Use of oxygen isotope exchange in CO2 to characterize active sites

The characterization of carbon surface activity in the absence of gasification was attempted using oxygen isotope exchange in CO₂ over spectroscopically pure natural graphite, the surface activity being characterized by the rate of approach to isotopic equilibrium. The probable mechanism of exchange is via the first step in the carbon-CO₂ reaction, the dissociation of CO₂ over a carbon free site: $\text{CO}{}_2\text{+}\text{C}{}_{\mathrm{f}}\text{?}\text{i}{}_1\text{j}{}_1\text{C(O)}\text{+}\text{CO}$. Assuming this mechanism to hold for isotopic exchange, the theoretical rate equation was derived. The rate constants i₁, and j₁, were obtained from previous studies. Theoretical calculations show that the exchange rate is negligible over natural graphite at temperatures much below gasification conditions. Experimental verification of the theoretical analysis was not possible due to the activity of the quartz boat, holding the graphite, for catalyzing the exchange reaction. The exchange reaction was successfully followed over the Pt and CaO supported on a graphitized carbon black, in which case the activity was much, much greater than that ovgr the empty quartz boat.     

Flash pyrolysis of coal: effect of nitrogen,argon and other atmospheres in increasing olefin concentration and its significance on the mechanism of coal pyrolysis

Samples of three Indian coals, of widely differing origin and rank, were subjected to flash pyrolysis at a temperature of about 1150 °C for 30 s in vacuo, and under atmospheres of nitrogen, argon, ammonia, and perdeuterobenzene. The gaseous products of the pyrolyses were analysed by infra-red and mass spectroscopy and by gas chromatography. Observed variations in gas compositions are discussed relative to the possible mode of influence by the pyrolytic atmospheres. It would appear that the pyrolytic atmosphere is an important factor in determining the composition of the pyrolysis products; the influence of nitrogen, argon and perdeuterobenzene is a physical one, leading especially to higher yields of olefins.     

INVISCID LIQUID CIRCULATION IN BUBBLE COLUMNS

For circulation in axi-symmetric (cylindrical) bubble columns, the recently developed mathematical model^25,26 has been used along with the criterion of minimum circulation strength to determine the height of each circulation cell in a tall column. This is then used to derive a theoretical expression, first of its kind, for gas hold-up inside a bubble column. The predictions of this equation as well as the equation derived here for axial liquid velocity at column axis have been compared with available data and the comparison is found to be excellent for both the variables. An explicit relation is derived for the average liquid circulation velocity. The model is also used to derive an expression for liquid axial dispersion coefficient which compares almost exactly with Deckwer et al.'s⁴ correlation.

For circulation in two-dimensional bubble columns a new mathematical model is developed. The predictions of bubble envelope shape and bubble envelope area compare well with published data. The predictions of number of circulation cells in the horizontal direction also compare well with published data.     

Photocrosslinking of stilbene-modified polymers

The reactions of trans-2,5-dimethoxy-4′-aminostilbene with poly(maleic anhydride-co-methylvinyl ether) and trans-2,5-dimethoxy-4′-isocyanatostilbene with poly(oxy-1,4-phenyleneisopropylidene:1,4-phenyleneoxy-2-hydroxytrimethylene) yield polymeric systems which undergo rapid crosslinking upon short exposure to ultraviolet light. The extent of photocrosslinking as a function of exposure time was determined by the decrease of the trans-stilbene ultraviolet absorption at 350 nm.     

Grafting onto polyester fibers. III. Electrokinetic properties of acrylic acid and acrylonitrile-grafted polyester fibers in the presence of cationic dyes

The electrokinetic properties such as zeta potential, surface charge density, and surface conductivity of polyester fibers grafted with acrylic acid and acrylonitrile were measured when cationic dye solutions were streamed through. The presence of the cationic dyes on the surface of the fibers and their specific adsorption at the carboxylic groups in the acrylic acid graft copolymer produce lowering of zeta potential. The decrease in surface charge density as the percent graft increases is due to the decrease in surface area of the fibers due to the adsorption of the cationic dyes. The same trend is observed with acrylonitrile-grafted fibers. The surface conductivity of the acrylonitrile-grafted polyester fibers increases with increase in dye concentration of the streaming solution. The results for the 27.4% grafted sample differed from those of the 7.32% and 12.1% grafts, which is indicative of the formation of a three-dimensional network causing change in both the physical structure as well as the chemical nature of the surface of the substrate.     

