Temperature-programmed desorption and surface reaction of thiophene over co-mo/.gamma.-Al2O3 hydrodesulfurization catalysts

The temperature-programmed desorption (TPD) and temperature-programmed surface reaction (TPSR) of thiophene over a series of Co-Mo/gamma-Al2O3, hydrodesulfurization (HDS) catalysts with varying Co to Mo ratios have been studied with the objective of understanding the promotional role of Co in the HDS reaction. As part of the study, the desorptions (TPD) and hydrogenations (TPSR) of butane, butene, and butadiene over these catalysts have also been investigated. The TPD of the hydrocarbons over catalysts containing no Co showed a single desorption profile while incorporation of Co created an additional site, with higher heats of desorption, without significantly affecting desorption from the original site. The TPSR measurements showed that the two sites had separate and independent activity for the hydrogenation of the C-4 hydrocarbons. The TPD of thiophene over catalysts with varying Co to Mo ratios showed a single desorption profile with identical heats of desorption, implying that Co does not affect or influence the adsorption sites for thiophene. The TPSR of the HDS of thiophene, however, showed that, although the products of the HDS reaction-butane, butene, and H2S-are the same irrespective of the Co content, the temperature profiles and the activation barriers for the formation of these species show considerable change with the Co/Co+Mo ratio. The results are discussed in light of the existing models for the promotional role of Co in the HDS reaction.

A study of over-reflection in Hartmann flow

It is observed that Hartmann flow sustains wave propagation in its centre region for waves whose phase speed is less than the maximum flow speed. Similar to the previous observations it is found that viscous boundary layers around the critical level and at the wall replace the exponential regions and wave sinks required for over-reflection in the inviscid flow. The uniform magnetic field stabilizes the flow for small-wave-number disturbances along thez-direction. Over-reflection is confined to a few ranges of phase speeds for which the two boundary layers are close together rather than widely separated. These ranges correspond exactly to those for which unstable eigenmodes exist. Over-reflection is associated with a wave phase tilt opposite in direction to the shear.

Wind loading over the top portions of tall stacks with and without external landing platforms

The variation of the drag force near the top portions of tall stacks with and without external landing platforms, and with the exit open and closed, has been examined by model studies in a wind tunnel at Reynolds numbers of about 10(5). Pressure measurements on three models of different height to diameter ratios have been supplemented by flow visualisation studies. Observations confirm that when there is no platform, significant load enhancement over the top three to four diameters occurs, due to the high suction caused by the sharp separation of the flow over the top from the rim, in the aft regions of the stack. The enhanced loading is found to be greater if the exit is closed. A platform at the top, of less than twice the exit diameter, further increases the drag force near the top, but a still larger platform at the top, of about three times the exit diameter, decreases the drag force to values less than those much further below, effectively nullifying the enhanced drag force. It was found that such a reduction of the enhanced drag force in the top regions can also be achieved by a smaller platform of 1.1 to 1.3 times the local diameter, located at about three to five diameters below the top.

Methanation of CO2 over Ru?SiO2 catalyst

Using Ru - SiO2 catalyst, the kinetics of methanation of carbon dioxide has been studied. In the temperature range of 320-460-degrees-C a simple power law model is found to predict experimental results with a good agreement over the range of variables studied.

Methanol-to-gasoline (MTG) conversion over ZSM-5. A temperature programmed surface reaction study

The conversion of methanol to gasoline over zeolite ZSM-5 has been studied by temperature programmed surface reaction (TPSR). The technique is able to monitor the two steps in the process: the dehydration of methanol to dimethyl ether and the subsequent conversion of dimethyl ether to hydrocarbons. The activation barriers associated with each step were evaluated from the TPSR profiles and are 25.7 and 46.5 kcal/mol respectively. The methanol desorption profile shows considerable change with the amount of methanol molecules adsorbed per Bronsted site of the zeolite. The energy associated with the desorption process, (CH3OHH+-ZSM5 --> (CH3OHH+-ZSM5 + CH3OH, shows a spectrum of values depending on n.

