Markov analysis of qualitative dynamics1

Common sense sometimes predicts events to be likely or unlikely rather than merely possible. We extend methods of qualitative reasoning to predict the relative likelihoods of possible qualitative behaviors by viewing the dynamics of a system as a Markov chain over its transition graph. This involves adding qualitative or quantitative estimates of transition probabilities to each of the transitions and applying the standard theory of Markov chains to distinguish persistent states from transient states and to calculate recurrence times, settling times, and probabilities for ending up in each state. Much of the analysis depends solely on qualitative estimates of transition probabilities, which follow directly from theoretical considerations and which lead to qualitative predictions about entire classes of systems. Quantitative estimates for specific systems are derived empirically and lead to qualitative and quantitative conclusions, most of which are insensitive to small perturbations in the estimated transition probabilities. The algorithms are straightforward and efficient.     

Study of the morphology and mechanical properties of polypropylene composites with silica or rice‐husk

The mechanical, morphological behavior and water absorption characteristics of polypropylene (PP) and silica, or PP and rice‐husk, composites have been studied. The silica used in this study as filler was a commercial type produced from soluble glass or rice husks. The compatibilizing effect of PP grafted with monomethyl itaconate (PP‐g‐MMI) and/or with vinyltriethoxysilane (PP‐g‐VTES) as polar monomers on the mechanical properties and water absorption was also investigated. In general, a high loading of the studied fillers in the polymer matrix increases the stiffness and the water absorption capacity. This effect is more noticeable in the tensile modulus of the PP/silica composite with PP‐g‐VTES as compatibilizer. However, the increase of the rice‐husk charge as a natural filler in the PP matrix decreases the stiffness, and in the presence of PP‐g‐MMI as compatibilizer in PP/rice‐husk, the tensile modulus and water absorption of the composite were improved. The better adhesion and phase continuity in the PP/silica and PP/rice‐husk composites with different compatibilizers was confirmed by the morphological study. Copyright © 2004 Society of Chemical Industry     

Catalytic reduction of N2O with CH4 and C3H6 over Ag–Rh/Al2O3 bimetallic catalyst in the presence of oxygen

A study of nitrous oxide (N₂O) reduction with methane (CH₄) and propene (C₃H₆) in the presence of oxygen (5%) over Ag/Al₂O₃, Rh/Al₂O₃ and Ag–Rh/Al₂O₃ catalysts, with Ag and Rh loadings of 5 wt% and 0.05 wt% respectively, has been performed. From the results, it was observed that the Ag–Rh bimetallic catalyst was the most active for both nitrous oxide removal (more than 95%) and hydrocarbon oxidation. This high activity seems to be connected with a synergistic effect between Ag and Rh. The findings from X‐ray diffraction and X‐ray photoelectron spectroscopy studies showed also, that there were no strong interactions (eg alloying) between Ag and Rh. Copyright © 2005 Society of Chemical Industry     

2,4,6‐Trichlorophenol and phenol removal in methanogenic and partially‐aerated methanogenic conditions in a fluidized bed bioreactor

A fluidized bed bioreactor (FBBR) was operated for more than 575 days to remove 2,4,6‐trichlorophenol (TCP) and phenol (Phe) from a synthetic toxic wastewater containing 80 mg L^?1 of TCP and 20 mg L^?1 of Phe under two regimes: Methanogenic (M) and Partially‐Aerated Methanogenic (PAM). The mesophilic, laboratory‐scale FBBR consisted of a glass column (3 L capacity) loaded with 1 L of 1 mm diameter granular activated carbon colonized by an anaerobic consortium. Sucrose (1 g COD L^?1) was used as co‐substrate in the two conditions. The hydraulic residence time was kept constant at 1 day. Both conditions showed similar TCP and Phe removal (99.9 + %); nevertheless, in the Methanogenic regime, the accumulation of 4‐chlorophenol (4CP) up to 16 mg L^?1 and phenol up to 4 mg L^?1 was observed, whereas in PAM conditions 4CP and other intermediates were not detected. The specific methanogenic activity of biomass decreased from 1.01 ± 0.14 in M conditions to 0.19 ± 0.06 mmolCH₄ h^?1 gTKN^?1 in PAM conditions whereas the specific oxygen uptake rate increased from 0.039 ± 0.008 in M conditions to 0.054 ± 0.012 mmolO₂ h^?1 gTKN^?1, which suggested the co‐existence of both methanogenic archaea and aerobic bacteria in the undefined consortium. The advantage of the PAM condition over the M regime is that it provides for the thorough removal of less‐substituted chlorophenols produced by the reductive dehalogenation of TCP rather than the removal of the parent compound itself. Copyright © 2005 Society of Chemical Industry     