Cellulose triacetate membranes for seawater desalination

Experimental data on reverse osmosis using a sodium chloride solution by cellulose triacetate membranes are presented. The investigation involved studies on the composition of membrane casting solutions and their effects on the performance. A higher polymer concentration (11–13%) is found suitable for production of a uniform and highly salt rejecting membrane. Salt rejection of 99.0% and 4–5 GFD product water flux were obtained at 1000 psi operating pressure using 30,000 ppm TDS seawater in the initial experiments.     

Water Desalination a perspective for membrane processes in India

A crying need of the day in India is to supply safe drinking water to its villages, towns and cities. Though the urban needs are partially met by organized water supply schemes, acute water shortages are felt at various times in this sector also with the expanding industrialization of the country. In many areas of arid and semi-arid regions, only brackish waters are available which are unfit for human consumption.Research and development effort at CSMCRI on the two membrane processes, reverse osmosis and electrodialysis, during the past decade has been reviewed. Some of the current activities in the rural sector and the future potential for these two processes in tackling the pressing needs of potable water to the rural masses in India are outlined. In the industrial sector, these two processes have immense potentialities in pollution abatement and water reuse.     

Characteristics and compositions ofCarissa spinarum,Leucaena leucocephala andPhysalis minima seeds and oils

The seeds and extracted oils ofCarissa spinarum (Apocynaceae), (I),Leucaena leucocephala (Leguminosae) (II) andPhysalis minima (Solanaceae) (III) were analyzed for characteristics and compositions. The seeds of I, II and III contained 22.4, 6.4 and 40.0% oil and 10.1, 27.6 and 17.9% protein, respectively. The oils of I, II and III had, respectively, iodine values 70.1, 113.5 and 122.5; saponification values 186, 188 and 189; unsaponifiable matter 5.2, 2.5 and 0.8%, and the following fatty acid compositions (area %): palmitic 12.6, 14.2, 10.5; stearic 7.6, 6.1, 8.6; oleic 72.7, 20.1, 17.3; linoleic 5.2, 53.8, 61.4; linolenic 0.9, 1.8, 0.0, and arachidic 1.0, 2.3, 0.0. II contained 1.7% lignoceric acid. III contained small amounts of hexadecenoic (0.1%), epoxy (0.6%) and hydroxy (1.5%) fatty acids.     

Loss of Curing Agent During Thin Film (Droplet) Curing of Thermoset Material

Recently, it has been reported by our group and others^1.2 that loss of curing agent is encountered during the curing of small droplets or thin films of amine cured epoxies. In our earlier study³ results were reported on loss of curing agent in small droplets used in conducting the rnicrobond, single fiber test for determination of interfacial shear strength (ISS). It was reported that use of a volatile curing agent (meta-phenylene diamine (m-PDA) with DGEBA resin) resulted in increasing amounts of curing agent being lost (as measured by T₈ of the cured droplets) with decreasing droplet size during the processing procedure. Droplets smaller than 150 micrometers were seen to lose up to 40% of the curing agent leading to alteration of the mechanical properties of the droplet and, therefore, causing measured values of ISS to be exceedingly low. Use of a less volatile curing agent (Jeffamine 700, a polyether diamine, Texaco Specialty Chemicals) in combination with DGEBA resin produced results which indicated that loss of curing agent was not occuring. This study was undertaken to show the relationships between film (or droplet) size and the amount of curing agent lost (during the processing) for three different aminecured epoxy systems.     

An EXAFS study of the Mo/TiO2 hydrodesulphurization catalysis

In-situ EXAFS studies of sulphided Mo/TiO₂ catalysts have shown that at low Mo loadings (2–4 wt%), an active species with a short Mo-S distance of 2.25 Å is formed, while on Mo/TiO₂ with high Mo loadings as well as on Mo/-Al₂O₃, bulk MoS₂ (Mo-S, 2.42 Å) is formed. The species with the short Mo-S distance has Mo in an oxidation state close to 6 + and is likely to result from the sulphidation of the tetrahedral molybdate species present in the oxidic precursor at low Mo loadings. The calcination temperature of the oxidic precursor appears crucial, a high calcination temperature of 973 K favouring the formation of MoS₃ on sulphidation, and a low calcination temperature of 623 K favouring MoS₂.Contribution No. 790 from the Solid State and Structural Chemistry Unit.