In situ Fourier transform infrared spectroscopy as an efficient tool for determination of reaction kinetics

The performance of new FTIR-based monitoring technology to representatively determine reaction kinetics has been demonstrated on an example of homogeneously catalyzed liquid-phase sucrose hydrolysis to fructose and glucose. The reaction kinetics were investigated by using the ReactIR 1000 reaction analysis system, which enables determination of the component concentration from its characteristic FTIR spectrum. During the sucrose inversion, the ReactIR 1000 instrument connected to a computer controlled standard glass batch reactor provided the required operating conditions and information about the component concentration in real-time. We have studied the influence of hydrogen ion concentration, temperature and initial concentration of sucrose on the sucrose disappearance rate. It was found out that the inversion of sucrose is an irreversible reaction, which is not affected by the formation of fructose and glucose in the liquid-phase. Then, the parameters of the kinetic model (i.e., reaction rate constant and activation energy) were calculated. A comparison of the model output and the measured data showed that the kinetics of the sucrose inversion could be well described by means of the pseudo first-order kinetic model. Finally, the method of determining the kinetic model by FTIR spectroscopy was verified by comparing the results obtained in the batch reactor with the results obtained in the continuously stirred tank reactor.     

Synthèse du mèthyl-1 diformyl-2,3 pyrrole,de la méthyl-1 pyrrolo[2,3-d] pyridazine et de la méthyl-1 oxo-6 (6h)cycloheptatrieno[b] pyrrole

This communication describes the synthesis of l-methyl-2,3-diformylpyrrole. This new compound is used to prepare a new heterocycle, l-methylcyclohepta[b]pyrrol-6-one and thus allows a new synthesis of l-methylpyrrolo[2,3-d]pyridazine.     

TPR, TPO, and TPD examinations of Cu0.15Ce0.85O(2-y) mixed oxides prepared by co-precipitation, by the sol-gel peroxide route, and by citric acid-assisted synthesis

Temperature-programmed reduction (TPR), oxidation (TPO), and desorption (TPD) studies were performed on three copper-ceria mixed oxide samples having the same nominal composition, Cu0.15Ce0.85O(2-y), but prepared in three different ways: by co-precipitation, the sol-gel peroxide route, and the sol-gel citric acid route. The obtained results reveal that despite a drastic initial drop in specific surface area after consecutive redox cycles, the hydrogen consumption remains constant. This is because CuO is highly dispersed over the surface of CeO2 nanocrystallites and remains highly dispersed even after the agglomeration of CeO2 nanocrystallites in a denser secondary structure. The dispersed CuO is reduced to Cu(0) during the TPR, forming agglomerated metal particles on the surface of partially reduced CeO2. However, after subsequent temperature-programmed oxidation all the Cu(0) is oxidized back into CuO and redispersed over the CeO2 crystallites.     

Design of a high-power NMR probe for low-temperature studies

A low-temperature, high-power NMR probe head design is described which eliminates the problem of electric arc discharge commonly experienced during radiofrequency pulse cycling in a helium environment. A polychlorotrifluoroethylene (Kel-F) coil former, fitted with a solenoid coil, is heat-shrunk onto stainless-steel flanges and spot-welded inside a stainless-steel probe head assembly connected to a hollow coaxial transmission-line probe shaft. By this means, the sample coil and all high-voltage elements can effectively be isolated in a vacuum, while at the same time permitting good thermal contact between the sample and cryogenic gas. This design was used in NMR studies in the 4.6 K < or = T < or = 77 K temperature range for RF pulse durations < or = 50 ms (and longer for low RF amplitudes) and amplitudes up to approximately 60 G.     

Synthèse dc la pyrido[2,3-f] phtalazine et des diformyl-6,7; -4,6; -4,7; -2,4 quinoleines

This article describes the synthesis of a new heterocycle, pyrido[2,3,f]phtalazine and three new diformylquinolincs.     

Nuclear magnetic relaxation study of the establishment of order in the ammonium halides

The temperature dependence and thermal hysteresis of proton and deuteron spin—lattice relaxation times at high fields and a study of the recovery of the proton and deuteron magnetizations in ammonium halides are reported. The anomalies occurring near the order—disorder phase transition are related to structural, dielectric and Raman data. The hysteresis effect and the establishment of long range order are shown to be related.