Study of transpiration cooling over a flat plate at hypersonic Mach numbers

Transpiration cooling over a flat plate at hypersonic Mach numbers is analyzed using Navier-Stokes equations, without the assumption of an isothermal wall with a prescribed wall temperature. A new criterion is proposed for determining a relevant range of blowing rates, which is useful in the parametric analysis. The wall temperature is found to decrease with the increasing blowing rate, but this effect is not uniform along the plate. The effect is more pronounced away from the leading edge. The relative change in the wall temperature is affected stronger by blowing at high Reynolds numbers. (AIAA)

Turbulent heat flux variation over the Monsoon-Trough region during MONTBLEX-90

Tower data collected during the Monsoon-Trough Boundary Layer Experiment (MONTBLEX-90) have been analysed to understand the observed structure of the surface layer over an arid region (Jodhpur) and a moist region (Kharagpur) during active and weak phases of the 1990 southwest monsoon. Turbulent heat and momentum fluxes are estimated by the eddy correlation method using sonic data. The turbulent momentum flux at both Jodhpur and Kharagpur was larger when the winds were stronger, reaching a maximum of the order of 0.5 N m(-2) on 5 and 6 August when a low pressure system was located over the region. The heat flux at Jodhpur is high during weak monsoon days, the maximum being 450 W m(-2), whereas during active days the flux never exceeds 200 W m(-2). At Kharagpur, the flux does not vary significantly between active and weak monsoon days, the maximum in either phase being 160 W m(-2) At Jodhpur, there is significant contrast in the near-surface air temperature, being higher during weak monsoon days as compared to active days. Cloud cover did not vary significantly in both the regions. The turbulent heat flux variation at both the sites appears to be correlated mainly with soil mixture, and less sensitive to cloud cover.

Vesicle formation from dimeric surfactants through ion-pairing. Adjustment of polar headgroup separation leads to control over vesicular thermotropic properties

Eight new vesicle-forming dimeric surfactants are synthesized: the polar headgroup separation in such dimeric amphiphiles strongly influences their vesicular thermotropic phase-transition behaviour.

Covalent Grafting of Polydimethylsiloxane over Surface-Modified Alumina Nanoparticles

The synthesis of ``smart structured'' conducting polymers and the fabrication of devices using them are important areas of research. However, conducting polymeric materials that are used in devices are susceptible to degradation due to oxygen and moisture. Thus, protection of such devices to ensure long-term stability is always desirable. Polymer nanocomposites are promising materials for the encapsulation of such devices. Therefore, it is important to develop suitable polymer nanocomposites as encapsulation materials to protect such devices. This work presents a technique based on grafting between surface-decorated gamma-alumina nanoparticles and polymer to make nanocomposites that can be used for the encapsulation of devices. Alumina was functionalized with allyltrimethoxysilane and used to conjugate polymer molecules (hydride-terminated polydimethylsiloxane) through a platinum-catalyzed hydrosilylation reaction. Fourier transform infrared spectroscopy, X-ray-photoelectron spectroscopy, and Raman spectroscopy were used to characterize the surface chemistry of the nanoparticles after surface modification. The grafting density of alkene groups on the surface of the modified nanoparticles was calculated using CHN and thermogravimetric analyses. The thermal stability of the composites was also evaluated using thermogravimetric analysis. The nanoindentation technique was used to analyze the mechanical characteristics of the composites. The densities of the composites were evaluated using a density gradient column, and the morphology of the composites was evaluated by scanning electron microscopy. All of our studies reveal that the composites have good thermal stability and mechanical flexibility and, thus, can potentially be used for the encapsulation of organic photovoltaic devices.

Airborne measurements of aerosol scattering properties above the MABL over Bay of Bengal during W_ICARB - characteristics and spatial gradients

Realizing the importance of aerosol characterization and addressing its spatio-temporal heterogeneities over Bay of Bengal (BoB), campaign mode observations of aerosol parameters were carried out using simultaneous cruise, aircraft and land-based measurements during the Winter Integrated Campaign for Aerosols gases and Radiation Budget (W_ICARB). Under this, airborne measurements of total and hemispheric backscatter coefficients were made over several regions of coastal India and eastern BoB using a three wavelength integrating nephelometer. The measurements include high resolution multi-level (ML) sorties for altitude profiles and bi-level (BL) sorties for spatial gradients within and above the Marine Atmospheric Boundary Layer (MABL) over BoB. The vertical profiles of the scattering coefficients are investigated in light of the information on the vertical structure of the atmospheric stability, which was derived from the collocated GPS (Global Positioning System) aided radiosonde ascents. In general, the altitude profiles revealed that the scattering coefficient remained steady in the convectively well-mixed regions and dropped off above the MABL. This decrease was quite rapid off the Indian mainland, while it was more gradual in the eastern BoB. Investigation on horizontal gradients revealed that the scattering coefficients over northern BoB are 3 to 4 times higher compared to that of central BoB within and above the MABL. A north-south gradient in scattering coefficients is observed over Port Blair in the eastern BoB, with values decreasing from south to north, which is attributed to the similar gradient in the surface wind speed, which can be replicated in the sea salt abundance. The gradients are parameterized using best-fit analytical functions.

