U与CO,CO2反应动力学的初步研究

在一定湿度下，将不同形态的铀样品密闭贮存在容器中并充入一定压力的高纯CO或CO2气体，通过定期测量贮存容器中气体组成，初步研究了铀与CO或CO2的反应动力学。结果表明，铀的形态，温度及气体种类对反应速度影响很大。与管状铀相比，铀粉与CO或CO2反应的速率要大得多；温度升高有利于铀与CO或CO2的反应；在相同温度条件下，CO与铀反应生成CO2的速度大于CO2与铀反应生成的CO的速度。     

Pt(110)表面催化CO氧化反应原位研究

CO氧化作为最重要的原型反应之一始终受到广泛关注,而Pt系金属表面催化CO氧化反应的机理目前仍存争议。为了研究Pt表面催化CO氧化反应的机理,借助近常压光电子能谱(AmbientPressureX-ray PhotoelectronSpectroscopy,APXPS)结合在线质谱(MassSpectra,MS),原位分析了Pt(110)表面催化CO氧化反应过程中表面物种以及反应产物的变化。实验结果表明:Pt(110)表面催化CO氧化反应过程可以分为三个状态:1)低反应活性状态,Pt(110)表面CO中毒,CO2的产生速率很低;2)高反应活性状态,Pt(110)表面发生点火反应并伴随大量反应热的释放;3)传质速率限制的反应状态,Pt(110)表面O过量,反应速率受到CO扩散速率的限制。保持反应气体总压强为100 Pa,通过改变不同的CO和O2比例,发现Pt(110)表面催化CO氧化反应的点火温度随着CO含量的增加而升高。本工作对于理解Pt(110)表面催化CO氧化反应机理具有重要帮助,同时为进一步弄清催化反应的活性物种提供了基础。     

LiD与H2O反应机理及动力学

在6-311G（d）水平下,采用微扰理论的MP2方法,研究了LiD与H2O的反应。结果表明,反应存在两个通道：LiD+H2O→LiOH+HD（R1）;LiD+H2O→LiOD+H2（R2）。298K下,两通道的势垒高度分别为9.31和195.08kJ/mol,反应速率常数分别为1.88×1010和3.74×10－26（mol•dm－3）－1•s－1。     

铀金属在H_2 CO气氛中表面反应的XPS研究

用X射线光电子能谱(XPS)分析研究了铀金属在H_2及H_2-CO气氛中的表面反应以及温度和CO对氢化反应的影响。在25℃条件下由于痕量水汽的作用,铀金属表面主要发生氧化反应。在200℃时铀金属表面发生氢化反应,氢化反应随H_2通入量的增加而增加。当H_2含有一定量的CO气体时,表面氢化反应和氧化反应均受到抑制。     

H2O2对Pu(Ⅴ)的还原动力学研究

在0.1 mol/L NaClO4溶液中研究了Pu(Ⅴ)与H2O2反应的动力学。测定了Pu(Ⅴ)与H2O2的反应速率。探讨了温度以及Fe2 ,SO42-,HCO3-,F-等无机离子的存在对反应的影响。实验结果表明,反应对Pu(Ⅴ)与H2O2呈一级,对溶液中H 呈-1级;速率方程可表示为:-dc(Pu(Ⅴ))dt=(3.93±1.93)×10-9c(Pu(Ⅴ))c(H2O2)c(H )。随着温度升高,反应速率明显加快,根据Arrhenius规律,计算出了反应的活化能为Ea=84 kJ/mol。地下水中Fe2 ,SO42-,HCO3-,F-等离子的存在,有利于Pu(Ⅴ)的还原。     

铀金属在H_2 CO气氛中表面反应的XPS研究

用X射线光电子能谱(XPS)分析研究了铀金属在H_2及H_2-CO气氛中的表面反应以及温度和CO对氢化反应的影响。在25℃条件下由于痕量水汽的作用,铀金属表面主要发生氧化反应。在200℃时铀金属表面发生氢化反应,氢化反应随H_2通入量的增加而增加。     

脉冲辐解研究α-生育酚清除三氯过氧自由基(CCl3O2·)机理

采用脉冲辐解技术研究了α- 生育酚清除三氯过氧自由基(CCl3O2)的反应机理和动力学.空气饱和的异丙醇与水的混合溶液(含10-2 M 四氯化碳,CCl4),经脉冲辐解产生CCl3O2.在上述体系中加入α-生育酚,记录到α-生育酚自由基在340nm 和 430nm 2个特征瞬态吸收峰. 结果表明,α-生育酚与CCl3O2通过氢转移进行反应,生成了α-生育酚自由基,其氢转移反应速率常数为2.65×108 M-1s-1.     

