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首页> 外文学位 >Decomposition mechanisms related to Hanford waste: Characterization of nitric oxide from organic nitroxyl derivatives.
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Decomposition mechanisms related to Hanford waste: Characterization of nitric oxide from organic nitroxyl derivatives.

机译：与汉福德废料有关的分解机理：有机硝酰衍生物中一氧化氮的表征。

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摘要

This thesis has its origins in understanding the chemical mechanisms of gas formation in nuclear waste storage at Hanford, Washington. Research began at Georgia Tech in 1990 to investigate the thermal mechanisms that led to the formation of hydrogen, nitrous oxide, nitrogen, and ammonia from the high level waste. Mechanisms from these studies suggested that NO − was an intermediate generated from the deterioration of HEDTA in Hanford waste. NO−, which is isoelectronic with molecular oxygen, and the tautomeric HNO and NOH, its conjugate bases, have often been postulated as intermediates in reactions in aqueous solution where N 2O appears as a final product.; The existence of HNO and NOH has been substantiated by gas phase spectroscopy and matrix isolation studies. The ground state of NO− is 3Σ in the gas phase while the 1Δ state is 17.2 kcal mol−1 higher in energy. Extensive gas phase calculations suggest that the heats of formation for the ground state singlet HNO and ground state triplet NOH are respectively 26.0 and 51.0 kcal mol−1 (at 298 K). Contrary to the considerable experimental and theoretical work with NO−, HNO, and NOH in the gas phase, relatively little is known about these species in condensed phases.; Here, evidence for the generation of NO− and HNO in the condensed phase was two-fold. From base-induced decomposition reactions with 9,10-nitroso-9,10-dimethylanthracene, the parent 9,10-dimethylanthracene was formed via a retro-Diels-Alder reaction. A solid hyponitrite salt, the dimer of singlet NO−, was also isolated and characterized by infrared and ultraviolet spectroscopy. In oxidation reactions intended to be a suitable source of NOH or/and triplet NO−, the decomposition of the N-oxide intermediate of 9,10-dihydroanthracen-9,10-imine produced anthracene and revealed evidence of HNO instead. Nitrous oxide, the dimerization and dehydration product of HNO, was detected in the headspace of the sealed reaction flask by gas chromatography.
机译：本论文的起源是了解华盛顿汉福德核废料储存中气体形成的化学机理。 1990年，佐治亚理工学院开始进行研究，以研究导致高水平废物形成氢，一氧化二氮，氮和氨的热机制。这些研究的机制表明，NO -是汉福德废料中HEDTA降解产生的中间产物。 NO -与分子氧是等电子的，互变异构的HNO和NOH及其共轭碱经常被假定为水溶液中N 2 O反应的中间体出现为最终产品。气相色谱法和基质分离研究证实了HNO和NOH的存在。气相中NO -的基态为 3 Σ，而 1 Δ态为17.2 kcal mol -1 更高的能量。大量的气相计算表明，基态单重态HNO和基态三重态NOH的形成热分别为26.0和51.0 kcal mol -1 （在298 K下）。与气相中NO -，HNO和NOH的大量实验和理论工作相反，在冷凝相中对这些物质的了解相对较少。在这里，在冷凝相中生成NO -和HNO的证据是两倍的。由碱诱导的与9,10-亚硝基-9,10-二甲基蒽的分解反应，通过逆Diels-Alder反应形成了母体9,10-二甲基蒽。还分离出固态亚硝酸盐，即单线态NO -的二聚体，并通过红外和紫外光谱对其进行了表征。在旨在作为NOH或/和三重态NO -的合适来源的氧化反应中，9,10-二氢蒽-9,10的 N 氧化物中间体分解-亚胺生成蒽并显示出HNO的证据。通过气相色谱法在密闭反应烧瓶的顶部空间检测出一氧化二氮（HNO的二聚和脱水产物）。

著录项

  • 作者

    Belcher, Marcus Anthony.;

  • 作者单位

    Georgia Institute of Technology.;

  • 授予单位 Georgia Institute of Technology.;
  • 学科 Chemistry Organic.; Engineering Environmental.
  • 学位 Ph.D.
  • 年度 2001
  • 页码 131 p.
  • 总页数 131
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 有机化学;环境污染及其防治;
  • 关键词

  • 入库时间 2022-08-17 11:47:19

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