Optical detection of NO3 and NO2 in “pure” HNO3 vapor,the liquid-phase decomposition of HNO3

Flowing and static gas-phase samples of HNO₃ in O₂ and N₂ were analyzed by long-path ultraviolet/visible (UV/VIS) spectroscopy to reveal the presence of both NO₂ and NO₃, the concentrations of which were calculated using differential absorption cross sections. NO₂ is produced predominantly by the heterogeneous decomposition of HNO₃, whereas NO₃ is generated in the gas phase by the thermal decomposition of N₂O₅, a product of the self-disproportionation of liquid HNO₃. © 1993 John Wiley & Sons, Inc.     

Selective quenching of tryptophanyl fluorescence in bovine serum albumin by the iodide ion

Modified Stern-Volmer equation is obeyed by bovine serum albumin (BSA)-iodide system showing selective quenching of tryptophanyl fluorescence of BSA. The fraction of accessible protein fluorescence is 0.56 and the effective Stern-Volmer constant is 290 M^-1 at pH 7.4 in 0.005 M phosphate buffer at 25°C. Collisional quenching is operative both in the BSA -I⁻¹ system and the model system, tryptophan-I⁻¹. It is supported by the observed relationship between the ratio of quenching rate constants (k _q ) and diffusion coefficients and alsok _q with bulk viscosity.     

EPMA of interfaces applied to the solid oxide fuel cell

Chemical interactions at the phase boundaries of materials applied for the solid oxide fuel cell (SOFC) have been studied by EPMA. The chemical reactivity at the interface of La_y-xSr_xMnO₃/ZrO₂-Y₂O₃ is dependent on the stoichiometry (y) and the Sr content (x) of the perovskite. Typical reaction products (zirconates) and a diffusion zone in the ZrO₂–Y₂O₃ have been observed. The extension of cation release (Mn) is related to the increasing chemical activity of Mn oxide in the perovskite by the Sr substitution for La. The wettability of the metal/oxide interface in the anode cermet (Ni/ZrO₂–Y₂O₃) has been found to be influenced by chemical reactions resulting from the applied reducing atmosphere with high carbon activity. The disintegration of ZrO₂–Y₂O₃ in contact with molten Ni or Ni-Ti and Ni-Cr alloys leads to the redeposition of Y₂O₃-enriched oxides and also to Zr-rich intermetallic compounds and eutectics.     

Silver nitrate-acetonitrile and iodine-benzene complexes as studied by NMR in thermotropic liquid crystals

Silver nitrate-acetonitrile and π iodine-benzene complexes in thermotropic liquid crystals have been studied by ¹H, ²H, and ¹³C NMR spectroscopy and by optical microscopy. Evidence for at least two silver complexes in each liquid crystal is presented.     

On practical metrology and chemical analysis: etalons and traceability systems

 National measurement systems are infrastructures to ensure, for each nation, a consistent and internationally recognised basis for measurement. Such complex systems have historical, technical, legal, organisational and institutional aspects to connect scientific metrology with practical measurements. Underlying any valid measurement is a chain of comparisons linking the measurement to an accepted standard. The ways the links are forged and the etalons (measurement standards) to which they connect are defining characteristics of all measurement systems. This is often referred to as traceability which aims at basing measurements in common measurement units – a key issue for the integration of quantitative chemical analysis with the evolving physical and engineering measurement systems. Adequate traceability and metrological control make possible new technical capabilities and new levels of quality assurance and confidence by users in the accuracy and integrity of quantitative analytical results. Traceability for chemical measurements is difficult to achieve and harder to demonstrate. The supply of appropriate etalons is critical to the development of metrology systems for chemical analysis. An approach is suggested that involves the development of networks of specialised reference laboratories able to make matrix-independent reference measurements on submitted samples, which may then be used as reference materials by an originating laboratory using its practical measurement procedures. Received: 31 July 1995 Accepted: 19 August 1995     

Erratum: Synthesis and characterization of diorganotin(IV) complexes of Schiff bases with ONO‐type donors and crystal structure of [N‐(2‐hydroxy‐4‐nitrophenyl)‐3‐ethoxysalicylideneiminato]diphenyltin(IV)

The article referenced above was first published online on 30 August 2007 with incorrect pagination; the pagination has now been corrected online and in print. Copyright © 2007 John Wiley & Sons, Ltd.     

Nonlinear optical properties of regioregular main‐chain polyesters

We have prepared new polyesters containing quadratic, nonlinear optical (NLO) active chromophores covalently incorporated into the main chain. In these polymers, the sequence of the chromophore units along the main chain is rigorously head to tail. All the polyesters are processable, both in the melt and in solution. For one polyester, a full second‐order NLO characterization has been performed. An out‐of‐resonance d₃₃ coefficient of 21 pm/V at 1368 nm has been measured. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2719–2725, 2007     

Microstructural evolution of decagonal quasicrystal in the undercooled Al72Ni12Co16 alloy melts

The microstructure evolution of decagonal quasicrystals in Al₇₂Ni₁₂Co₁₆ alloy was investigated by the electromagnetic melting and cyclic superheating method. Single-phase decagonal quasicrystals have been obtained when the undercoolings were larger than 60 K. The decagonal quasicrystals formed at various undercoolings show different microstructural morphologies. Furthermore, grain refinement was found near the undercooling of 120 K. Based on current thermodynamic and dendrite growth theories, a dimensionless superheating parameter was adopted to explain the effect of processing conditions on the microstructure of Al₇₂Ni₁₂Co₁₆ alloy. The result indicate that the fine equiaxied microstructure of decagonal quasicrystal (D-phase) formed near on undercooling of 120 K originates from the break-up of dendrites.     

Application of N,N‐bis(diphenylphosphino)aniline palladium(II) complexes as pre‐catalysts in Heck coupling reactions

Palladium(II) complexes with N,N‐bis(diphenylphosphino)aniline ligands catalyse the Heck reaction between styrene and aryl bromides, affording stilbenes in good yield. The structures of two of the complexes used as pre‐catalysts have been determined by single‐crystal X‐ray diffraction. Copyright © 2007 John Wiley & Sons, Ltd.