The gas-phase reaction between silylene and 2-butyne: kinetics, isotope studies, pressure dependence studies and quantum chemical calculations

Time-resolved kinetic studies of the reactions of silylene, SiH2, and dideutero-silylene, SiD2, generated by laser. ash photolysis of phenylsilane and phenylsilane-d(3), respectively, have been carried out to obtain rate coefficients for their bimolecular reactions with 2-butyne, CH3C CCH3. The reactions were studied in the gas phase over the pressure range 1-100 Torr in SF6 bath gas at five temperatures in the range 294-612 K. The second-order rate coefficients, obtained by extrapolation to the high pressure limits at each temperature, fitted the Arrhenius equations where the error limits are single standard deviations: log(k(H)(infinity)/cm(3) molecule(-1) s(-1)) = (-9.67 +/- 0.04) + (1.71 +/- 0.33) kJ mol(-1)/RTln10 log(k(D)(infinity)/cm(3) molecule(-1) s(-1)) = (-9.65 +/- 0.01) + (1.92 +/- 0.13) kJ mol(-1)/RTln10 Additionally, pressure-dependent rate coefficients for the reaction of SiH2 with 2-butyne in the presence of He (1-100 Torr) were obtained at 301, 429 and 613 K. Quantum chemical (ab initio) calculations of the SiC4H8 reaction system at the G3 level support the formation of 2,3-dimethylsilirene [cyclo-SiH2C(CH3)=C(CH3)-] as the sole end product. However, reversible formation of 2,3-dimethylvinylsilylene [CH3CH=C(CH3)SiH] is also an important process. The calculations also indicate the probable involvement of several other intermediates, and possible products. RRKM calculations are in reasonable agreement with the pressure dependences at an enthalpy value for 2,3-dimethylsilirene fairly close to that suggested by the ab initio calculations. The experimental isotope effects deviate significantly from those predicted by RRKM theory. The differences can be explained by an isotopic scrambling mechanism, involving H - D exchange between the hydrogens of the methyl groups and the D-atoms in the ring in 2,3-dimethylsilirene-1,1-d(2). A detailed mechanism involving several intermediate species, which is consistent with the G3 energy surface, is proposed to account for this.

A new method for multipath channel characterisation for terrestrial transmitted video

Under the multipath conditions of terrestrial television transmission, ghost carriers cause additive information to be generated by the VSB filter within the television receiver. By analysis of this a priori effect of the VSB filter under a ghosted condition the inphase and phase quadrature detected video signals are defined. Derived from these results, a new algorithm based upon correlation techniques is presented which finds the characteristics of the amplitude and delay of individual ghosts. These characteristics are then passed to a deterministic deghoster to minimise ghost effects.

Deposition of charged inhaled aerosols with transient airflow in sequential lung airway model

Transport and deposition of charged inhaled aerosols in double planar bifurcation representing generation three to five of human respiratory system has been studied under a light activity breathing condition. Both steady and oscillatory laminar inhalation airflow is considered. Particle trajectories are calculated using a Lagrangian reference frame, which is dominated by the fluid force driven by airflow, gravity force and electrostatic forces (both of space and image charge forces). The particle-mesh method is selected to calculate the space charge force. This numerical study investigates the deposition efficiency in the three-dimensional model under various particle sizes, charge values, and inlet particle distribution. Numerical results indicate that particles carrying an adequate level of charge can improve deposition efficiency in the airway model.

Cooperative task support for the control room

The National Grid Company plc. owns and operates the electricity transmission network in England and Wales, the day to day running of the network being carried out by teams of engineers within the national control room. The task of monitoring and operating the transmission network involves the transfer of large amounts of data and a high degree of cooperation between these engineers. The purpose of the research detailed in this paper is to investigate the use of interfacing techniques within the control room scenario, in particular, the development of an agent based architecture for the support of cooperative tasks. The proposed architecture revolves around the use of interface and user supervisor agents. Primarily, these agents are responsible for the flow of information to and from individual users and user groups. The agents are also responsible for tackling the synchronisation and control issues arising during the completion of cooperative tasks. In this paper a novel approach to human computer interaction (HCI) for power systems incorporating an embedded agent infrastructure is presented. The agent architectures used to form the base of the cooperative task support system are discussed, as is the nature of the support system and tasks it is intended to support.

