高放废物地质处置中的模型

我国将采用深地质处置的方法处理核能发展所产生的大量高水平放射性废物。为了准确地预测核素的迁移行为,评估处置库的安全性,除了实验之外,还必须使用模型。本文对高放废物地质处置中所涉及的模型,以及与模型相关的软件、数据库做了综述,重点叙述了用于化学种态分析的地球化学模型,扼要介绍了多场耦合模型。此外还简要报告了本实验室核素迁移实验数据的处理方法和程序。     

X射线吸收谱学在锕系环境放射化学中的应用

锕系环境放射化学对于核废料尤其是高放废物的安全处理和处置至关重要,同步辐射技术尤其是X射线吸收谱学在解析锕系元素在不同介质表面的配位结构方面可以发挥关键作用,对于理解锕系元素在环境介质中的迁移转化行为意义重大.本文综述了近年来国内外利用X射线吸收谱学研究锕系元素环境化学方面的最新进展,主要包括锕系核素在不同地质条件下的迁移和转化以及微生物对核素迁移的影响等方面.     

Fe（Ⅱ）-矿物对亚硒酸的还原作用

79Se是核反应过程中产生的长半衰期（T1/2=2.95×105年）裂片产物核素,具有化学和辐射双重毒性,是高放废物地质处置中重点关注的几个放射性核素之一.硒的溶液化学性质比较特殊,以高价态形式存在的硒酸和亚硒酸,几乎不受溶解度控制,并难以被黏土或花岗岩等处置库围岩介质所吸附,迁移性极强,而当其以低价态（0、–I、–II）形式存在时,易形成固体沉淀.因此将高价态的硒还原生成沉淀是阻滞79Se迁移的最主要方式.从另一方面讲,Fe（II）-矿物是自然界中普遍存在的具有还原性的物质.本文对近年来国内外在Fe（II）-矿物还原亚硒酸方面开展的研究工作进行了一个回顾,并从热力学的角度,对这些矿物还原亚硒酸的可行性及控制产物生成的因素进行了分析.     

基于格子的链状流体分子热力学模型

格子模型是高分子溶液理论最常采用的流体模型,在此基础上建立的分子热力学模型在流体混合物的热力学性质、相平衡行为的计算等方面有广泛的应用．最近,我们对基于格子的混合亥氏函数模型重新进行了审视,采用统计力学理论推导与计算机模拟相结合的现代分子热力学研究方法建立了新的分子热力学模型,可以反映高分子链枝化、配位数、链刚性、共聚物链组成、氢键、压力等的影响,对小分子系统和高分子溶液的热力学性质和相平衡关系的计算不仅与Monte Carlo模拟结果吻合,比现有其他理论预测效果更好,对高分子溶液、离子液体混合物等实际系统的相平衡计算也取得令人满意的结果,显示出模型优越的工程应用价值．本文对上述工作进行了系统总结．     

量子化学现状和展望(上)

量子化学是应用量子力学的原理和方法解决化学问题的一门科学,它包括基础研究和应用研究两个方面。在基础量子化学方面,主要是建立了三种化学键理论,也就是分子轨道理论、价键理论和配位场理论,以及创建了多种计算方法,包括从头算方法和各种半经验方法,例如HMO、EHMO、CNDO与X_α方法等。在应用量子化学方面,过去主要是稳定态分子及其有关性质的研究,近年来激发态分子,催化与表面化学,微观反应动力学,生物大分子与药物大分子的计算正在逐渐增多。量子化学的发展过程是与合成化学、结构化学的发展密切结合的,并且相互促进。本文对上述内容作一简要介绍。     

温度对二甲基亚砜水溶液的结构和热力学性质的影响

应用参考作用格位模型理论计算了二甲基亚砜(DMSO)摩尔分数为0.002时不同温度下溶液的微观结构和热力学性质. 计算结果表明, DMSO加入到水中能够增强溶液的分子网络结构. 温度升高, 配位数减小, 溶液中分子排布趋向无序. 平均力势的波动增大表明分子间的诱导力表现为斥力. 计算得到的各种热力学性质显示: 温度升高, 溶液的熵和溶剂化自由能增加, 相互作用能和过剩化学位也增加, 即高温下溶液越来越偏离理想溶液; 空位形成能降低表明溶液分子结构在高温下更容易重组.     

