Time-resolved gas-phase kinetic and quantum chemical studies of reactions of silylene with chlorine-containing species. 1. HCl

Time-resolved kinetic studies of the reaction of silylene, SiH2, generated by laser flash photolysis of phenylsilane, have been carried out to obtain rate constants for its bimolecular reaction with HCL The reaction was studied in the gas phase at 10 Torr total pressure in SF6 bath gas, at five temperatures in the range of 296-611 K. The second-order rate constants fitted the Arrhenius equation: log(k/cm(3) molecule(-1) s(-1)) = (-11.51 +/- 0.06) + (1.92 +/- 0.47 kJ mol(-1))/RTIn10 Experiments at other pressures showed that these rate constants were unaffected by pressure in the range of 10-100 Torr, but showed small decreases in value of no more than 20% ( +/- 10%) at I Toff, at both the highest and lowest temperatures. The data are consistent with formation of an initial weakly bound donor-acceptor complex, which reacts by two parallel pathways. The first is by chlorine-to-silicon H-shift to make vibrationally excited chlorosilane, SiH3Cl*, which yields HSiCl by H-2 elimination from silicon. In the second pathway, the complex proceeds via H-2 elimination (4-center process) to make chlorosilylene, HSiCl, directly. This interpretation is supported by ab initio quantum calculations carried out at the G3 level which reveal the direct H-2 elimination route for the first time. RRKM modeling predicts the approximate magnitude of the pressure effect but is unable to determine the proportions of each pathway. The experimental data agree with the only previous measurements at room temperature. Comparisons with other reactions of SiH2 are also drawn.

Time-resolved gas-phase kinetic and quantum chemical studies of reactions of silylene with chlorine-containing species. 2. CH3Cl

Time-resolved kinetic studies of the reaction of silylene, SiH2, generated by laser flash photolysis of both silacyclopent-3-ene and phenylsilane, have been carried out to obtain second-order rate constants for its reaction with CH3Cl. The reaction was studied in the gas phase at six temperatures in the range 294-606 K. The second-order rate constants gave a curved Arrhenius plot with a minimum value at T approximate to 370 K. The reaction showed no pressure dependence in the presence of up to 100 Torr SF6. The rate constants, however, showed a weak dependence on laser pulse energy. This suggests an interpretation requiring more than one contributing reaction pathway to SiH2 removal. Apart from a direct reaction of SiH2 with CH3Cl, reaction of SiH2 with CH3 (formed by photodissociation of CH3Cl) seems probable, with contributions of up to 30% to the rates. Ab initio calculations (G3 level) show that the initial step of reaction of SiH2 with CH3Cl is formation of a zwitterionic complex (ylid), but a high-energy barrier rules out the subsequent insertion step. On the other hand, the Cl-abstraction reaction leading to CH3 + ClSiH2 has a low barrier, and therefore, this seems the most likely candidate for the main reaction pathway of SiH2 with CH3Cl. RRKM calculations on the abstraction pathway show that this process alone cannot account for the observed temperature dependence of the rate constants. The data are discussed in light of studies of other silylene reactions with haloalkanes.

Synthesis of hyperbranched poly(aryl ether)s via carbene insertion processes

Homopolymerization of alkylarylcarbenes derived from diazirine monomers that featured benzyl alcohol or phenol residues was found to lead to the production of soluble hyperbranched poly(aryl ether)s. The polymerization process was influenced by the solvents employed, monomer concentration, and the reaction time. An increase in the monomer concentration and reaction time was found to lead to an increase in the molecular weight characteristics of the resulting polymers as determined by gel permeation chromatography (GPC). The composition and architecture of the polyethers were determined by nuclear magnetic resonance (NMR) spectroscopic analysis and were found to be highly complex and dependent on the structure of the monomers used. All of the polymers were found to contain ether linkages formed via carbene insertion into O-H bonds, although polymers derived from phenolic carbenes also contained linkages arising from C-alkylation.

