Measurements of excess enthalpies at high temperature and pressure using a new type of mixing unit

A flow mixing unit (calorimetric cell and auxiliary devices) has been designed for measuring the enthalpy of mixing or reaction of two fluids (gas+liquid or liquid+liquid). The indicator of the heat effect is a differential heat flux calorimeter, SETARAM C-80, allowing measurements at temperatures up to 300°C. The mixing cell is made of a stainless-steel capillary (o.d 1.6 mm, length 2.4m) which is coiled in a cylindrical form and tightly fitted in the thermopile well of the calorimeter. The fluids are delivered from the high pressure piston pumps and circulated through the system at controlled flow rates ranging from 100 to 1500 L-min^–1. The tests were carried out at pressures up to 20 MPa. Special care was taken to allow good thermostatting of fluids entering the mixing cell. Check measurements were made with one liquid-liquid system (C₂H₅OH+H₂O) and one gas-liquid system (CO₂+C₆H₅CH₃); our enthalpies of mixing agreed with the literature values in most cases to 2%. For the system ethanol+water the experiments have been also performed at temperature of 250°C and pressures of 15 and 20 MPa. The endothermal mixing effect was higher than expected indicating an increase in the excess heat capacity.     

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Effect of trans-Resveratrol and Ascorbigens on the Fire Blight Pathogen Erwinia amylovora in the BioArena System

JPC – Journal of Planar Chromatography – Modern TLC - On the basis of our earlier observations, preliminary experiments were conducted with the fire blight pathogen Erwinia amylovora...     

Insights into a surprising reaction: the microwave-assisted direct esterification of phosphinic acids

It is well-known that phosphinic acids do not undergo direct esterifications with alcohols under thermal conditions. However, the esterifications take place under microwave (MW) irradiation due to the beneficial effect of MW. As a comparison, maximum 12-15% conversions were observed on traditional heating. It was proved experimentally that the MW-assisted esterifications are not reversible under the conditions applied that may be the consequence of the hydrophobic medium established by the long chain alcohol/phosphinic ester. Neither the thermodynamic, nor the kinetic data obtained by high level quantum chemical calculations justify the direct esterification of phosphinic acids under thermal conditions. The thermodynamic data show that there is no driving force for the reactions under discussion. As a consequence of the relatively high values of activation enthalpy (102-161 kJ mol(-1)), these esterifications are controlled kinetically. Comparing the energetics of the esterification of phosphinic acids and the preparative results obtained under MW conditions, one can see the potential of the MW technique in the synthesis of phosphinates. During our study, a series of new cyclic phosphinates with lipophilic alkyl groups was synthesized.     

Photoelectron spectroscopy of silicon doped gold and silver cluster anions

Photoelectron spectra of low temperature silicon doped gold cluster anions Au(n)Si(-) with n = 2-56 and silver cluster anions Ag(n)Si(-) with n = 5-82 have been measured. Comparing the spectra as well as the general size dependence of the electron detachment energies to the results on undoped clusters shows that the silicon atom changes the apparent free electron count in the clusters. In the case of larger gold clusters (with more than about 30 gold atoms) the silicon atom seems to consistently delocalize all of its four valence electrons, while in the case of the silver clusters a less uniform behavior is observed. Here the silicon atoms act partly as electron donors, partly as electron acceptors, without following an obvious simple principle. Additionally some structural information can be obtained from the measured spectra: while Ag(54)Si(-) seems to adopt an icosahedral structural motif, Au(54)Si(-) seems to take on a low symmetry structure, much like the corresponding pure 55 atom clusters. This indicates that for such larger clusters the incorporation of a single silicon atom does not change the ground state geometry significantly.