Revealing the catalytic mechanism of an ionic liquid with an isotope exchange method

The alkylation mechanism catalyzed by an ionic liquid （as a Lewis acid） may be different from the traditional alkylation mechanism catalyzed by Br nsted acid,especially as their initiation steps are still not clear.In this paper,an isotope exchange method is used to investigate the catalytic mechanism of AlCl 3 /butyl-methyl-imidazolium chloride ionic liquid in the alkylation of benzene with 1-dodecene.The proposed catalytic mechanism was confirmed by analysis of ionic liquid before and after reaction and of the alkylation products of deuterated benzene （C 6 D 6） with 1-dodecene.The proposed mechanism consists of the equilibrium reaction between [Al 2 Cl 7 ] ＋H ＋ and [AlHCl 3 ] ＋ ＋[AlCl 4 ],in which the Br nsted acid [AlHCl 3 ] ＋ is supplied by the reaction of 2-H on the imidazolium ring and [Al 2 Cl 7 ].The alkylation reaction is initiated by the Br nsted acid [AlHCl 3 ] ＋ which reacts with 1-dodecene to form a carbonium ion,then the carbonium ion reacts with benzene to form an unstable σ complex,leading to the formation of 2-phenyldodecane.

Oxygen Isotope Exchange Kinetics Between Coexisting Minerals and Water in the Aral Granite Pluton of the Altay Mountains, Northern Xinjiang

Coexisting quartz, feldspar and biotite vary widely in their δ18O values and display a remarkable 18O/16O disequilibrium relation; especially, a quartz-feldspar reversal (△ 18OQUartz_feldspar< 0) exsists in the Aral granite pluton of the Altay Mountains, northern Xinjiang. The 18O / 16O exchange reaction definitely occurred between granite and water. Initial δ18O values of the granite and exotic fluid are evaluated by the mass balance consideration. The conventional method of discrimination between various magma derivations simply with δ18O values of either whole rock or separate minerals is misleading and unreliable. Experiments carried out by the authors show that the 18O / 16O exchange reaction is not accompanied by what geologists describe as petrological and mineralogical alteration effect. This decoupling relation implies that exchange reaction occurs at a relatively high temperature during subsolidus-postmagmatic cooling of magmas. The exchange mechanism is mainly diffusion-controlled. It is demonstrated through quantitative modelling that the hydrothermal system associated with the Aral pluton is long-lived (0.8-6 Ma), with a relatively high fluid flow rate (3 ×10-14 mol. s-1) and high W/ R ratio (0.79-6.14). This means that an intense flow and convection may exist at the midcrustal level of erogenic magmatic arcs.

Kinetic study on the reaction between CO_2-CO and wustite using the isotope exchange method

To investigate the reaction between CO2-CO and wustite using the isotope exchange method at 1073, 1173, 1273, and 1373 K, the experiment apparatus was designed to simulate the fluidized bed. The chemical rate constant was estimated by considering the effect of gas phase mass transfer on the reaction. It is found that the chemical rate constant is inversely decreased with the increase in the ratio of CO2/CO by volume. The activation energy of reaction is in a linear relationship with the ratio of COs/CO by volume, and the average activation energy is 155.37 kJ/mol.

Visible Light Promoted Direct Deuteration of Alkenes via Co(III)–H Mediated H/D Exchange

We report herein a visible light-mediated direct deuteration of alkenes with D_(2)O or deuterated methanol(MeOD)using a cobaloxime as a hydrogen/deuterium(H/D)exchange catalyst.The synergistic photoredox/Co catalysis enabled facile deuterium(D)-incorporation of a variety of terminal and internal alkenes at either terminal or benzylic positions.We proposed that this process proceeded through a sequence of reversible addition-elimination reactions and fast proton exchange involving Co(III)–H,which was generated in situ by photoreduction.

Improvement of hydrogen isotope exchange reactions on Li_4SiO_4 ceramic pebble by catalytic metals

Li4SiO4 ceramic pebble is considered as a candidate tritium breeding material of Chinese Helium Cooled Solid Breeder Test Blanket Module （CH HCSB TBM） for the International Thermonuclear Experimental Reactor （ITER）. In this paper, LiaSiO4 ceramic pebbles deposited with catalytic metals, including Pt, Pd, Ru and Ir, were prepared by wet impregnation method. The metal particles on Li4SiO4 pebble exhibit a good promotion of hydrogen isotope exchange reactions in H2-D20 gas system, with conversion equilibrium temperature reduction of 200-300 ~C. The out-of-pile tritium release experiments were performed using 1.0 wt% Pt/Li4SiO4 and Li4SiO4 pebbles irradiated in a thermal neutron reactor. The thermal desorption spectroscopy shows that Pt was effective to increase the tritium release rate at lower temperatures, and the ratio of tritium molecule （HT） to tritiated water （HTO） of 1.0 wt% Pt/LiaSiO4 was much more than that of Li4SiO4, which released mainly as HTO. Thus, catalytic metals deposited on LiaSiO4 pebble may help to accelerate the recovery of bred tritium particularly in low temperature region, and increase the tritium molecule form released from the tritium breedin~ materials.

A Kinetic Study on the Control of Nitrogen in Molten Slag and Metal

Nitrogen can easily contaminate molten steel during the steelmaking process and due to the low nitrogen capacity in slag, it is difficult to remove entrapped nitrogen from liquid steel. Degassing is often done to the steel at secondary steelmaking to lower the nitrogen content, but the control can often be kinetically limited by the steel grade and also the slag composition. Thus, a fundamental understanding of nitrogen dissolution into molten slag and metal including the rate of nitrogen dissolution can help in controlling nitrogen content in the final product.The kinetics of nitrogen dissolution in the molten calcium aluminate based slags and in molten steel with various element additions was investigated by measuring the 14N-15N isotope exchange reaction using a mass spectrometer at 1873 K.Results show that effect of elements on the rate constant of nitrogen dissolution such as Ni in Fe is relatively minimal similar to molybdenum. The surface rate constant of nitrogen dissolution in liquid Fe-10%Ni alloy was found to be 3.77×10-5 (mol/cm2·s·atm).The rate constant of nitrogen dissolution in the CaO-Al2O3-CaF2 slag was found to be wedge shaped, which decreased with increasing CaF2 to about 20 mol% followed by an increase through the rest of the CaF2 composition range. This was related to the effect of CaF2 on the structure of Al-O bonds for this slag.