Rheology of milk foams produced by steam injection

Rheology of milk foams generated by steam injection was studied during the transient destabilization process using steady flow and dynamic oscillatory techniques: yield stress (τ_y) values were obtained from a stress ramp (0.2 to 25 Pa) and from strain amplitude sweep (0.001 to 3 at 1 Hz of frequency); elastic (G') and viscous (G") moduli were measured by frequency sweep (0.1 to 150 Hz at 0.05 of strain); and the apparent viscosity (η_a) was obtained from the flow curves generated from the stress ramp. The effect of plate roughness and the sweep time on τ_y was also assessed. Yield stress was found to increase with plate roughness whereas it decreased with the sweep time. The values of yield stress and moduli—G' and G"—increased during foam destabilization as a consequence of the changes in foam properties, especially the gas volume fraction, φ, and bubble size, R_32 (Sauter mean bubble radius). Thus, a relationship between τ_y, φ, R_32, and σ (surface tension) was established. The changes in the apparent viscosity, η, showed that the foams behaved like a shear thinning fluid beyond the yield point, fitting the modified Cross model with the relaxation time parameter (λ) also depending on the gas volume fraction. Overall, it was concluded that the viscoelastic behavior of the foam below the yield point and liquid-like behavior thereafter both vary during destabilization due to changes in the foam characteristics.

Numerical-asymptotic boundary integral methods in high-frequency acoustic scattering

In this article we describe recent progress on the design, analysis and implementation of hybrid numerical-asymptotic boundary integral methods for boundary value problems for the Helmholtz equation that model time harmonic acoustic wave scattering in domains exterior to impenetrable obstacles. These hybrid methods combine conventional piecewise polynomial approximations with high-frequency asymptotics to build basis functions suitable for representing the oscillatory solutions. They have the potential to solve scattering problems accurately in a computation time that is (almost) independent of frequency and this has been realized for many model problems. The design and analysis of this class of methods requires new results on the analysis and numerical analysis of highly oscillatory boundary integral operators and on the high-frequency asymptotics of scattering problems. The implementation requires the development of appropriate quadrature rules for highly oscillatory integrals. This article contains a historical account of the development of this currently very active field, a detailed account of recent progress and, in addition, a number of original research results on the design, analysis and implementation of these methods.

Effect of high-hydrostatic pressure and pH on the rheological properties of gum arabic

The effect on the viscoelastic behaviour, of pressure-treating hydrated gumarabic samples (800 MPa) at different pH values (2.8, 4.2 and 8.0) was investigated, using controlled stress rheometry. The treated samples were analysed for their complex (G∗), storage (G′) and loss (G″) moduli as a function of frequency, using dynamic oscillatory testing. Significant changes in the rheologicalproperties were observed in both the pressurised gum solutions and in those previously buffered at pH 2.8. The gum, at its natural pH (4.25) and at alkaline pH (8.0), was enhanced by pressure treatment, but only for the already “good” quality gum samples. High-pressure treatment had substantial effects on the frequency-dependence of the moduli of both the pressurised and the pressurised/pH-treated solutions, with the latter being more pronounced, suggesting differing structures or changes in the overall degree of interaction of the gum systems after pressure treatment.

Occasional publishers: producing and marketing books in England 1771–1844

Purpose – To investigate the way in which a series of related printing businesses, owned by members of the Gye and Balne families in Bath and London from 1771 to 1844, selected and marketed their titles when they ventured into book printing and publishing. Design/methodology/approach – The basis of this research is extensive archival research analyzing primary sources, mainly the books and ephemera printed by the various firms, supported by information in contemporary newspapers and journals and in biographies of printers and publishers. Findings – The focus of these businesses was not solely on production but that marketing was also considered, and that there was each title was conceived and produced with a particular market in mind. In doing so it provides evidence of relatively advanced marketing strategies in use before 1850 and thus questions the validity of the four-eras model of marketing history. Research limitations/implications – The available primary sources are limited; while a number of books and other printed items have survived there are no extant accounts, correspondence, or other records for any of the firms that were studied. Originality/value – There has been very little research into the way small businesses during this period approached the marketing of their products. This paper is a potential model for further such historical research and also provides an example of how research into specific companies can illuminate the larger history of marketing, potentially changing the way in which we understand the development of consumer society.

Drag produced by trapped lee waves and propagating mountain waves in a two-layer atmosphere

