Higher oxides of chlorine: absorption cross-sections of Cl2O6 and Cl2O4, the decomposition of Cl2O6, and the reactions of OClO with O and O-3

The absorption cross-sections of Cl2O6 and Cl2O4 have been obtained using a fast flow reactor with a diode array spectrometer (DAS) detection system. The absorption cross-sections at the wavelengths of maximum absorption (lambda(max)) determined in this study are those of Cl2O6: (1.47 +/- 0.15) x 10(-17) cm(2) molecule(-1), at lambda(max) = 276 nm and T = 298 K; and Cl2O4: (9.0 +/- 2.0) x 10(-19) cm(2) molecule(-1), at lambda(max) = 234 nm and T = 298 K. Errors quoted are two standard deviations together with estimates of the systematic error. The shapes of the absorption spectra were obtained over the wavelength range 200-450 nm for Cl2O6 and 200-350 nm for Cl2O4, and were normalized to the absolute cross-sections obtained at lambda(max) for each oxide, and are presented at 1 nm intervals. These data are discussed in relation to previous measurements. The reaction of O with OCIO has been investigated with the objective of observing transient spectroscopic absorptions. A transient absorption was seen, and the possibility is explored of identifying the species with the elusive sym-ClO3 or ClO4, both of which have been characterized in matrices, but not in the gas-phase. The photolysis of OCIO was also re-examined, with emphasis being placed on the products of reaction. UV absorptions attributable to one of the isomers of the ClO dimer, chloryl chloride (ClClO2) were observed; some Cl2O4 was also found at long photolysis times, when much of the ClClO2 had itself been photolysed. We suggest that reports of Cl2O6 formation in previous studies could be a consequence of a mistaken identification. At low temperatures, the photolysis of OCIO leads to the formation of Cl2O3 as a result of the addition of the ClO primary product to OCIO. ClClO2 also appears to be one product of the reaction between O-3 and OCIO, especially when the reaction occurs under explosive conditions. We studied the kinetics of the non-explosive process using a stopped-flow technique, and suggest a value for the room-temperature rate coefficient of (4.6 +/- 0.9) x 10(-19) cm(3) molecule(-1) s(-1) (limit quoted is 2sigma random errors). The photochemical and thermal decomposition of Cl2O6 is described in this paper. For photolysis at k = 254 nm, the removal of Cl2O6 is not accompanied by the build up of any other strong absorber. The implications of the results are either that the photolysis of Cl2O6 produces Cl-2 directly, or that the initial photofragments are converted rapidly to Cl-2. In the thermal decomposition of Cl2O6, Cl2O4 was shown to be a product of reaction, although not necessarily the major one. The kinetics of decomposition were investigated using the stopped-flow technique. At relatively high [OCIO] present in the system, the decay kinetics obeyed a first-order law, with a limiting first-order rate coefficient of 0.002 s(-1). (C) 2004 Elsevier B.V. All rights reserved.

Solvent-induced dynamic single-crystal-to-single-crystal transformation of a synthetic peptide-based cyclic compound

Solvent induced single-crystal-to-single-crystal transformation has been demonstrated indicating the dynamic behavior of one dimensional arrays obtained from a self-assembled new synthetic cyclic peptide.

The trapping and decomposition of toxic gases such as hydrogen cyanide using modified mesoporous silicates

Selected silicas were modified with the covalently bound ligand 2,6-bis(benzoxazoyl)pyridine (BBOP), equilibrated with copper(II) nitrate, then challenged with toxic vapour containing HCN (8000 mg m(-3) at 80% relative humidity). The modified SBA-15 material (Cu-BBOP-SBA-15) had an improved breakthrough time for HCN (36 min at a flow rate of 30 cm(3) min(-1)) when compared to the other siliceous materials prepared in this study, equating to a hydrogen cyanide capacity of 58 mg g(-1), which is close to a reference activated carbon adsorbent (24 min at 50 cm(3) min(-1)) that can trap 64 mg g(-1). The enhanced performance observed with Cu-BBOP-SBA-15 has been related to the greater accessibility of the functional groups, arising from the ordered nature of the interconnected porous network and large mesopores of 5.5 nm within the material modified with the Cu(II)-BBOP complex. Modified MCM-41 and MCM-48 materials (Cu-BBOP-MCM-41 and Cu-BBOP-MCM-48) were found to have lower hydrogen cyanide capacities (38 and 32 mg g(-1) respectively) than the Cu-BBOP-SBA-15 material owing to the restricted size of the pores (2.2 and <2 nm respectively). The materials with poor nano-structured ordering were found to have low hydrogen cyanide capacities, between 11 and 19 mg g(-1), most likely owing to limited accessibility of the functional groups. (C) 2004 Elsevier Inc. All rights reserved.

The kinetics of the gas-phase decomposition of the 2-methyl-2-butoxyl and 2-methyl-2-pentoxyl radicals

The kinetics of the title reactions have been studied by relative-rate methods as a function of temperature. Relative-rate coefficients for the two decomposition channels of 2-methyl-2-butoxyl have been measured at five different temperatures between 283 and 345 K and the observed temperature dependence is consistent with the results of some previous experimental studies. The kinetics of the two decomposition channels of 2-methyl-2-pentoxyl have also been investigated, as a function of temperature, relative to the estimated rate of isomerisation of this radical. Room-temperature rate coefficient data for the two decomposition channels of both 2-methyl-2-pentoxyl and 2-methyl-2-butxoyl (after combining the relative rate coefficient for this latter with a value for the rate coefficient of the major channel, extrapolated from the data presented by Batt et al., Int. J. Chem. Kinet., 1978, 10, 931) are shown to be consistent with a non-linear kinetic correlation, for alkoxyl radical decomposition rate data, previously presented by this laboratory (Johnson et al., Atmos. Environ., 2004, 38, 1755-1765).

