Formation of Ammonia during the NO-H-2 Reaction over Pt/ZrO2

The mechanism for the formation of NH3 during the NO-H-2 reaction over Pt/ZrO2 was studied. Steady-state isotopic transient kinetic analysis was carried out with isotopic switching from (NO)-N-15-D-2 to (NO)-N-14-D-2, and the results revealed that formation of N-2 and N2O was associated with linearly adsorbed NO on the Pt surface, whereas ammonia formation was associated with NDx species adsorbed on ZrO2. The adsorbed NHx species were not observed on the surface of ZrO2 during NH3 adsorption. From transient kinetic experiments, the formation rates of NHx species and of gaseous NH3 agreed with each other, suggesting that the NHx species on ZrO2 was an ammonia intermediate. The NDx species did not react with D-2 directly, but H-D exchange occurred easily. The addition of H2O to the NO-H-2 feed gas enhanced the formation of NH3. In situ diffuse reflectance spectra and transient kinetic analysis revealed that H2O enhanced the conversion of NHx species to NH3.

Formation of Novel Di-Nuclear Lanthanide Luminescent Sm(III), Eu(III) and Tb(III) Triple Stranded Helicates from a C2 Symmetrically 2,6-Dicarboxylic Amide based 1,3-Xylene Ligand in CH3CN

The synthesis of the C2-symmetrical ligand 1 consisting of two naphthalene units connected to two pyridine-2,6-dicarboxamide moieties linked by a xylene spacer and the formation of LnIII-based (Ln1/4 Sm, Eu, Tb, and Lu) dimetallic helicates [Ln2 · 13] in MeCN by means of a metal-directed synthesis is described. By analyzing the metal-induced changes in the absorption and the fluorescence of 1, the formation of the helicates, and the presence of a second species [Ln2 · 12] was confirmed by nonlinear- regression analysis. While significant changes were observed in the photophysical properties of 1, the most dramatic changes were observed in the metal-centred lanthanide emissions, upon excitation of the naphthalene antennae. From the changes in the lanthanide emission, we were able to demonstrate that these helicates were formed in high yields (ca. 90% after the addition of 0.6 equiv. of LnIII), with high binding constants, which matched well with that determined from the changes in the absorption spectra. The formation of the LuIII helicate, [ Lu2 · 13 ] , was also investigated for comparison purposes, as we were unable to obtain accurate binding constants from the changes in the fluorescence emission upon formation of [Sm2 · 13], [Eu2 · 13], and [Tb2 · 13].

Gas-Phase Formation of Doubly-Deuterated Species

We present the first results from a time-dependent chemical model to include a gas-phase reaction scheme for producing doubly-deuterated species. Under normal conditions the formation of these species is inefficient. However, when the effects of the freeze out of gas phase species onto grains is included in the chemistry we find that the fractionation of both singly and doubly deuterated species is enhanced. We compare the predictions from our models with recent observations of deuterated molecules in L134N and find that, contrary to previous expectations, we can reproduce the observed levels of fractionation without recourse to an active grain-surface chemistry.

Ionic liquids via reaction of the zwitterionic 1,3-dimethylimidazolium-2-carboxylate with protic acids. Overcoming synthetic limitations and establishing new halide free protocols for the formation of ILs

The previously reported preparation of 1,3-dimethylimidazolium salts by the reaction of 1,3-dialkylimidazolium-2-carboxylate zwitterions with protic acids has been reinvestigated in detail, leading to the identification of two competing reactions: isomerisation and decarboxylation. The ability to control both pathways allows this methodology to be used as an effective, green, waste-free approach to readily prepare a wide range of ionic liquids in high yields. Additionally, this reaction protocol opens new possibilities in the formation of other imidazolium salts, whose syntheses were previously either very expensive (due to ion exchange protocols involving metals like Ag) or difficult to achieve (due to multiple extractions and large quantities of hard to remove inorganic by-products).

Approaches to crystallization from ionic liquids: complex solvents-complex results, or, a strategy for controlled formation of new supramolecular architectures?

There are now more than 1200 papers a year describing research results using the 'neoteric' solvents, known as ionic liquids (ILs). If ILs are such highly studied solvents, why has there been so comparatively little research in their use in crystallization? Here we explore this question and discuss possible strategies for utilization of the mundane and the unique aspects of ILs for novel crystallization strategies including crystallization of high and low melting solids using thermal shifts; ''solvothermal'' techniques; slow diffusion; electrocrystallization; and use of a co-solvent. The results presented here and those appearing in the literature indicate both the complex nature of these solvents and their promise in delivering unique solvation, metal ion coordination numbers, coordination polymer motifs, and metal-anion interactions, to name but a few. These complex, but fascinating, results and the promise of much more intimate control over crystallization processes will drive a growing interest in using ILs as crystallization solvents.

Sonic Geography, Place and Race in the Formation of Local Identity: Liverpool and Scousers

The concept of identity has attracted significant academic attention. This article unpacks what constitutes the Scouse identity, how it is constructed and its different dimensions, with particular reference to place, phonology and race. Its novelty lies in developing the underused concept of “sonic geography” to examine the extent to which sound, for example a distinctive accent and/or dialect, affects the construction of local identity. Empirically this is conducted through a detailed analysis of the Scouse, or Liverpudlian, identity. The article also deploys the concept of “sonic exclusion” to examine the role a distinguishing vernacular plays in shaping local identity and the extent to which it determines “who is in” and “who is out” as a Scouser. The conclusion is that an effective understanding of a Scouser is not only spatial – someone born in Liverpool – because the sonoric landscape of spoken Scouse, and thereby Scouse identity, extends beyond the contemporary political and geographic boundaries of the City of Liverpool.

Formation of NH4[Hg-3(NH)(2)](NO3)(3) and transformation to [Hg2N](NO3)

NH4[Hg-3(NH)(2)](NO3)(3) (1) and [Hg2N](NO3) (2) are obtained from cone. aqueous ammonia solutions of Hg(NO3)(2) at ambient temperature and under hydrothermal conditions at 180 degreesC, respectively, as colourless and dark yellow to light brown single crystals. The crystal structures {NH4[Hg-3(NH)(2)](NO3)(3): cubic, P4(I)32, a = 1030.4(2) pm, Z = 4, R-all = 0.028; [Hg2N](NO3): tetragonal, P4(3)2(1)2, a = 1540.4(1), c = 909.8(1) pm, Z = 4, R-all = 0.054} have been determined from single crystal data. Both exhibit network type structures in which [HNHg3] and [NHg4] tetrahedra of the partial structures of 1 and 2 are connected via three and four vertices, respectively. 1 transforms at about 270 degreesC in a straightforward reaction to 2 whereby the decomposition products of NH4NO3 are set free. 2 decomposes at about 380 degreesC forming yellow HgO. Most certainly, I is identical with a mineral previously analyzed as