Latitude variation of boundary layer height over Indian Ocean during pre- and First Field Phase (FFP-98) of INDOEX

This paper describes the results of the measurement of the Marine Boundary Layer (MBL) height from spectral analysis of the u and v components of the wind and from CLASS/radiosonde temperature profiles. The data were collected on ORV Sagar Kanya during the pre-INDOEX (27 December 1996 through 31 January 1997) and FFP-98 (18 February to 31 March 1998) over the latitude range 15 degrees N to 14 degrees S and 15 degrees N to 20 degrees S respectively. During the pre-INDOEX, the MBL heights gradually decrease from 2.5 km at 13 degrees N to around 500 to 600 m at 10 degrees S, Similar results are observed in the return track. The MBL heights (0.5 to 1 km) obtained during FFP-98 are less compared to those obtained during pre-INDOEX. The MBL heights during FFP-98 are less compared to the pre-INDOEX and are believed to be due to the presence of stratus, stratocumulus and cumulus clouds during the cruise period, compared to a relatively cloud free pre-INDOEX cruise.

Levitation of a drop over a film flow

A vertical jet of water impinging on a horizontal surface produces a radial film flow followed by a circular hydraulic jump. We report a phenomenon where fairly large (1 mi) drops of liquid levitate just upstream of the jump on a thin air layer between the drop and the film flow. We explain the phenomenon using lubrication theory. Bearing action both in the air film and the water film seems to be necessary to support large drops. Horizontal support is given to the drop by the hydraulic jump. A variety of drop shapes is observed depending on the volume of the drop and liquid properties. We show that interaction of the forces due to gravity, surface tension, viscosity and inertia produces these various shapes.

Vesicle formation from dimeric ion-paired amphiphiles. Control over vesicular thermotropic and ion-transport properties as a function of intra-amphiphilic headgroup separation

A novel series of vesicle-forming ion-paired amphiphiles, bis(hexadecyldimethylammonium)alkane dipalmitate (1a-1h), containing four chains were synthesized with two isolated headgroups. In each of these amphiphiles, the two headgroup charges are separated by a flexible polymethylene spacer chain -[(CH2)(m)]- of varying lengths (m) such that the length and the conformation of the spacer chain determine the intra-"monomer" headgroup separation. Transmission electron microscopy indicated that each of these forms bilayer membranes upon dispersion in aqueous media. The vesicular properties of these aggregates have been examined by differential scanning calorimetry and temperature-dependent fluorescence anisotropy measurements. Interestingly, their T-m values decreased with the increase in the m value. Thus while the apparent T-m of the lipid with m = 2 (1a) is 74.1 degrees C, the corresponding value observed for the lipid with m = 12 (1h) is 38.9 degrees C. The fluorescence anisotropy values (r) for 1b-1g were quite high (r similar to 0.3) compared to that of 1h (r similar to 0.23) at 20-30 degrees C in their gel states. On the other hand, the r value for vesicular 1b beyond melting was higher (0.1) compared to any of those for 1c-1h (similar to 0.04-0.06). X-ray diffraction of the cast films was performed to understand the nature and the thickness of these membrane organizations. The membrane widths ranged from 30 to 51 A as the m values varied. The entrapment of a small water-soluble solute, riboflavin, by the individual vesicular aggregates, and their sustenance: under an imposed transmembrane pH gradient have also been examined. These results show that all lipid vesicles entrap riboflavin and that generally the resistance to OH- permeation decreases with the increase in m value. Finally,all the above observations were comparatively analyzed, and on the basis of the calculated structures of these lipids, it was possible to conclude that membrane propel-ties can be modulated by spacer chain length variation of the ion-paired amphiphiles.

Aerosol radiative forcing over land: effect of surface and cloud reflection

It is now clearly understood that atmospheric aerosols have a significant impact on climate due to their important role in modifying the incoming solar and outgoing infrared radiation. The question of whether aerosol cools (negative forcing) or warms (positive forcing) the planet depends on the relative dominance of absorbing aerosols. Recent investigations over the tropical Indian Ocean have shown that, irrespective of the comparatively small percentage contribution in optical depth (similar to11%), soot has an important role in the overall radiative forcing. However, when the amount of absorbing aerosols such as soot are significant, aerosol optical depth and chemical composition are not the only determinants of aerosol climate effects, but the altitude of the aerosol layer and the altitude and type of clouds are also important. In this paper, the aerosol forcing in the presence of clouds and the effect of different surface types (ocean, soil, vegetation, and different combinations of soil and vegetation) are examined based on model simulations, demonstrating that aerosol forcing changes sign from negative (cooling) to positive (warming) when reflection from below (either due to land or clouds) is high.