Physico-Chemistry of the Limestone Sulphation Process

Aspects of the mechanism of the overall reaction between CaCO₃/CaO and SO₂/SO₃ under oxidizing conditions are discussed. The limestone and lime sulphation processes were carried out in a thermobalance under conditions relevant to atmospheric fluidized bed combustion. Sulphated samples, prepared in the form of cross-section particles, were examined in a scanning electron microscope by energy-dispersive X-ray and back-scattered electron imaging. Photomicrographs are presented. The reaction proceeded from the outer surface of the particles and along the pores. Surface textural changes during the reaction were considered. The layer of products was identified as controlling both the rate and extent of limestone/lime sulphation. In the products, two sulphur-bearing solids (CaSO₄ and CaS) were identified. The presence of CaS, which may cause difficulties in practice, is attributed to CaSO₃ disproportionation. This revised version was published online in August 2006 with corrections to the Cover Date.     

Mechanosynthesis of zinc ferrite in hardened steel vials: Influence of ZnO on the appearance of Fe(II)

Nanocrystalline ZnFe₂O₄ spinel powders are synthesized by high-energy ball milling, starting from a powder mixture of hematite (α-Fe₂O₃) and zincite (ZnO). The millings are performed under air using hardened steel vials and balls. X-ray diffraction and Mössbauer spectrometry are used to characterize the powders. A spinel phase begins to appear after 3 h of milling and the synthesis is achieved after 9 h. Phase transformation is accompanied by a contamination due to iron coming from the milling tools. A redox reaction is also observed between Fe(III) and metallic iron during milling, leading to a spinel phase containing some Fe(II). The mechanism for the appearance of this phase is studied: ZnO seems to have a non-negligeable influence on the synthesis, by creating an intermediate wüstite-type phase solid solution with FeO.     

Effect of film thickness and supercooling on the performance of cholesteryl cinnamate liquid crystal capillary columns

Improved separations of the isomers of olefinic aliphatic insect pheromones were obtained on cholesteryl cinnamate glass capillary columns by operating in the supercooled temperature range of the liquid crystal. Capillary columns were prepared with varying film thickness of the stationary phase; choice of the correct film thickness ensured optimum retention for a wide range of compounds within the most effective temperature range of the liquid crystal. The deactivation procedures described made the liquid crystal columns suitable for separation of the geometric isomers of polar and nonpolar compounds.     

Phasentransferkatalysatoren auf Basis von Saccharose-Ethylenoxid-Addukten

Sucrose ethyleneoxide adducts have been prepared by reaction of sucrose with various amounts of ethyleneoxide inDMSO. The resulting polypode molecules were found to be efficient phase transfer catalysts in nucleophilic substitutions, oxidation and dichlorcarbene generation. Polymerisable polypodes have been obtained by reaction of sucrose ethyleneoxide adducts with methacrylic anhydride or methacryloylchloride in pyridine. Free radical polymerisation of the resulting mixtures of mono- and polyfunctional methacrylic esters of sucrose ethyleneoxide adducts yielded crosslinked gels. These polymer-supported octopus-molecules were found to be efficient triphase catalysts.

     

Amorphous phase evolution during crystallization of poly(ethylene-terephthalate)

Crystallization of poly(ethylene terephthalate) from the amorphous state has been studied in the temperature range 90°–120°C to characterize the amorphous phase when crystalline microstructure is developing. Small-angle x-ray scattering, scanning electron microscopy, and density measurements were used to investigate the morphology of semi-crystalline materials. Differential scanning calorimetry and dynamical mechanical spectroscopy experiments were carried out on amorphous, partially crystallized and crystallized specimens and, when structural relaxation is allowed (thermal treatments close to but below glass transition temperature), strong evidence is obtained for the existence of two different amorphous phases with different mobilities.     

Synthesis and structure of complex compound Rh(III) of (NH4)2[Rh(NO2)3(NH3)(µ-OH)]2 composition

The crystalline structure of a new compound Rh(III) of (NH₄)₂[Rh(NO₂)₃(NH₃)(μ-OH)]₂ composition has been determined. The crystallographic characteristics are H₁₆N₁₀O₁₄Rh₂: a = 6.3963(2) Å, b = 9.3701(4) Å, c = 13.6646(5) Å, β = 102.266(1)°, V = 800.28(5) ų, Z = 2, d _calc = 2.432 g/cm³. The distance Rh...Rh in the dimer is 3.200 Å. Original Russian Text Copyright ? 2006 by S. P. Khranenko, I. A. Baidina, and S. A. Gromilov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 47, No. 2, pp. 380–384, March–April, 2006.     