Chemoselective catalytic hydrogenation of acrolein on Ag(111): effect of molecular orientation on reaction selectivity

The adsorption and hydrogenation of acrolein on the Ag(111) surface has been investigated by high resolution synchrotron XPS, NEXAFS, and temperature programmed reaction. The molecule adsorbs intact at all coverages and its adsorption geometry is critically important in determining chemoselectivity toward the formation of allyl alcohol, the desired but thermodynamically disfavored product. In the absence of hydrogen adatoms (H(a)), acrolein lies almost parallel to the metal surface; high coverages force the C=C bond to tilt markedly, likely rendering it less vulnerable toward reaction with hydrogen adatoms. Reaction with coadsorbed H(a) yields allyl alcohol, propionaldehyde, and propanol, consistent with the behavior of practical dispersed Ag catalysts operated at atmospheric pressure: formation of all three hydrogenation products is surface reaction rate limited. Overall chemoselectivity is strongly influenced by secondary reactions of allyl alcohol. At low H(a) coverages, the C=C bond in the newly formed allyl alcohol molecule is strongly tilted with respect to the surface, rendering it immune to attack by H(a) and leading to desorption of the unsaturated alcohol. In contrast with this, at high H(a) coverages, the C=C bond in allyl alcohol lies almost parallel to the surface, undergoes hydrogenation by H(a), and the saturated alcohol (propanol) desorbs.

Structure, and thermal, magnetic and chemical properties of copper(II)iodoacetate monohydrate

Reaction of iodoacetic acid with cupric carbonate in water in dimmed light yields green Cu(ICH2COO)(2 center dot)H2O (1). From X-ray crystallography, it is found to be a tetra-acetato bridged copper(II) dimer with the water molecules occupying the apical positions. In thermogravimetry, the coordinated water molecules are lost in the temperature range 50-100 degrees C. From magnetic susceptibility measurements in the temperature range 300-1.8 K, the exchange coupling constant J is found to be -142(1) cm(-1) and g = 2.18(2) with the spin Hamiltonian H = -2J{S-Cu1 center dot S-Cu2}. It reacts with 2,2'-bipyridine (bpy) to yield [Cu(bpy)(2)I]I. It oxidises thiophenol to Ph-S-S-Ph under dry N-2 atmosphere.

Chemical, physical and electrical properties of aged dodecylbenzene: thermal ageing of mixed isomers in air

A commercial dodecylbenzene (DDB) cable oil was aged at temperatures between 90 and 135 degrees C in air and was analyzed using various analytical techniques including optical and infra-red spectroscopy and dielectric analysis. On ageing, the oil darkened, significant oxidation features were found by infra-red spectroscopy and the acid number, water content and dielectric loss all increased. Ageing in the presence of paper or aluminum did not affect the ageing process, whereas ageing was significantly modified by the presence of copper. An absorption at 680 nm ("red absorbers") was detected by ultra-violet/visible spectroscopy followed by the production of an opaque precipitate. A reaction between copper and the acid generated on ageing is thought to produce copper carboxylates, and X-ray fluorescence confirmed that copper was indeed present in both the aged oil and the precipitate. Significantly, once red absorbers were detected, the dielectric loss increased to catastrophically high values and, therefore, the appearance of these compounds may serve as a useful diagnostic indicator. The development of acidity on ageing appears to be key in initiating the destructive copper conversion reaction and hence the control of oil acidity may be key to prolonging the life of DDB cable oils.

Gas-solid reactions of single crystals: a study of the reaction of bromine with single crystals of trans-cinnamic acid and a range of its derivatives by infrared and Raman microspectroscopy

Single crystals of trans-cinnamic acid and of a range of derivatives of this compound containing halogen substituents on the aromatic ring have been reacted with 165 Torr pressure of bromine vapour in a sealed desiccator at 20 degrees C for 1 week. Infrared and Raman microspectroscopic examination of the crystals shows that bromination of the aliphatic double bond, but not of the aromatic ring, has occurred. It is demonstrated also that the reaction is truly gas-solid in nature. A time-dependent study of these reactions shows that they do not follow a smooth diffusion-controlled pathway. Rather the reactions appear to be inhomogeneous and to occur at defects within the crystal. The reaction products are seen to flake from the surface of the crystal. It is shown, therefore, that these are not single crystal to single crystal transitions, as have been observed previously for the photodimerisation of trans-cinnamic acid and several of its derivatives. It is shown that there are no by-products of the reaction and that finely ground samples react to form the same products as single crystals.

