Aqueous Chemistry of Metals under Supercritical Water Reactor Coolant Conditions

这项提案寻求为一个合作项目的第二阶段寻求资金，该项目使用最先进的仪器来确定简单酸、碱、溶解金属和金属络合物在近临界和超临界条件下的电离和缔合常数，这将在拟议的第四代超临界水冷却核反应堆(SCWR)中遇到。仪器方法包括拉曼光谱和紫外-可见光谱；以及可视化技术；由从头计算支持。这些都是极其专业的高精度设备，具有北美很少有其他实验室所具备的能力，专为在SCWR反应堆运行条件下进行定量测量而建造。该项目的第一阶段包括建造在超临界区域运行的高压室和仪器。完成了铜、镍和钴配合物的理论和拉曼研究，以及锶离子对的电导研究，最高可达350℃。第二阶段将把这些研究扩展到更多的物种，以及临界点(T&gt；373oC)以上的温度。将开发半经验方程来预测这些和其他含水物种在与第四代蒸汽发生器化学相关的极端条件下的行为。被研究的金属包括Co2+、Ni2+、Cu2+、Fe3+、Fe2+、Pb2+和ZrO2+，以及它们与污染物物种和可能的pH调节剂的反应产物。

This proposal seeks funding for the second phase of a collaborative project that uses state-of-the-art instruments to determine ionization and association constants for simple acids, bases, dissolved metals, and metal complexes under near-critical and super-critical conditions that will be encountered in the proposed Generation IV Super-Critical-Water-cooled nuclear Reactor (SCWR). The instrumental methods include Raman and UV-visible spectroscopy; and visualization techniques; supported by ab initio computations. These are extremely specialized pieces of high-precision equipment, with capabilities shared by few other laboratories in North America, constructed for the specific purpose of making quantitative measurements under SCWR reactor operating conditions. The first phase of the project included the construction of high-pressure cells and instruments for operation in the supercritical region. Theoretical and Raman studies on copper, nickel and cobalt complexes, and conductivity studies on strontium ion pairing up to 350 oC were completed. The second phase will extend these studies to more species, and to temperatures above the critical point (T > 373 oC). Semi empirical equations will be developed to predict the behaviour of these and other aqueous species under the extreme conditions relevant to Gen IV steam generator chemistry. The metals to be studied include Co2+, Ni2+, Cu+, Fe3+, Fe2+, Pb2+ and ZrO2+, along with their reaction products with contaminant species and possible pH control agents.