Reactivity of Cationic Terminal Borylene Complexes: Novel Mechanisms for Insertion and Metathesis Chemistry Involving Strongly Lewis Acidic Ligand Systems

The reactions of terminal borylene complexes of the type [CpFe(CO)(2)(BNR2)](+) (R = `Pr, Cy) with heteroallenes have been investigated by quantum-chemical methods, in an attempt to explain the experimentally observed product distributions. Reaction with dicyclohexylcarbodiimide (CyNCNCy) gives a bis-insertion product, in which 1 equiv of carbodiimide is assimilated into each of the Fe=B and B=N double bonds to form a spirocyclic boronium system. In contrast, isocyanates (R'NCO, R' = Ph, 2,6-wXy1, CY; XYl = C6H3Me2) react to give isonitrile complexes of the type [CpFe(CO)(2)(CNR')]+, via a net oxygen abstraction (or formal metathesis) process. Both carbodiimide and socyanate substrates are shown to prefer initial attack at the Fe=B bond rather than the B=N bond of the borylene complex. Further mechanistic studies reveal that the carbodiimide reaction ultimately leads to the bis-insertion compounds [CpFe(CO)(2)C(NCy)(2)B(NCY)(2)CNR2](+), rather than to the isonitrile system [CpFe(CO)(2)(CNCy)](+), on the basis of both thermodynamic (product stability) and kinetic considerations (barrier heights). The mechanism of the initial carbodiimide insertion process is unusual in that it involves coordination of the substrate at the (borylene) ligand followed by migration of the metal fragment, rather than a more conventional process: i.e., coordination of the unsaturated substrate at the metal followed by ligand migration. In the case of isocyanate substrates, metathesis products are competitive with those from the insertion pathway. Direct, single-step metathesis reactivity to give products containing a coordinated isonitrile ligand (i.e. [CpFe(CO)(2)(CNR')](+)) is facile if initial coordination of the isocyanate at boron occurs via the oxygen donor (which is kinetically favored); insertion chemistry is feasible when the isocyanate attacks initially via the nitrogen atom. However, even in the latter case, further reaction of the monoinsertion product so formed with excess isocyanate offers a number of facile (low energetic barrier) routes which also generate ['CpFe(CO)(2)(CNR')](+), rather than the bis-insertion product [CpFe(CO)(2)C(NR')(O)B(NR')(O)CNR2](+) (i.e., the direct analogue of the observed products in the carbodiimide reaction).

Instabilities induced by variation of Brunt-Vaisala frequency in compressible stratified shear flows

The stability characteristics of a Helmholtz velocity profile in a stably stratified, compressible fluid in the presence of a lower rigid boundary are studied. A jump in the Brunt-Vaisala frequency at a level different from the shear zone is introduced and the variation of the Brunt-Vaisala frequency with respect to the vertical coordinate in the middle layer of the three-layered model is considered. An analytic solution in each of the layers is obtained, and the dispersion relation is solved numerically for parameters relevant to the model. The effect of shear in the lowermost layer of the three-layered model for a Boussinesq fluid is discussed. The results are compared with the earlier studies of Lindzen and Rosenthal, and Sachdev and Satya Narayanan. In the present model, new unstable modes with larger growth rates are obtained and the most unstable gravity wave modes are found to agree closely with the observed ones at various heights. Physics of Fluids is copyrighted by The American Institute of Physics.

Stability of Slopes by Method of Characteristics

The method of characteristics with some simplifying assumptions is made applicable for analyzing a given straight slope. By assuming that the mobilized shear strength varies with depth, and treating the whole soil mass as a series of layers, factors of safety of a given slope at different heights and a series of lines with different mobilized shear strength are obtained. The results show that the factors of safety obtained by the present method are lower than those obtained by friction circle method.

Conformation And C-N Rotational Barrier Of Dithiocarbamate Esters Nmr And Molecular-Orbital Studies

The variable temperature proton and ambient temperature carbon-13 NMR spectra of S-methyl dithiocarbamate esters have been recorded. The results of the theoretical energy calculations (CNDO/2 and EHT types) together with the experimental data have been interpreted in terms of the molecular conformations. The barrier heights for the rotation about the thioamide C—N bond are calculated using the CNDO/2 method and the results are discussed in terms of the computed charge densities and bond orders.

Experimental investigation of cowl shape and location on inlet characteristics at hypersonic Mach number

An experimental study is presented to show the effect of the cowl location and shape on the shock interaction phenomena in the inlet region for a 2D, planar scramjet inlet model. Investigations include schlieren visualization around the cowl region and heat transfer rate measurement inside the inlet chamber.Both regular and Mach reflections are observed when the forebody ramp shock reflects from the cowl plate. Mach stem heights of 3.3 mm and 4.1 mm are measured in 18.5 mm and 22.7 mm high inlet chambers respecively. Increased heat transfer rate is measured at the same location of chamber for cowls of longer lenghs is indicating additional mass flow recovery by the inlet.