The surface drag force produced by trapped lee waves and upward propagating waves in non-hydrostatic stratified flow over a mountain ridge is explicitly calculated using linear theory for a two-layer atmosphere with piecewise-constant static stability and wind speed profiles. The behaviour of the drag normalized by its hydrostatic single-layer reference value is investigated as a function of the ratio of the Scorer parameters in the two layers l_2/l_1 and of the corresponding dimensionless interface height l_1 H, for selected values of the dimensionless ridge width l_1 a and ratio of wind speeds in the two layers. When l_2/l_1 → 1, the propagating wave drag approaches 1 in approximately hydrostatic conditions, and the trapped lee wave drag vanishes. As l_2/l_1 decreases, the propagating wave drag progressively displays an oscillatory behaviour with l_1 H, with maxima of increasing magnitude due to constructive interference of reflected waves in the lower layer. The trapped lee wave drag shows localized maxima associated with each resonant trapped lee wave mode, occurring for small l_2/l_1 and slightly higher values of l_1 H than the propagating wave drag maxima. As l1a decreases, i.e. the flow becomes more non-hydrostatic, the propagating wave drag decreases and the regions of non-zero trapped lee wave drag extend to higher l_2/l_1. These results are confirmed by numerical simulations for l_2/l_1 = 0.2. In parameter ranges of meteorological relevance, the trapped lee wave drag may have a magnitude comparable to that of propagating wave drag, and be larger than the reference single-layer drag. This may have implications for drag parametrization in global climate and weather-prediction models.

The potential to intensify sulforaphane formation in cooked broccoli (Brassica oleracea var. italica) using mustard seeds (Sinapis alba)

Sulforaphane, a naturally occurring cancer chemopreventive, is the hydrolysis product of glucoraphanin, the main glucosinolate in broccoli. The hydrolysis requires myrosinase isoenzyme to be present in sufficient activity; however processing leads to its denaturation and hence reduced hydrolysis. In this study, the effect of adding mustard seeds, which has a more resilient isoform of myrosinase, to processed broccoli was investigated with a view to intensify the formation of sulforaphane. Thermal inactivation of myrosinase from both broccoli and mustard seeds was studied. Thermal degradation of broccoli glucoraphanin was investigated in addition to the effects of thermal processing on the formation of sulforaphane and sulforaphane nitrile. Limited thermal degradation of glucoraphanin (less than 12 %) was observed when broccoli was placed in vacuum sealed bag (sous vide) and cooked in a water bath at 100 ºC for 8 and 12 min. Boiling broccoli in water prevented the formation of any significant levels of sulforaphane due to inactivated myrosinase. However, addition of powdered mustard seeds to the heat processed broccoli significantly increased the formation of sulforaphane.

A mechanism for Atlantic multidecadal variability in the Kiel Climate Model

Atlantic Multidecadal Variability (AMV) is investigated in a millennial control simulation with the Kiel Climate Model (KCM), a coupled atmosphere–ocean–sea ice model. An oscillatory mode with approximately 60 years period and characteristics similar to observations is identified with the aid of three-dimensional temperature and salinity joint empirical orthogonal function analysis. The mode explains 30 % of variability on centennial and shorter timescales in the upper 2,000 m of the North Atlantic. It is associated with changes in the Atlantic Meridional Overturning Circulation (AMOC) of ±1–2 Sv and Atlantic Sea Surface Temperature (SST) of ±0.2 °C. AMV in KCM results from an out-of-phase interaction between horizontal and vertical ocean circulation, coupled through Irminger Sea convection. Wintertime convection in this region is mainly controlled by salinity anomalies transported by the Subpolar Gyre (SPG). Increased (decreased) dense water formation in this region leads to a stronger (weaker) AMOC after 15 years, and this in turn leads to a weaker (stronger) SPG after another 15 years. The key role of salinity variations in the subpolar North Atlantic for AMV is confirmed in a 1,000 year long simulation with salinity restored to model climatology: No low frequency variations in convection are simulated, and the 60 year mode of variability is absent.

Time-resolved gas-phase kinetic, quantum chemical, and RRKM studies of reactions of silylene with alcohols

Time-resolved kinetic studies of silylene, SiH2, generated by laser flash photolysis of 1-silacyclopent-3-ene and phenylsilane, have been carried out to obtain rate constants for its bimolecular reactions with methanol, ethanol, 1-propanol, 1-butanol and 2-methyl-1-butanol. The reactions were studied in the gas phase over the pressure range 1-100 Torr in SF6 bath gas, at room temperature. In the study with methanol several buffer gases were used. All five reactions showed pressure dependences characteristic of third body assisted association reactions. The rate constant pressure dependences were modelled using RRKM theory, based on Eo values of the association complexes obtained by ab initio calculation (G3 level). Transition state models were adjusted to fit experimental fall-off curves and extrapolated to obtain k∞ values in the range 1.9 to 4.5 × 10-10 cm3 molecule-1 s-1. These numbers, corresponding to the true bimolecular rate constants, indicate efficiencies of between 16 and 67% of the collision rates for these reactions. In the reaction of SiH2 + MeOH there is a small kinetic component to the rate which is second order in MeOH (at low total pressures). This suggests an additional catalysed reaction pathway, which is supported by the ab initio calculations. These calculations have been used to define specific MeOH-for-H2O substitution effects on this catalytic pathway. Where possible our experimental and theoretical results are compared with those of previous studies.