies at temperatures above and below the critical temperature. Structural information of 1 from synchrotron X-ray diffraction data collected at room temperature and 16 K suggests that the antiferromagnetic ordering is caused by an enhanced pi-pi interaction between chi-picoline groups from adjacent layers.     

Formal Mathematical Analysis of the Existence of the Common Intersection Point in Relation to Determining the Parameters Describing Ion Adsorption at the Oxide/Electrolyte Interface: Comparison of the Triple and Four-Layer Models

For most oxide/electrolyte systems potentiometric titration curves measured for different ionic strengths have a Common Intersection Point (CIP) which corresponds to the Point of Zero Charge (PZC). However, there are systems where a CIP exists but the surface charge at this point does not equal zero (PZC CIP). In this paper theoretical analysis of the systems in which the PZC and CIP do not coincide is presented. It is based on the well-known 2-pK surface charging approach and Triple Layer Model (TLM) as well as the Four Layer Model (FLM) of the electric double layer. The appropriate mathematical criterion for CIP existence was applied with detailed derivations, both for TLM and FLM. Having determined in this manner the parameter values, one can draw proper conclusions about the features of oxide/electrolyte adsorption systems, in which PZC and CIP do not coincide. The values of adsorption parameters are found by fitting simultaneously the obtained theoretical expressions to both of the experimental titration isotherms, and to the individual isotherms of electrolyte cation adsorption measured using radiometric methods.