Investigations of separated flow over backward facing steps in IISc hypersonic shock tunnel

Two backward facing step (2 mm and 3 mm step height) models are selected for surface heat transfer measurements. The platinum thin film gauges are deposited on the Macor inserts using both hand paint and vacuum sputtering technique. Using the Eckert reference temperature method the heating rates has been theoretically calculated along the flat plate portion of the model and the theoretical estimates are compared with experimentally determined surface heat transfer rate. Theoretical analysis of heat flux distribution down stream of the backward facing step model has been carried out using Gai’s non-dimensional analysis. Based on the measured surface heating rates on the backward facing step, the reattachment distance is estimated for 2 and 3 mm step height at nominal Mach number of 7.6. It has been found from the present study that for 2 and 3 mm step height, it approximately takes about 10 and 8 step heights downstream of the model respectively for the flow to re-attach.

Vertical distribution of aerosols over the east coast of India inferred from airborne LIDAR measurements

The information on altitude distribution of aerosols in the atmosphere is essential in assessing the impact of aerosol warming on thermal structure and stability of the atmosphere.In addition, aerosol altitude distribution is needed to address complex problems such as the radiative interaction of aerosols in the presence of clouds. With this objective,an extensive, multi-institutional and multi-platform field experiment (ICARB-Integrated Campaign for Aerosols, gases and Radiation Budget) was carried out under the Geosphere Biosphere Programme of the Indian Space Research Organization (ISRO-GBP) over continental India and adjoining oceans during March to May 2006. Here, we present airborne LIDAR measurements carried out over the east Coast of the India during the ICARB field campaign. An increase in aerosol extinction (scattering + absorption) was observed from the surface upwards with a maximum around 2 to 4 km. Aerosol extinction at higher atmospheric layers (>2 km) was two to three times larger compared to that of the surface. A large fraction (75-85%) of aerosol column optical depth was contributed by aerosols located above 1 km. The aerosol layer heights (defined in this paper as the height at which the gradient in extinction coefficient changes sign) showed a gradual decrease with an increase in the offshore distance. A large fraction (60-75%) of aerosol was found located above clouds indicating enhanced aerosol absorption above clouds. Our study implies that a detailed statistical evaluation of the temporal frequency and spatial extent of elevated aerosol layers is necessary to assess their significance to the climate. This is feasible using data from space-borne lidars such as CALIPSO,which fly in formation with other satellites like MODIS AQUA and MISR, as part of the A-Train constellation.

Bat foraging strategies and pollination of Madhuca latifolia (Sapotaceae) in southern India

The sympatrically occurring Indian short-nosed fruit bat Cynopterus sphinx and Indian flying fox Pteropus giganteus visit Madhuca latifolia (Sapotaceae), which offers fleshy corollas (approximate to 300 mg) to pollinating bats. The flowers are white, tiny and in dense fascicles The foraging activities of the two bat species were segregated in space and time. Cynopterus sphinx fed on resources at lower heights in the trees than P giganteus and its peak foraging activity occurred at 19 30 h, before that of P giganteus Foraging activities involved short searching flights followed by landing and removal of the corolla by mouth Cynopterus sphinx detached single corollas from fascicles and carried them to nearby feeding roosts, where it sucked the juice and spat out the Fibrous remains Pteropus giganteus landed on top of the trees and fed on the corollas in situ, its peak activity occurred at 20 30 11 This species glided and crawled between the branches and held the branches with claws and forearms when removing fleshy corollas with Its Mouth Both C sphinx and P giganteus consumed fleshy corollas with attached stamens and left the gynoecium intact Bagging experiments showed that fruit-set in bat-visited flowers was significantly higher (P < 0.001) than in self-pollinated flowers.

Prediction of flame liftoff height of diffusion/partially premixed jet flames and modeling of mild combustion burners

In this article, a new flame extinction model based on the k/epsilon turbulence time scale concept is proposed to predict the flame liftoff heights over a wide range of coflow temperature and O-2 mass fraction of the coflow. The flame is assumed to be quenched, when the fluid time scale is less than the chemical time scale ( Da < 1). The chemical time scale is derived as a function of temperature, oxidizer mass fraction, fuel dilution, velocity of the jet and fuel type. The present extinction model has been tested for a variety of conditions: ( a) ambient coflow conditions ( 1 atm and 300 K) for propane, methane and hydrogen jet flames, ( b) highly preheated coflow, and ( c) high temperature and low oxidizer concentration coflow. Predicted flame liftoff heights of jet diffusion and partially premixed flames are in excellent agreement with the experimental data for all the simulated conditions and fuels. It is observed that flame stabilization occurs at a point near the stoichiometric mixture fraction surface, where the local flow velocity is equal to the local flame propagation speed. The present method is used to determine the chemical time scale for the conditions existing in the mild/ flameless combustion burners investigated by the authors earlier. This model has successfully predicted the initial premixing of the fuel with combustion products before the combustion reaction initiates. It has been inferred from these numerical simulations that fuel injection is followed by intense premixing with hot combustion products in the primary zone and combustion reaction follows further downstream. Reaction rate contours suggest that reaction takes place over a large volume and the magnitude of the combustion reaction is lower compared to the conventional combustion mode. The appearance of attached flames in the mild combustion burners at low thermal inputs is also predicted, which is due to lower average jet velocity and larger residence times in the near injection zone.