Koexistenzbeziehungen,Darstellung und Eigenschaften ternärer Phasen im System Cu/Mo/O

Coexistence Relations, Preparation and Properties of Ternary Compounds in the System Cu/Mo/O The phase diagram of the ternary system Cu/Mo/O is presented at 773 K. The compounds CuMoO₄, Cu₃Mo₂O₉, Cu₄Mo₅O₁₇, Cu₆Mo₅O₁₈, Cu_4–xMo₃O₁₂, and Cu_xMoO₃ are found to be thermodynamical stable. The homogeneity range of Cu_4–xMo₃O₁₂ runs to x = 0.1–0.2. Single crystals of CuMoO₄ and Cu₃Mo₂O₉ were grown by chemical transport reactions with TeCl₄, Cl₂, HCl, and Br₂ as transport agent. The results were compared with thermochemical calculations. The decomposition of CuMoO₄ and Cu₃Mo₂O₉ was investigated with thermal analysis and decompositon pressure measurements.     

Pure Organic Phase Phenol Biosensor Based on Tyrosinase Entrapped in a Vapor Deposited Titania Sol‐Gel Membrane

A novel amperometric biosensor was constructed for the determination of phenols in pure organic phase. This biosensor was fabricated by immobilizing tyrosinase in a titania sol‐gel membrane which was obtained with a vapor deposition method. This method was facile and avoided the calcination step needed in conventional titania sol‐gel process. The titania sol‐gel membrane could effectively retain the essential water layer around the enzyme molecule needed for maintaining its activity in organic phase. The experimental parameters such as solvent and operating potential were optimized. At ?100 mV this biosensor showed a good amperometric response to phenols in pure chloroform without any mediator and rehydration of the enzyme. For catechol determination the sensor exhibited a fast response of less than 5 seconds. The sensitivity of different phenols was as follows: catechol > phenol > p‐cresol. Additionally, the apparent Michaelis‐Menten constants of the encapsulated tyrosinase to catechol, phenol and p‐cresol were found to be 0.15±0.003, 0.17±0.008 and 0.21±0.004 mM, respectively. The biosensor had also good reproducibility and stability. This work provided a promising platform for the construction of pure organic phase biosensors and the determination of substrates with poor water solubility.     

Multiple separatrix crossing in multi-degree-of-freedom Hamiltonian flows

Summary We study separatrix crossing in near-integrablek-degree-of-freedom Hamiltonian flows, 2 <k < , whose unperturbed phase portraits contain separatrices inn degrees of freedom, 1 <n <k. Each of the unperturbed separatrices can be recast as a codimension-one separatrix in the 2k-dimensional phase space, and the collection of these separatrices takes on a variety of geometrical possibilities in the reduced representation of a Poincaré section on the energy surface. In general 0 l n of the separatrices will be available to the Poincaré section, and each separatrix may be completely isolated from all other separatrices or intersect transversely with one or more of the other available separatrices. For completely isolated separatrices, transitions across broken separatrices are described for each separatrix by the single-separatrix crossing theory of Wiggins, as modified by Beigie. For intersecting separatrices, a possible violation of a normal hyperbolicity condition complicates the analysis by preventing the use of a persistence and smoothness theory for compact normally hyperbolic invariant manifolds and their local stable and unstable manifolds. For certain classes of multi-degree-of-freedom flows, however, a local persistence and smoothness result is straightforward, and we study the global implications of such a local result. In particular, we find codimension-one partial barriers and turnstile boundaries associated with each partially destroyed separatrix. From the collection of partial barriers and turnstiles follows a rich phase space partitioning and transport formalism to describe the dynamics amongst the various degrees of freedom. A generalization of Wiggins' higher-dimensional Melnikov theory to codimension-one surfaces in the multi-separatrix case allows one to uncover invariant manifold geometry. In the context of this perturbative analysis and detailed numerical computations, we study invariant manifold geometry, phase space partitioning, and phase space transport, with particular attention payed to the role of a vanishing frequency in the limit approaching the intersection of the partially destroyed separatrices. The class of flows under consideration includes flows of basic physical relevance, such as those describing scattering phenomena. The analysis is illustrated in the context of a detailed study of a 3-degree-of-freedom scattering problem.     

Damage spreading in a single-component irreversible reaction process: Dependence of the system's immunity on the Euclidean dimension

The spreading of a globally distributed damage, created in the stationary regime, is studied in a single-component irreversible reaction process, i.e., the BK model [Browne and Kleban,Phys. Rev. A 40, 1615 (1989)]. The BK model describes one variant of the A+AA₂ reaction process on a lattice in contact with a reservoir of A species. The BK model has a single parameter, namely the rate of arrival of A species to the lattice (Y). The model, exhibits an irreversible phase transition between a stationary reactive state with production of A₂ species and a poisoned state with the lattice fully covered by A species. The transition takes place at critical points (Y _C ) which solely depend on the Euclidean dimensiond. It is found that the system is immune ford=1 andd=2, in the sense that even 100% of initial damage is healed within a finite healing period (T _H ). Within the reactive regime,T _H diverges when approachingY _C according toT _H (Y _C –Y)^–, with 1.62 and 1.08 ford=1 andd=2, respectively. Ford=3 a frozen-chaotic transition is found close toY _s 0.4125, i.e., well inside the reactive regime 0YY _C 0.4985. Just atY _S the damageD(t) heals according toD(t) t ^–, with 0.71. For the frozen-chaotic transition atd=3 the order parameter critical exponent 0.997 is determined.