Exchange and oxidation of CO on O-predosed Rh---Al2O3 and Rh---CeO2 catalysts

Exchange and oxidation of C¹⁶O were investigated at 450°C on ¹⁸O-predosed Rh and Pt catalysts supported on A1₂O₃, CeO₂ and CeO₂-Al₂O₃. In all cases, a rapid exchange of C¹⁶O with the surface can be observed. CO oxidation leads to C¹⁶O₂, C¹⁶O¹⁸O and C¹⁸O₂. Significant formation of C¹⁶O₂ is due to the relatively high ¹⁶O coverage in reaction resulting from the C¹⁶O exchange and from an exchange between O surface species and ¹⁶O internal atoms. Hydrogen is also formed via a water-gas shift reaction (CO + surface OH) in higher proportion on CeO₂-containing catalysts than on A1₂O₃. Chlorine inhibits all the reactions (exchange, oxidation and WGS) and particularly the internal exchange.     

The greenhouse effect; Impact upon and the role to be played by construction

The authors highlight several possible ways in which the construction industry could lower present emissions of the greenhouse gas, carbon dioxide. It is an excellent discussion document and is recommended reading.     

Synthesis and characterization of poly(ethylene aspartate)-metal complexes

Poly(ethylene aspartate) [PEA] was synthesized by the melt condensation of D,L-aspartic acid and ethylene glycol. PEA containing pendent amino and carbonyl groups in its repeating chain was used as the polymeric ligand for complexation with transition metal ions, viz. Co(II), Ni(II), Cu(II), Mn(II), Zn(II), Cd(II), Ca(II), Mg(II), Pb(II) and Hg(II). Complexation was found to be most effective in DMSO. The resulting polyester-metal complexes were solid coloured materials which have been characterized by IR spectroscopy, elemental analysis and magnetic susceptibility measurements. The thermal stability of the polyester-metal complexes was investigated by thermogravimetric analysis (TGA). On the basis of the physico-chemical studies, an oxygen and nitrogen coordinated structure for the polyester-metal complexes is proposed.     

Morphology and structure of poly(p-phenylene terephthalamide) crystallized from dilute organic solution

The high-temperature crystallization of poly(p-phenylene terephthalamide) (PPTA) from dilute organic solutions was achieved through the introduction of a non-solvent, or precipitating agent, at the desired crystallization temperature. The morphology and crystal structure were examined for crystals produced from PPTA polymer with two different molecular weights (M_w = 46000 and 3430 g mol⁻¹), using transmission electron microscopy. For the high-molecular-weight polymer, ribbon-like crystals were produced, while the low-molecular-weight polymer yielded small needles or platelets. In both cases, electron diffraction showed that the Northolt allomorph was obtained. For the high-molecular-weight polymer, the molecular axes were parallel to the ribbon axes in a chain-extended type structure. A hypothesis for the orientation of the low-molecular-weight PPTA in the small platelets, is also given.     

Probing the early stages of polymerization of ethylene on a model chromium/silica catalyst by Fourier transform infrared spectroscopy

The nature of the interaction of monomer, and the early stages of growth of oligomers of ethylene on a rather more uniform surface of Cr/SiO₂ catalyst than hitherto studied has been investigated by differenceFTIR spectroscopy using C₂D₄ and C₂H₄ as reactants both with and without subsequent treatment of the catalyst with CO andTHF. The active catalyst was prepared by reaction of vapour phase CrO₂Cl₂ with the vicinal hydroxyls of the silica surface. Three distinct kinds of methylene groups were detected. Arguments are given for assigning the peaks at 2935 and 2860 cm^–1 to CH₂ groups directly bound to the active site and those at 2920 and 2850 to CH₂s in the growing chain well removed from the Cr. The peaks at 2160 and 2165 cm^–1 are attributed to CD₂ groups hydrogen bonded to surface hydroxyls.