Compliance of rough cylinders in compression

Compression of a rough turned cylinder between two hard, smooth, flat plates has been analysed with the aid of a mathematical model based on statistical analysis. It is assumed that the asperity peak heights follow Gaussian or normal and beta distribution functions and that the loaded asperities comply as though they are completely isolated from the neighbouring ones. Equations have been developed for the loadcompliance relation of the real surface using a simplified relation of the form W0 = K1δn for the load-compliance of a single asperity. Parameters K1 and n have considerable influence on the load-compliance curve and they depend on the material, tip angle of the asperity, standard deviation of the asperity peak height distribution and the density of the asperities.

A multi-station satellite radio beacon study of ionospheric variations during total solar eclipses

Faraday rotation data obtained at Delhi, Kurukshetra, Hyderabad, Bangalore, Waltair, Nagpur and Calcutta during the total solar eclipse of 16 February 1980 and at Delhi during the total solar eclipse of 31 July 1981 have been analysed to detect the gravity waves generated by a total solar eclipse as hypothesized by Chimonas and Hines (1970, J. geophys. Res. 75, 875). It has been found that gravity waves can be generated by a total solar eclipse but their detection at ionospheric heights is critically dependent on the location of the observing station in relation to the eclipse path geometry. The distance of the observing station from the eclipse path should be more than 500 km in order to detect such gravity waves.

Shell-model calculation of defect energies in alkali halides employing crystal-independent interionic potential parameters

Shell model calculation of defect energies in alkali halides have been carried out using the ion-dependent, crystal-independent potential parameters of Sangster and Atwood (1978). Results indicate that appreciable differences exist between barrier heights for migration of cations and anions. While barrier heights for cations are generally lower than for anions in alkali halides of NaCl structure, the opposite is true in alkali halides of CsCl structure.

Flow structure and heat transfer characteristics behind a diaphragm in the presence of a diffusion flame

The characteristics of the separated flow behind a diaphragm over a burning surface are investigated experimentally. This complex problem of practical significance involving recirculation, blowing and combustion reactions is studied in a two-dimensional combustion tunnel. The flame structure, recirculation patterns and heat transfer to the surface are presented for a range of values of free stream and fuel injection velocities as well as for different heights of the diaphragm. The trends of heat transfer vs axial distance are shown to be similar to those resulting from a non-reactive heated stream with a diaphragm. Treating the case of a boundary layer diffusion flame as that corresponding to the zero height of the diaphragm, the heat transfer augmentation due to recirculation is estimated. It is found that at considerable downstream distances (xfh > 3), the heat transfer rates with diaphragm overtake the rates from a developing boundary layer case. Flow visualization studies with particle track photography show that there are many similarities between the reactive and the non-reactive cases.

Boundary-layer heights over the monsoon trough region during active and break phases

The thermodynamic structure and the heights of the boundary layer over the monsoon trough region of the Indian southwest monsoon are presented for the active and break phases of the monsoon. Results indicate significant and consistent variation in boundary-layer heights between the active and break phases.

A Theory of the Lifted Temperature Minimum on Calm Clear Nights

Numerous reports from several parts of the world have confirmed that on calm clear nights a minimum in air temperature can occur just above ground, at heights of the order of $\frac{1}{2}$ m or less. This phenomenon, first observed by Ramdas & Atmanathan (1932), carries the associated paradox of an apparently unstable layer that sustains itself for several hours, and has not so far been satisfactorily explained. We formulate here a theory that considers energy balance between radiation, conduction and free or forced convection in humid air, with surface temperature, humidity and wind incorporated into an appropriate mathematical model as parameters. A complete numerical solution of the coupled air-soil problem is used to validate an approach that specifies the surface temperature boundary condition through a cooling rate parameter. Utilizing a flux-emissivity scheme for computing radiative transfer, the model is numerically solved for various values of turbulent friction velocity. It is shown that a lifted minimum is predicted by the model for values of ground emissivity not too close to unity, and for sufficiently low surface cooling rates and eddy transport. Agreement with observation for reasonable values of the parameters is demonstrated. A heuristic argument is offered to show that radiation substantially increases the critical Rayleigh number for convection, thus circumventing or weakening Rayleigh-Benard instability. The model highlights the key role played by two parameters generally ignored in explanations of the phenomenon, namely surface emissivity and soil thermal conductivity, and shows that it is unnecessary to invoke the presence of such particulate constituents as haze to produce a lifted minimum.