Oxygen isotope exchange in praseodymium nickelate

Oxygen surface exchange kinetics and diffusion were studied in Pr₂NiO_4?+?δ (PNO) by the isotope exchange method with gas phase equilibration in the temperature range of 600–800 °C and oxygen pressure range of 0.33–1.62 kPa. The oxygen heterogeneous exchange rate (r_H), oxygen diffusion coefficient (D), rates of oxygen dissociative adsorption (r_a), and oxygen incorporation (r_i) were calculated along with the apparent activation energies of oxygen surface exchange and diffusion processes. The temperature dependence of r_H was found to benon-linear in Arrhenius coordinates. The apparent activation energy changed from 1.4?±?0.2 eV at T?>?700 °C to 2.0?±?0.1 eV. This might be attributed to the change in the rate-determining stage of oxygen exchange for Pr₂NiO_4?+?δ at T ~?700 °C, because of a shift in the ratio between r_a and r_i caused by the difference in their activation energies. Possible reasons for the observed changes in the rate-determining stage are discussed.     

铀和铀同位素的离子交换过程研究

在浓缩铀同位索的阳离子交换法中,UC_2~(2+)在离子交换树脂中的传质问题具有特别重要的意义.但迄今未见有详细的报道.本文对阳离子交换树脂—HCl溶液体系中的UO_2~(2+)—H~+正、逆交换,特别对~(235)UO_2~(2+)—~(238)UO_2~(2+)交换动力学及机制作了研究和探讨.     

Modeling and analysis of uranium isotope enrichment by chemical exchange

Starting with an accurate mathematical model a theoretical study for the analysis of the separation of uranium isotopes by chemical exchange has been presented. The experimental data used in this study were obtained by reverse breakthrough technique and the numerical algorithm developed for simulation in previous studies was adapted and found to be suitable for this kind of processes. The model parameters were identified from experimental data and simulations were carried out for different experimental conditions. This revised version was published online in July 2006 with corrections to the Cover Date.     

Magnetic isotope effect of tin and isotope exchange in the reactions of organotin compounds

Conclusions Magnetic isotope effects from tin are not observed during the isotope analysis of the products from reactions involving trimethylstannyl radicals. One of the possible reasons for this is the demonstrated presence of degenerate exchange processes between the initial compounds and the products during the reaction.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2207–2211, October, 1985.     

Determination of iodine in organic iodine compounds by non-equilibrium isotope exchange in a heterogeneous exchange system

Some water-soluble organic iodine compounds (aqueous solution) can be analyzed for iodine by isotopically exchanging with labelled elementary iodine (organic solution). The method is applicable to exchange systems in which the rate of the exchange is rather small but measurable, before the exchange equilibrium is attained. The iodine content of iodoaromatic amino acids such as 5-iodouracil and 3,5-diiodotyrosine can be determined within an error of ±4%.     

Oxygen isotope exchange in the LSM-YSZ composite under the conditions of long-term tests

The stability of the properties of the composite 40 vol % La_0.6Sr_0.4MnO_{3 ? δ}-60 vol % Zr_0.83Y_0.17O_1.92 (LSM-YSZ) held for 1000 h at a temperature of 800°C and an oxygen pressure of 1.01 kPa and changes in its microstructure were studied by isotope exchange and gas-phase analysis. The oxygen exchange was found to occur by the dissociative adsorption mechanism involving the adsorption forms of oxygen on the triple-phase LSM-YSZ-O₂ boundary. The rate-determining step of the oxygen exchange of the composite did not change with time. The rate of oxygen exchange decreased by 22%, which is comparable to the decrease in the length of the LSM-YSZ-O₂ triple-phase boundary (～20%), on which oxygen exchange is dominant. The conductivity of the LSM-YSZ composite increased due to the connectivity of the material.     

Lithium isotope separation by chemical exchange with polymer-bound azacrown compounds

The chromatographic separation of lithium isotopes was investigated by chemical exchange with the recently synthesized polymer-bound dibenzo pyridino diamide azacrown (DBPDA) and reduced dibenzo pyridino diamide azacrown (RDBPDA). Column chromatography was employed for the determination of the effect of solvents and ligand conformation on the separation coefficients. The maximum separation coefficients, , for the DBPDA and RDBPDA at 20.0±0.02°C with acetonitrile as eluent, were found to be 0.034±0.002 and 0.035±0.002, respectively. The isotope separation coefficient and adsorption capability of the lithium ion on the DBPDA and RDBPDA were only slightly dependent on ligand structure, but strongly dependent on the solvent. DBPDA and RDBPDA appeared to have almost the same value for the isotope separation coefficient of lithium.     

Homogeneous isotope exchange between tungsten(VI) and Keggin and Dawson type uranium polyoxotungstophosphates

The present paper is concerned with the isotope exchange between¹⁸⁵W and tungsten, and³²P and phosphorus respectively, in uranium(IV) trivacant Keggin and Dawson polyoxotungstophosphate complexes, in water. These studies were carried out at different concentrations and temperature. The isotope exchange rate increases with the temperature and the reagents' concentration. The experimental results show that the complexes are labile kinetically.     