Rapid, uncatalyzed ring-opening polymerization of individual macrocyclic poly(arylene thioether ketone)s under dynamic heating conditions

Uncatalyzed, ring-opening polymerization of individual macrocyclic poly(arylene thioether ketone)s (1-4) and mixtures (5) under dynamic heating conditions has been demonstrated for the first time. High-molecular-weight, film-forming products were obtained after heating of the macrocycles up to 480 degreesC, with a heating rate of 10-20 degreesC /min. Depending on the macrocyclic structure and heat treatment conditions, the polymers obtained were amorphous or semicrystalline, soluble or slightly crosslinked. NMR analyses of the soluble polymers revealed their linear, highly regular structure. According to NMR, DSC, and TGA studies, the polymers obtained do not contain any residual macrocycles. The polymers with thio-p-arylene moieties in the main chain were thermally stabile. The catalyzed ring opening polymerization of 5 carried out in diphenyl sulfone solution is also reported for comparison. Using quantum mechanical calculations of the ring opening of macrocycles, a reaction mechanism is suggested. Preparation of nanosized poly(thioether ketone) fibrils by a replication method is described.

Dynamic modelling of a wind catcher/tower turret for natural ventilation

This paper discusses experimental and theoretical investigations and Computational Fluid Dynamics (CFD) modelling considerations to evaluate the performance of a square section wind catcher system connected to the top of a test room for the purpose of natural ventilation. The magnitude and distribution of pressure coefficients (C-p) around a wind catcher and the air flow into the test room were analysed. The modelling results indicated that air was supplied into the test room through the wind catcher's quadrants with positive external pressure coefficients and extracted out of the test room through quadrants with negative pressure coefficients. The air flow achieved through the wind catcher depends on the speed and direction of the wind. The results obtained using the explicit and AIDA implicit calculation procedures and CFX code correlate relatively well with the experimental results at lower wind speeds and with wind incidents at an angle of 0 degrees. Variation in the C-p and air flow results were observed particularly with a wind direction of 45 degrees. The explicit and implicit calculation procedures were found to be quick and easy to use in obtaining results whereas the wind tunnel tests were more expensive in terms of effort, cost and time. CFD codes are developing rapidly and are widely available especially with the decreasing prices of computer hardware. However, results obtained using CFD codes must be considered with care, particularly in the absence of empirical data.

Competitive strategy revisited: contested concepts and dynamic capabilities

Strategy is a contested concept. The generic literature is characterized by a diverse range of competing theories and alternative perspectives. Traditional models of the competitive strategy of construction firms have tended to focus on exogenous factors. In contrast, the resource-based view of strategic management emphasizes the importance of endogenous factors. The more recently espoused concept of dynamic capabilities extends consideration beyond static resources to focus on the ability of firms to reconfigure their operating routines to enable responses to changing environments. The relevance of the dynamics capabilities framework to the construction sector is investigated through an exploratory case study of a regional contractor. The focus on how firms continuously adapt to changing environments provides new insights into competitive strategy in the construction sector. Strong support is found for the importance of path dependency in shaping strategic choice. The case study further suggests that strategy is a collective endeavour enacted by a loosely defined group of individual actors. Dynamic capabilities are characterized by an empirical elusiveness and as such are best construed as situated practices embedded within a social and physical context.

Inverse problems in dynamic cognitive modeling

Inverse problems for dynamical system models of cognitive processes comprise the determination of synaptic weight matrices or kernel functions for neural networks or neural/dynamic field models, respectively. We introduce dynamic cognitive modeling as a three tier top-down approach where cognitive processes are first described as algorithms that operate on complex symbolic data structures. Second, symbolic expressions and operations are represented by states and transformations in abstract vector spaces. Third, prescribed trajectories through representation space are implemented in neurodynamical systems. We discuss the Amari equation for a neural/dynamic field theory as a special case and show that the kernel construction problem is particularly ill-posed. We suggest a Tikhonov-Hebbian learning method as regularization technique and demonstrate its validity and robustness for basic examples of cognitive computations.

Dynamic virtual environments using really simple syndication

This paper investigates the use of really simple syndication (RSS) to dynamically change virtual environments. The case study presented here uses meteorological data downloaded from the Internet in the form of an RSS feed, this data is used to simulate current weather patterns in a virtual environment. The downloaded data is aggregated and interpreted in conjunction with a configuration file, used to associate relevant weather information to the rendering engine. The engine is able to animate a wide range of basic weather patterns. Virtual reality is a way of immersing a user into a different environment, the amount of immersion the user experiences is important. Collaborative virtual reality will benefit from this work by gaining a simple way to incorporate up-to-date RSS feed data into any environment scenario. Instead of simulating weather conditions in training scenarios, actual weather conditions can be incorporated, improving the scenario and immersion.

Dynamic automata for mobile robot learning

Researchers at the University of Reading have developed over many years some simple mobile robots that explore an environment they perceive through simple ultrasonic sensors. Information from these sensors has allowed the robots to learn the simple task of moving around while avoiding dynamic obstacles using a static set of fuzzy automata, the choice of which has been criticised, due to its arbitrary nature. This paper considers how a dynamic set of automata can overcome this criticism. In addition, a new reinforcement learning function is outlined which is both scalable to different numbers and types of sensors. The innovations compare successfully with earlier work.