镎和钚与环境中无机阴离子的配位化学研究进展

镎(Np)和钚(Pu)是核能领域两种重要的锕系元素, 其在水溶液中的配位化学对于了解和控制其在水环境中的种态分布和迁移行为具有重要意义. Review了近十几年来国内外Np和Pu与环境中常见无机阴离子在水溶液中的配位化学研究进展, 重点阐述了不同价态Np/Pu离子与OH^–、 $CO_3^{2-}$、 $SO_4^{2-}$、Cl^–、 $NO_3^-$、F^–、 $PO_4^{3-}$等阴离子之间形成的配位物种和配位热力学信息, 并对该领域存在的关键科学问题和未来发展方向进行了分析和展望.     

金属间化合物NiAl晶格模型的蒙特卡罗模拟

采用巨正则系综蒙特卡罗(GCMC)方法对NiAl合金晶格模型在1273 K温度下的点缺陷浓度和Al原子相对化学活度等进行计算, 并与实验数据及缺陷关联模型(DCM)的理论计算结果进行比较. 结果发现, 当Ni原子比大于0.475时, 晶格模型能很好地描述NiAl合金的行为; 当Ni原子比小于0.475时, 空位浓度高于0.05, 晶格模型相互作用参数须作适当修正. 研究指出GCMC能很好地模拟晶格模型的热力学性质, DCM在描述富Ni区域Al空位的热激发行为和富Al区域Ni空位分布的关联性方面有局限性.     

放射性核素在固-液界面上的吸附：模型及其应用

放射性核素在固-液界面上的吸附行为是其在低浓度下物理化学行为研究的重要内容之一。本文综述了固-液界面吸附研究方面取得的主要进展,总结了放射性核素在固-液界面的吸附动力学、热力学模型,重点讨论了表面配位模型和亚稳态理论在固-液界面吸附行为研究中的应用和发展,较为详细地概括了部分先进光谱技术、理论计算方法和模型模拟手段等在...     

物理化学学报投稿范围

<正>1.热力学,动力学和结构化学(化学平衡与热力学参数、量热学、非平衡态热力学与耗散结构、统计热力学、宏观动力学、分子动态学、超快动力学、激发态、溶液化学、复杂流体、溶液结构、大气化学、动态结构、分子结构、体相结构、簇、谱学)2.理论与计算化学(量子化学、统计力学、模拟方法与应用、计算化学、化学信息学)3.电化学和新能源(电极过程动力学、界面电化学、电催化、谱学电化学、电化学表面科学、材料电     

Microstructures and speciation of radionuclides in natural environment studied by advanced spectroscopy and theoretical calculation

The environmental behavior of radionuclides is mainly dependent on their speciation and microstructures at solid particles.The speciation and microstructures of radionuclides at molecular level can be achieved from advanced spectroscopy techniques and theoretical calculations.In this perspective,we give a brief introduction of the advanced X-ray absorption fine structure(XAFS) technique and theoretical calculation in the analysis of the speciation and microstructures of radionuclides in the natural environment,which is crucial to evaluate the physicochemical behavior of radionuclides in the environment.     

Effect of temperature on the acid-base properties of the alumina surface: microcalorimetry and acid-base titration experiments

Sorption reactions on natural or synthetic materials that can attenuate the migration of pollutants in the geosphere could be affected by temperature variations. Nevertheless, most of the theoretical models describing sorption reactions are at 25 degrees C. To check these models at different temperatures, experimental data such as the enthalpies of sorption are thus required. Highly sensitive microcalorimeters can now be used to determine the heat effects accompanying the sorption of radionuclides on oxide-water interfaces, but enthalpies of sorption cannot be extracted from microcalorimetric data without a clear knowledge of the thermodynamics of protonation and deprotonation of the oxide surface. However, the values reported in the literature show large discrepancies and one must conclude that, amazingly, this fundamental problem of proton binding is not yet resolved. We have thus undertaken to measure by titration microcalorimetry the heat effects accompanying proton exchange at the alumina-water interface at 25 degrees C. Based on (i) the surface sites speciation provided by a surface complexation model (built from acid-base titrations at 25 degrees C) and (ii) results of the microcalorimetric experiments, calculations have been made to extract the enthalpic variations associated respectively to first and second deprotonation of the alumina surface. Values obtained are deltaH1 = 80+/-10 kJ mol(-1) and deltaH2 = 5+/-3 kJ mol(-1). In a second step, these enthalpy values were used to calculate the alumina surface acidity constants at 50 degrees C via the van't Hoff equation. Then a theoretical titration curve at 50 degrees C was calculated and compared to the experimental alumina surface titration curve. Good agreement between the predicted acid-base titration curve and the experimental one was observed.     