Precise titrimetric determination of uranium in high-purity uranium compounds

A procedure has been developed for the very precise determination of uranium in high-purity uranium compounds. Uranium(VI) is reduced in a strong hydrochloric acid solution with aluminium in the presence of cadmium ions to uranium(III). It is oxidised to uranium(IV) in the presence of excess orthophosphoric acid and then quantitatively oxidised to uranium(VI) with potassium dichromate using a potentiometric end-point detection. The coefficient of variation based on 20 analyses is -/+ 0.003%.     

Oxygen diffusion and isotope exchange behaviour of NdBa2Cu3O7−x

The oxygen diffusion and exchange behaviour of NdBa₂Cu₃O_7–x is investigated by means of isothermal and dynamic-thermal analytical techniques. From the results it is concluded that oxygen anions move along vacancies in the CuO₂-layers of the perovskite-like structure. In temperature regions where the diffusion rate is low (665 K<T<773 K) heterogeneous oxygen exchange reactions take place on the phase boundary. The higher the exchange rate the more the partially heterogeneous exchange is favoured in comparison to the completely heterogeneous isotope exchange. Depending on the oxygen deficiency of NdBa₂Cu₃O_7–x the out-diffusion of oxygen becomes dominating at higher temperatures.     

尿样中铀同位素的ICP-MS快速测量技术研究

核事故状态下的应急处理,要求对环境介质中的放射性核素进行快速分析。尿样中铀同位素测量作为内照射剂量评价的主要手段,其分析效率越高,则对核事故中涉铀人员的安全救治越及时、有效。而尿样中其它无机离子是铀含量的106倍,导致ICP-MS测量过程中尿盐堵塞进样毛细管。为降低样品的含盐量并获得较好的检测结果,本文对样品预处理过程进行优化。采用先加热氧化去除有机物,再进行1～10倍稀释后测试样品的铀同位素丰度及浓度。结果表明：将25 mL样品稀释至100 mL后效果最佳,分析方法不确定度为5.4 %,回收率95 %~105 %。     

Precise determination of uranium in pure uranium and uranium compounds by constant-current coulomeric titration

A procedure is described for very precise determination of uranium in high-purity uranium and uranium compounds. Uranium(VI) is reduced in a concentrated hydrochloric acid solution by metallic aluminium in the presence of cadmium ions to uranium(III). This is oxidized to uranium(IV) by protons on addition of an excess of orthophosphoric acid, and then oxidized to uranium(VI) by adding a weighed quantity of potassium dichromate in small excess. The excess of potassium dichromate is determined by constant-current coulometry. The coefficient of variation does not exceed 0.003%.     

Anion exchange kinetics of uranium in sulphate media

Experiments have shown that the sorption of uranium from acidic sulphate solutions onto strong base anion exchange resins is particle diffusion controlled in the uranium concentration range 0.0001–0.004M. A simplified diffusion model, based on Fick's Law, fits the kinetic data at each concentration. The rate of sorption falls significantly at lowered solution concentration. This corresponds with a lowered equilibrium loading of uranium and can be predicted with the Nernst-Planck equations using the measured self diffusion coefficient of uranium (1.65 × 10⁻⁸ cm²/s) and sulphate ions. The importance of this lowering of uranium sorption on the design of ion exchange equipment is stressed.     

Kinetic isotope effect in hydrogen isotope exchange between water and phosphines

The kinetic parameters of the tritium exchange between^*H₂O(^*D₂O) and (CH₃)₂PH in the gas phase and between^*H₂O(^*D₂O) and (C₆H₅)₂PH in liquid were measured. Both reactions appeared to be heterogeneous ones. The^*HH/^*DD kinetic isotope effects were estimated and compared with the results of exchange between methanol and phosphines. The differences in isotope effects are explained by the change of the symmetry of the four center cyclic transition complex resulting from the various type of solvation of this complex.     

Radioiodination of amitriptyline by isotope exchange

The catalysed isotope exchange method was studied with the aim to elaborate the optimal procedure for labeling of amitriptyline with iodine¹²⁵I. Besides the catalysts published, cuprous salts and ammonium sulphate, a series of transition metal complexes as catalysts were tested at different reaction conditions. The best result (91% radiochemical yield) was achieved with trans-chlorocarbonylbis-(triphenylphosphine) iridium complex (Vaska catalyst) and sonification.     

Determination of cadmium using isotope exchange

A radiometric method for the determination of cadmium based on two-phase isotope exchange has been developed. The sample containing cadmium is shaken in the presence of tartrate with a standard cadmium-115m diethyldithiocarbamate solution in chloroform. From the distribution of the activity between the aqueous and organic phases 0.05–7 g of cadmium in 5–20 ml sample can be determined.Dedicated to Prof. V. D. Nefedov on the occasion of his 70th birthday