Simulating the detailed chemical composition of secondary organic aerosol formed on a regional scale during the TORCH 2003 campaign in the southern UK

Following on from the companion study (Johnson et al., 2006), a photochemical trajectory model (PTM) has been used to simulate the chemical composition of organic aerosol for selected events during the 2003 TORCH (Tropospheric Organic Chemistry Experiment) field campaign. The PTM incorporates the speciated emissions of 124 nonmethane anthropogenic volatile organic compounds (VOC) and three representative biogenic VOC, a highly-detailed representation of the atmospheric degradation of these VOC, the emission of primary organic aerosol (POA) material and the formation of secondary organic aerosol (SOA) material. SOA formation was represented by the transfer of semi and non-volatile oxidation products from the gas-phase to a condensed organic aerosol-phase, according to estimated thermodynamic equilibrium phase-partitioning characteristics for around 2000 reaction products. After significantly scaling all phase-partitioning coefficients, and assuming a persistent background organic aerosol (both required in order to match the observed organic aerosol loadings), the detailed chemical composition of the simulated SOA has been investigated in terms of intermediate oxygenated species in the Master Chemical Mechanism, version 3.1 ( MCM v3.1). For the various case studies considered, 90% of the simulated SOA mass comprises between ca. 70 and 100 multifunctional oxygenated species derived, in varying amounts, from the photooxidation of VOC of anthropogenic and biogenic origin. The anthropogenic contribution is dominated by aromatic hydrocarbons and the biogenic contribution by alpha-and beta-pinene (which also constitute surrogates for other emitted monoterpene species). Sensitivity in the simulated mass of SOA to changes in the emission rates of anthropogenic and biogenic VOC has also been investigated for 11 case study events, and the results have been compared to the detailed chemical composition data. The role of accretion chemistry in SOA formation, and its implications for the results of the present investigation, is discussed.

Pinic and pinonic acid formation in the reaction of ozone with alpha-pinene

The mechanism of formation of key compounds in atmospheric secondary aerosol (SOA) has been investigated by studying the products of the ozonolysis of an enal derived from alpha-pinene using gas chromatography coupled to mass spectrometry.

Aziridine synthesis via nucleophilic attack of carbene equivalents on imines: the aza-Darzens reaction

The development of new methods for the efficient synthesis of aziridines has been of considerable interest to researchers for more than 60 years, but no single method has yet emerged as uniformly applicable, especially for asymmetric synthesis of chiral aziridines. One method which has been intensely examined and expanded of late involves the nucleophilic addition to imines by anions bearing a-leaving groups; by analogy with the glycidate epoxide synthesis, these processes are often described as "aza-Darzens reactions". This Microreview gives a summary of the area, with a focus on contemporary developments. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Sigmatropic rearrangements of 'onium' ylids

Rearrangement reactions occupy a special place within the canon of organic synthesis, by virtue of the inherently high efficiency of chemical processes which form and breyak bonds by redistribution of electrons around a retained atomic framework. Within the broader class, sigmatropic rearrangements are chemical processes defined by mechanisms involving unimolecular migration of sigma-bonds with concomitant redistribution of one or more pi-bonds. Sigmatropic processes may involve uncharged or charged species, with the charges located on carbon or heteroatoms; the latter reaction type is the subject of this tutorial review.

A reaction surface Hamiltonian study of malonaldehyde

We report calculations using a reaction surface Hamiltonian for which the vibrations of a molecule are represented by 3N-8 normal coordinates, Q, and two large amplitude motions, s(1) and s(2). The exact form of the kinetic energy operator is derived in these coordinates. The potential surface is first represented as a quadratic in Q, the coefficients of which depend upon the values of s(1),s(2) and then extended to include up to Q(6) diagonal anharmonic terms. The vibrational energy levels are evaluated by solving the variational secular equations, using a basis of products of Hermite polynomials and appropriate functions of s(1),s(2). Our selected example is malonaldehyde (N=9) and we choose as surface parameters two OH distances of the migrating H in the internal hydrogen transfer. The reaction surface Hamiltonian is ideally suited to the study of the kind of tunneling dynamics present in malonaldehyde. Our results are in good agreement with previous calculations of the zero point tunneling splitting and in general agreement with observed data. Interpretation of our two-dimensional reaction surface states suggests that the OH stretching fundamental is incorrectly assigned in the infrared spectrum. This mode appears at a much lower frequency in our calculations due to substantial transition state character. (c) 2006 American Institute of Physics.

