Comparison of mass transfer effects in the heterogeneously catalysed hydrogenation of phenyl acetylene in heptane and an ionic liquid

The selective heterogeneous catalytic reduction of phenyl acetylene to styrene over palladium supported on calcium carbonate is reported in both an ionic liquid and a molecular solvent. By using a rotating disc reactor in conjunction with results from a stirred tank reactor it is possible, for the first time, to disentangle the mass transfer contributions in the ionic liquid system. For both heptane and 1-butyl-3-methyl imidazolium bis{(trifluoromethyl)sulfonyl}imide, the reaction in the rotating disc reactor is dominated by reaction in the entrained film on the disc compared with very limited reaction in the bulk liquid. The lower reaction rate obtained in the ionic liquid compared with the organic solvent is shown to be due to the slow transport of the hydrogen dissolved in the liquid. It is clear from the results presented herein that, although the hydrodynamics of similar reactors used for biological treatment of wastewater are well understood, on using a more viscous fluid and higher rotation speeds necessary for fine chemical catalysis these simple relationships breakdown.

Geochemistry and morphometry on planktonic foraminifera

About one third of the anthropogenic carbon dioxide (CO2) released into the atmosphere in the past two centuries has been taken up by the ocean. As CO2 invades the surface ocean, carbonate ion concentrations and pH are lowered. Laboratory studies indicate that this reduces the calcification rates of marine calcifying organisms, including planktic foraminifera. Such a reduction in calcification resulting from anthropogenic CO2 emissions has not been observed, or quantified in the field yet. Here we present the findings of a study in the Western Arabian Sea that uses shells of the surface water dwelling planktic foraminifer Globigerinoides ruber in order to test the hypothesis that anthropogenically induced acidification has reduced shell calcification of this species. We found that light, thin-walled shells from the surface sediment are younger (based on 14C and d13C measurements) than the heavier, thicker-walled shells. Shells in the upper, bioturbated, sediment layer were significantly lighter compared to shells found below this layer. These observations are consistent with a scenario where anthropogenically induced ocean acidification reduced the rate at which foraminifera calcify, resulting in lighter shells. On the other hand, we show that seasonal upwelling in the area also influences their calcification and the stable isotope (d13C and d18O) signatures recorded by the foraminifera shells. Plankton tow and sediment trap data show that lighter shells were produced during upwelling and heavier ones during non-upwelling periods. Seasonality alone, however, cannot explain the 14C results, or the increase in shell weight below the bioturbated sediment layer. We therefore must conclude that probably both the processes of acidification and seasonal upwelling are responsible for the presence of light shells in the top of the sediment and the age difference between thick and thin specimens.