A review of the studies on environmental transport and speciation analysis of radionuclides in India

Department of Atomic Energy, India, has a systematic environmental monitoring program to ensure that the impact of radionuclides on human and environment is well within the limits, stipulated by the regulatory body. Concentrations of radionuclides are estimated in air, water, soil, sediment and biota in the environment around the power plant site on a regular basis. The environmental migration pattern and impact of radionuclides in the environment depends upon not only on the total concentration but the physico-chemical nature of radionuclide also. This paper presents a brief review of the studies of environmental transportation of radionuclides and influence of speciation with special reference to Indian conditions. A fairly good amount of results are available on the influence of speciation of radionuclides on the wet and dry deposition and preliminary results are available on the speciation analysis in dietary items, in soil and in ground water. Initial studies are concentrated on tritium, ¹³⁷Cs, Uranium, ⁹⁰Sr and their chemical analogues.     

Main sources of radioactive contamination in Russia and methods for their determination and speciation

This paper desribes the main sources of radioactive contamination of Russia and some techniques elaborated in the V. I. Vernadsky Institute of Geochemistry and Analytical Chemistry for the determination and speciation of radionuclides in the environment. Data on radioecological monitoring of the zone affecting by Production Association “Mayak” are presented as example of the use of these techniques. Some problems of the calculation of radionuclide migration coefficients and the determination of their so called geochemical forms of occurrence are discussed.     

Sorption of Arsenic Oxyanions from Aqueous Solution on Goethite: a Study of Process Modelling

In the course of researching methods of sampling and monitoring toxic metals (as arsenic ions) in water and wastewaters, we selected the use of sorption for in-depth examination. Among other things, sorption modelling was investigated by the mechanism of surface complexation in order to describe the process or even predict the outcome for the expected rate, and in general, to develop this detection technique for pollutants. This investigation will include the application of goethite mineral as the suitable metal ion sorbent and the use of appropriate computer software. The relative thermodynamic aqueous speciation of the solution, in similar experimental conditions, was also studied.     

Vibration Spectroscopy Study of Phenylphosphonate at the Water–Aluminum (Hydr)Oxide Interface

Two previously published surface complexation models of phenylphosphonate on aged γ-Al₂O₃and boehmite (γ-AlOOH), respectively, have been examined by means of FTIR and FT-Raman spectroscopy. The spectral features of adsorbed phenylphosphonate were studied as a function of pH and total phenylphosphonate concentration. No evidence for a phase transformation into a three-dimensional aluminum phenylphosphonate phase was found. This suggested that phenylphosphonate is sorbed as surface complexes under the conditions used in this study. Both the infrared and the Raman data showed that the surface-bound phenylphosphonate ions undergo protonation reactions as pH is varied. These results together with the fact that the ligand has only two donor atoms for complexation and protonation led to the conclusion that a monodentate coordination to the surface is most likely in both systems. Overall, the spectroscopic results were in good qualitative agreement with the thermodynamic surface complexation models.     

Aggravation of licensing procedures by doubtful thermodynamic data

Environmental prognosis by geochemical modelling is a scientific approach to several open questions of general public interest. Two prominent fields where geochemical modelling holds an important share are the remediation of contaminated former uranium mining areas and safety assessment of radioactive waste repositories in the geosphere. In both fields, application of geochemical modelling is stipulated by public authorities. The enormous complexity of models that can be handled by computers rises the awareness on the meaningfulness of a modelling result and demands for provision of an estimate of the dependability of a calculation output by the computers. It is obvious that bias, over- and underestimation of uncertainty in input data reduces the relevance of the calculation output. Chemistry contributes important data to geochemical modelling, both from field analysis and in the fundamental physico-chemical quantities enclosed into the thermodynamic data base. Some examples will be given where progress in quality assessment of chemical data may further the predictive power of geochemical modelling.     

Chemical speciation of radionuclides through the microbial process in soils

Environmental factors (nutrients and pH) influence the retention of Sr, Cs, and Ba as analogue of long-lived radionuclides by the microorganism. The effect of pH and concentration of organic nutrients are proved to be significant factors for retention of cations (Sr, Cs and Ba) by the microorganisms inoculated from surface soil. Microorganisms can affect the speciation of Sr, Cs, and Ba in the environment. Concentration of organic nutrients and pH are indicated to be the important environmental factors in the consideration of the migration of the radionuclides through microbial processes in the terrestrial environment.