Evaluation of data for atmospheric models: master equation/RRKM calculations on the combination reaction, BrO+NO2 -> BrONO2, a conundrum

Experimental data for the title reaction were modeled using master equation (ME)/RRKM methods based on the Multiwell suite of programs. The starting point for the exercise was the empirical fitting provided by the NASA (Sander, S. P.; Finlayson-Pitts, B. J.; Friedl, R. R.; Golden, D. M.; Huie, R. E.; Kolb, C. E.; Kurylo, M. J.; Molina, M. J.; Moortgat, G. K.; Orkin, V. L.; Ravishankara, A. R. Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation Number 15; Jet Propulsion Laboratory: Pasadena, California, 2006)(1) and IUPAC (Atkinson, R.; Baulch, D. L.; Cox, R. A.: R. F. Hampson, J.; Kerr, J. A.; Rossi, M. J.; Troe, J. J. Phys. Chem. Ref. Data. 2000, 29, 167) 2 data evaluation panels, which represents the data in the experimental pressure ranges rather well. Despite the availability of quite reliable parameters for these calculations (molecular vibrational frequencies (Parthiban, S.; Lee, T. J. J. Chem. Phys. 2000, 113, 145)3 and a. value (Orlando, J. J.; Tyndall, G. S. J. Phys. Chem. 1996, 100,. 19398)4 of the bond dissociation energy, D-298(BrO-NO2) = 118 kJ mol(-1), corresponding to Delta H-0(circle) = 114.3 kJ mol(-1) at 0 K) and the use of RRKM/ME methods, fitting calculations to the reported data or the empirical equations was anything but straightforward. Using these molecular parameters resulted in a discrepancy between the calculations and the database of rate constants of a factor of ca. 4 at, or close to, the low-pressure limit. Agreement between calculation and experiment could be achieved in two ways, either by increasing Delta H-0(circle) to an unrealistically high value (149.3 kJ mol(-1)) or by increasing , the average energy transferred in a downward collision, to an unusually large value (> 5000 cm(-1)). The discrepancy could also be reduced by making all overall rotations fully active. The system was relatively insensitive to changing the moments of inertia in the transition state to increase the centrifugal effect. The possibility of involvement of BrOONO was tested and cannot account for the difficulties of fitting the data.

Multivariate analysis of phenol mineralisation by combined hydrodynamic cavitation and heterogeneous advanced Fenton processing

Phenolic compounds in wastewaters are difficult to treat using the conventional biological techniques such as activated sludge processes because of their bio-toxic and recalcitrant properties and the high volumes released from various chemical, pharmaceutical and other industries. In the current work, a modified heterogeneous advanced Fenton process (AFP) is presented as a novel methodology for the treatment of phenolic wastewater. The modified AFP, which is a combination of hydrodynamic cavitation generated using a liquid whistle reactor and the AFP is a promising technology for wastewaters containing high organic content. The presence of hydrodynamic cavitation in the treatment scheme intensifies the Fenton process by generation of additional free radicals. Also, the turbulence produced during the hydrodynamic cavitation process increases the mass transfer rates as well as providing better contact between the pseudo-catalyst surfaces and the reactants. A multivariate design of experiments has been used to ascertain the influence of hydrogen peroxide dosage and iron catalyst loadings on the oxidation performance of the modified AFP. High er TOC removal rates were achieved with increased concentrations of hydrogen peroxide. In contrast, the effect of catalyst loadings was less important on the TOC removal rate under conditions used in this work although there is an optimum value of this parameter. The concentration of iron species in the reaction solution was measured at 105 min and its relationship with the catalyst loadings and hydrogen peroxide level is presented.

Techno-economic modelling and cost functions of CO2 capture processes

The paper presents the techno-economic modelling of CO2 capture process in coal-fired power plants. An overall model is being developed to compare carbon capture and sequestration options at locations within the UK, and for studies of the sensitivity of the cost of disposal to changes in the major parameters of the most promising solutions identified. Technological options of CO2 capture have been studied and cost estimation relationships (CERs) for the chosen options calculated. Created models are related to the capital, operation and maintenance cost. A total annualised cost of plant electricity output and amount of CO2 avoided have been developed. The influence of interest rates and plant life has been analysed as well. The CERs are included as an integral part of the overall model.