CD_4合成工艺研究

采用自制催化剂Ni Mo/Al2O3催化CO2甲烷化反应,制备了大气示踪剂CD4。考察了反应温度、D2与CO2体积比、催化剂负荷等工艺参数对CD4产率和副产物CO体积分数的影响。结果表明:反应温度为350℃、D2与CO2体积比为6、催化剂负荷为6 4μmol/(gcat.·min)时,CD4产率大于96%,反应混合物中CO体积分数低于2 0×10-3。     

H2O2对Pu(Ⅴ)的还原动力学研究

在0.1 mol/L NaClO4溶液中研究了Pu(Ⅴ)与H2O2反应的动力学。测定了Pu(Ⅴ)与H2O2的反应速率。探讨了温度以及Fe2+，SO2-4，HCO-3，F-等无机离子的存在对反应的影响。实验结果表明，反应对Pu(Ⅴ)与H2O2呈一级，对溶液中H+呈-1级；速率方程可表示为： -dc(Pu(Ⅴ))/dt=(3.93±1.93)×10-9c(Pu(Ⅴ))c(H2O2)/c(H+)。 随着温度升高，反应速率明显加快，根据Arrhenius规律，计算出了反应的活化能为Ea=84 kJ/mol。地下水中Fe2+，SO2-4，HCO-3，F-等离子的存在，有利于Pu(Ⅴ)的还原。     

硝酸体系中AHA与HNO_2的反应动力学研究

本工作研究HNO3体系下AHA与HNO2的反应动力学。研究得到该反应的反应动力学速率方程式为-dc(HNO2)/dt=kc(HNO2)c0.25(AHA)c(HNO3)。在t=10℃、I=0.5mol·kg-1条件下,反应速率常数k=(0.4814±0.0375)L1.25·mol-1.25·s-1。实验研究了反应温度对反应速率的影响。结果表明,随着反     

Vaporization and Surface Ionization of LaC2, CeC2, PrC2, NdC2, ThC2 and UC2

The Langmuir vaporization and the surface ionization of LaC₂, CeC₂, PrC₂, NdC₂, ThC₂ and UC₂ from a heated graphite filament have been studied mass spectrometrically. It was found that there were present small amounts of neutral and ionic metal dicarbide molecules in addition to neutral and ionic metal atoms in the LaC₂, CeC₂, PrC₂, ThC₂ and UC₂-C systems with the exception of NdC₂-C, where neither neutral nor ionic metal dicarbide molecules were observed. The reason for this exceptional behavior of the NdC₂-C system is explained by the very small vaporization coefficients, as estimated from the measurements of neutral MC₂/M ratios and ionic MC₂/M ratios.

From the measurements of the heats of vaporization, it was surmised that the ionization potential of Th measured by the surface ionization comparison technique might be too high.     

UO22+在羟基磷灰石上的吸附

以羟基磷灰石（HA）作骨体外模型结合计算机模拟的方法,研究了UO₂²⁺在HA上的吸附行为以及不同种类的螯合剂对其吸附行为的影响。结果表明,15 min后HA对UO₂²⁺的吸附达到平衡,HA颗粒形貌未发生明显改变,吸附过程符合拟二级动力学方程;乙二胺四乙酸（EDTA）和二乙基三胺五乙酸（DTPA）对HA上UO₂²⁺的促排作用类似,能与UO₂²⁺螯合形成大量的络合离子从而达到促排的目的,但会对骨骼无机相表面造成损伤;柠檬酸对吸附在HA上的UO₂²⁺具有较强的解吸作用,但高浓度的柠檬酸会造成HA颗粒形貌显著变化,因此不适合作为铀的促排剂;抗坏血酸对UO₂²⁺在HA上的解吸没有作用,而氨基三乙酸（NTA）会导致HA对铀的吸附率增加。     

Thermal Conductivity of ThO2-UO2 System

The thermal diffusivity of the ThO₂-UO₂ system in solid solution was measured by laser pulse method at temperatures ranging from 20° to 500°C. Reproducibility of the data was confirmed to be within 3%. The compositions of the samples were ThO₂, ThO₂-1%UO₂, ThO₂-5%UO₂ and ThO₂-10%UO₂.

The thermal conductivity was calculated from measured thermal diffusivity data and the specific heat data available in literature and corrected to zero porosity by using Loeb's equation, in which the shape factor is unity.

The values on ThO₂ thus obtained agreed very well with the data found in literature, throughout the range of temperature of the experiments. The thermal conductivity of ThO₂, ThO₂-1%UO₂, ThO₂-5%UO₂ and ThO₂-10%UO₂, at 20°C, were 0.0312, 0.0288, 0.247 and 0.0184 cal·cm/sec· °C·cm², respectively.     

Study on Redox Equilibrium of UO2 2+/U2 + in Molten NaCl-2CsCl by UV-Vis Spectrophotometry

In order to enhance the understanding of the redox equilibriums of uranyl ions in molten NaCl-2CsCl eutectic salt UV-Vis absorption spectrophotometry measurements were performed for UO₂ ²⁺ in molten NaCl-2CsCl at 923 K under simultaneous electrolytic control of their ratio. A prominent absorption band at 395 nm was assigned to UO₂ ⁺, and its molar absorptivity was determined to be 832±27 mol^-1·l·cm^-1. From the dependence of the rest potential of the melt on the spectrophotometrically determined ratio of [UO₂ ²⁺]/[UO₂ ⁺], the standard redox potential of the couple UO₂ ²⁺/UO₂ ⁺ was determined to be ?0.903±0.007 V vs. Cl₂/Cl^—.     

Vapor Species over Na2O-B2O3-SiO2-Cs2O Glass

Methods for suppression and control of the axisymmetric vertical positional instability are described on the basis of conceptural design studies with the International Tokamak Reactor (INTOR). The shell effect is well known to be useful for suppression of the fast instability. Here shell structures are presented and their usefulness is assessed. Included in the assessments are required modellings of the plasma current for determination of mutual inductances between the plasma and the inductive components around it. Three kinds of models are described and their features are compared to the shell effect. Two kinds of simplified reactor structures are described and studied by comparing them with some control characteristics of the slow instability by a pair of control coils. Their structures are selected so as to result in different shell effects between them, and are consequently found to produce different capacities of power supply, too.