超临界水的文献摘要临界水的文献摘要.docVIP

Organic Chemical Reactions in Supercritical Water 背景：作者Phillip E.Savage Chem.Rev.1999(化学综述) I. Introduction II. Chemical Synthesis A. Hydrogenation/Dehydrogenation 604 B. C?C Bond Formation 605 C. Rearrangements 605 D. Hydration/Dehydration 605 E. Elimination 606 F. Hydrolysis 606 G. Partial Oxidation 606 H. H?D Exchange 607 III. Chemical Conversion 607 A. Decomposition 607 1. Complex Materials 608 2. Individual Organic Compounds 609 B. Oxidation 612 1. Technology Developments 613 2. Homogeneous Reactions 613 3. Heterogeneous Reactions 618 IV. Summary 618 V. Acknowledgments 619 VI. References Introduction 1. The dielectric constant is much lower, and the number and persistence of hydrogen bonds are both diminished. As a result, high-temperature water behaves like many organic solvents in that organic compounds enjoy high solubilities in near-critical water and complete miscibility with SCW. Moreover, gases are also miscible in SCW so employing a SCW reaction environment provides an opportunity to conduct chemistry in a single fluid phase that would otherwise occur in a multiphase system under more conventional conditions. The advantages of a single supercritical phase reaction medium are that higher concentrations of reactants can often be attained and that there are no interphase mass transport processes to hinder reaction rates. 2. The ion product, or dissociation constant (Kw) for water as it approaches the critical point, is about 3 orders of magnitude higher than it is for ambient liquid water. As such, dense high-temperature water is an effective medium for acid- and base- catalyzed reactions of organic compounds. 3. As one exceeds the critical point, however, Kw decreases dramatically. SCW in this high-temperature, low-density region is a poor medium for ionic chemistry. 4. This review is organized around two major themes: chemical synthesis and chemical conversion The chemical synthesis articles tend to be product-oriented, whereas the chemical conversi