Polynuclear Sulfide, Polysulfides and Thiol Complexes in Anoxic Water

目前的许多研究都是为了了解微量金属在缺氧水生环境中的行为。这些研究产生了对含有还原硫配体的金属配合物的化学计量学和稳定性的准确数据的需求。在许多情况下，现有的数据在数量级上是不确定的。在其他情况下，没有任何可用的数据（例如，大多数亲硫微量金属的多硫化物和脂肪族硫醇络合物）。关于这些数据存在的一个主要问题是，这些配合物是单核的还是多核的。以前的实验学家提出了这个问题，但没有回答。将多核配合物误解为单核配合物会在预测自然界的化学行为时产生巨大的错误。要回答这些问题，需要一个进行基本测量的程序。铜和锌将是大部分工作的重点，但如果时间允许，将对铁进行一些研究。所有测量将在250℃下进行。这些研究将以本实验室以前的工作为基础。它们将为破译金属在缺氧环境中的溶解度提供重要信息，并应用于污染、废水处理和各种地球化学问题。

Much current research is directed toward understanding the behavior of trace metals in anoxic aquatic environments. These studies have created a need for accurate data on the stoichiometry and stability of metal complexes containing reduced sulfur ligands. Existing data in many cases are uncertain at the order of magnitude level. In other cases, no data whatever are available (e.g., polysulfide and aliphatic thiol complexes of most sulfophile trace metals). A major question about such data as do exist concerns whether the complexes are mononuclear or poly- nuclear. Previous experimentalists have raised this question but not answered it. Misinterpretation of polynuclear complexes as mononuclear can create immense errors in predictions of chemical behavior in nature. A program to make the fundamental measure- ments is needed to answer such questions. Copper and zinc will be the focus of most of the work, although some studies on Fe will be undertaken if time permits. All measurements will be made at 250C. These studies will build upon previous work in this laboratory. They will add significant information in deciphering metal solubility in anoxic environments with applications to pollution, waste water treatment and a variety of geochemical problems.