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Title: Organic chemical reactions in supercritical water

Journal Article · · Chemical Reviews
DOI:https://doi.org/10.1021/cr9700989· OSTI ID:350273
 [1]
  1. Univ. of Michigan, Ann Arbor, MI (United States). Chemical Engineering Dept.

Water near or above its critical point (374 C, 218 atm) is attracting increased attention as a medium for organic chemistry. Most of this new attention is driven by the search for more green or environmentally benign chemical processes. Using near-critical or supercritical water (SCW) instead of organic solvents in chemical processes offers environmental advantages and may lead to pollution prevention. Interest in doing chemistry in SCW is not entirely new, however. There has been much previous research in this area with applications in synthetic fuels production, biomass processing, waste treatment, materials synthesis, and geochemistry. Water near its critical point possesses properties very different from those of ambient liquid water. 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 paper discusses the use of supercritical water in the following reactions: hydrogenation/dehydrogenation; C-C bond formation; rearrangements; hydration/dehydration; elimination; hydrolysis; partial oxidation; H-D exchange; decomposition; and oxidation.

Sponsoring Organization:
National Science Foundation, Washington, DC (United States); USDOE, Washington, DC (United States)
DOE Contract Number:
FG22-95PC95213
OSTI ID:
350273
Journal Information:
Chemical Reviews, Vol. 99, Issue 2; Other Information: PBD: Feb 1999
Country of Publication:
United States
Language:
English