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Photochemistry of monodentate and bidentate carbonato complexes of rhodium (3)A scheme for the photochemical fixation of water is proposed which involves a five-step reaction sequence; the first step involves the 2 electron reduction of a metal by a coordinated carbonate ligand, with corresponding oxidation of the carbonate to CO2 and O2. Ligand field photolysis of trans- (RH(en)2 H2O CO3) ClO4, and (Rh(en)2 CO3) CLO4 have been studied in the solid state and in aqueous solution at various pH values. Both salts are photoinert in the solid phase, but are quite photoreactive in aqueous solution. In solution, the monodentate ion undergoes efficient isomerization to a mixture of cis and trans - (Rh(en)2 H2O CO3)+, presumably with water exchange. A minor pH increase upon photolysis is evidence of inefficient carbonate (CO3 =) release, with formation of (Rh(en)2 (H2O)2)3+. In contrast, aqueous solutions of the bidentate carbonato complex undergo efficient pH decrease upon ligand field photolysis. Changes in the electronic spectrum (200-500 nm) and pH changes indicate that the desired redox is occurring. The pH increase is due to the aqueous behavior of CO2.
Document ID
Document Type
Sheridan, P. S. (Colgate Univ. Hamilton, NY, United States)
Date Acquired
August 11, 2013
Publication Date
October 1, 1980
Publication Information
Publication: Alabama Univ. Res. Rept.: The 1980 NASA(ASEE Summer Fac. Fellowship Program
Subject Category
Distribution Limits
Work of the US Gov. Public Use Permitted.

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IDRelationTitle19810003469Analytic PrimaryResearch reports: The 1980 NASA/ASEE Summer Faculty Fellowship Program