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.

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.

DIFFUSIVITY OF RARE EARTH ION IN POROUS ION EXCHANGE RESINS

The self-diffusion of E.3+ ion in porous resins D72 and D751 was studied by isotope exchange reaction. .Applying Kataoka’s bidisperse pore model, the intraparticle effective diffusivity De were resolved into a solid diffusivity Dg and a macropore diffusivity Dp. The experiments show that De, Dp and Dg all increase with the increase of reaction temperature; the response DP and Dg to temperature of D72 restin is more sensitive than that of D751; De, Dp and Dg of D721 resin is smaller that that of D72 resin; the diffusivity of Eu3+ ion in solution is larger than Dp, which leads to the conclusion that the diffusion of ion in the pore of resin can not completely be equal to that in solution.

^(15)N/^(14)N Isotopic Exchange in the Dissociative Adsorption of N_(2) on Tantalum Nitride Cluster Anions Ta_(3)N_(3)

Adsorption and activation of dinitrogen(N_(2)) is an indispensable process in nitrogen fixation.Metal nitride species continue to attract attention as a promsing catalyst for ammonia synthesis.However,the detailed mechanisms at a molecular level between reactive nitride species and N_(2) remain unclear at elevated temperature,which is important to understand the temperature effect and narrow the gap between the gas phase system and condensed phase system.Herein,the ^(15)N/^(14)N isotopic exchange in the reaction between tantalum nitride cluster anions Ta_(3)^(14)N_(3)^(-) and ^(15)N_(2) leading to the regeneration of ^(14)N_(2)/^(14)N^(15)N was observed at elevated temperature(393-593 K)using mass spectrometry.With the aid of theoretical calculations,the exchange mechanism and the effect of temperature to promote the dissociation of N_(2) on Ta_(3)N_(3)^(-) were elucidated.A comparison experiment for Ta_(3)^(14)N_(4)^(-)/^(15)N_(2) couple indicated that only desorption of ^(15)N_(2) from Ta_(3)^(14)N_(4)^(15)N_(2)^(-) took place at elevated temperature.The different exchange behavior can be well understood by the fact that nitrogen vacancy is a requisite for the dinitrogen activation over metal nitride species.This study may shed light on understanding the role of nitrogen vacancy in nitride species for ammonia synthesis and provide clues in designing effective catalysts for nitrogen fixation.

Detailed Description of Pulse Isotopic Exchange Method for Analyzing Oxygen Surface Exchange Behavior on Oxide Ion Conductors

A novel pulse 18O-16O isotopic exchange (PIE) technique for measurement of the rate of oxygen surface exchange of oxide ion conductors was presented. The technique employs a continuous flow packed-bed micro-reactor loaded with the oxide powder. The isothermal response to an 18O-enriched pulse passing through the reactor, thereby maintaining chemical equilibrium, is measured by on-line mass spectrometry. Evaluation of the apparent exchange rate follows from the uptake of 18O by the oxide at given reactor residence time and surface area available for exchange. The developed PIE technique is rapid, simple and highly suitable for screening and systematic studies. No rapid heating/quenching steps are required to facilitate 18O tracer anneal or analysis, as in other commonly used techniques based upon oxygen isotopic exchange. Moreover, the relative distribution of the oxygen isotopologues 18O2, 16O18O, and 16O2 in the effluent pulse provides insight into the mechanism of the oxygen exchange reaction. The PIE technique has been demonstrated by measuring the exchange rate of selected oxides with enhanced oxide ionic conductivity in the range of 350?900 oC. Analysis of the experimental data in terms of a model with two consecutive, lumped steps for the isotopic exchange reaction shows that for mixed conductors Ba0.5Sr0.5Co0.8Fe0.2O3-δ(BSCF) and La2NiO4+δ the reaction is limited by the apparent rate of dissociative adsorption of O2 molecules at the oxide surface. For yttria-stabilized zirconia (YSZ), a change-over takes place, from rate-limitations by oxygen incorporation below ∽800 oC to rate-limitations by O2 dissociative adsorption above this temperature. Good agreement is obtained with exchange rates reported for these materials in literature.

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.

Evaluation of Soil Labile Phosphorus Using a Double-Labeling (^(32)P and ^(33)P) Technique

Isotopic exchangeability of phosphorus in four Chinese soils with and without P application was studied by 32P and 33P double-labeling technique in relation to routine chemical extractions. The results showed that Bray- Ⅰ and Bray-Ⅱ reagents could extract most of the fast exchangeable P. Not all of the Olsen-P belonged to fast exchangeable P, but it was about the same quantity of fast exchangeable P in a calcareous soil and a neutral soil without P application. Sequential fractionation of the soil phosphorus showed that most of the added radioisotopes in high P fixation red soils were tightly held by iron and aluminium oxides, which could be totally extracted only by 0.1M NaOH solution. In the neutral and calcareous soils most of the radioisotopes added were loosely held on the surface of soil particles and could be extracted by anion exchange resin. Phosphate application increased the resin-P fraction significantly for all the soils studied.

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.

Competition of surface reactions of tritium release from irradiated Li_4SiO_4 pebbles

Out-of-pile tritium release experiments were performed on Li4 Si O4 pebbles produced from lithium hydroxide under various compositions of sweep gas(He, 1.1% H2/He) and environmental moisture conditions. The experimental results indicate that tritium gas can be released directly from "dry" Li4 Si O4 under pure He gas. This phenomenon did not happen on "wet" samples, which means that the chemical form of released tritium is sensitive to moisture. Adding H2 to sweep gas may increase the overall desorption rate of tritium gas through H2 isotope exchange reaction, which occurs at a lower temperature than those of directly released tritium gas. Yet, the threshold of the H2 isotope exchange reaction is higher than the desorption reaction of tritiated water. Consequently, the effect of H2 isotope exchange reaction would reduce significantly on water adsorbed Li4 Si O4 samples.