Aspects of the structure and solution chemistry of some technetium-tripolyphosphate complexes

Thesis/Dissertation · Sat Jan 01 04:00:00 EST 1983

OSTI ID:5622116

Miller, G G

Several distinctly different complexes of Tc(III) and Tc(IV) with the ligand tripolyphosphate were prepared and studied electrochemically. In acidic solution, a transient Tc(III) species was observed, the electrochemical behavior of which proves that it is not monomeric in Tc and strongly suggests that it is a dimer. This material is radically different in its polarographic behavior from the Tc(III) complex resulting from the controlled potential electrolysis of TcO/sub 4//sup -/ at a mercury pool cathode in the same electrolyte. The latter, air sensitive, complex can be reversibly oxidized to a Tc(IV) complex which is stable towards further oxidation but which undergoes hydrolysis in both acidic and alkaline media. The rate law for the hydrolysis in basic solution is: rate = 582 I mol/sup -1/ min/sup -1/ (Tc(IV))(OH/sup -/). The hydrolytic reaction in acidic solution is accelerated by hydrogen ion, indicating that a mechanism different from that in basic media is involved. Tc(IV) tripolyphosphate complexes prepared by ligand exchange reactions of TcBr/sub 6//sup 2 -/ were shown by polarography to be different from the complexes prepared electrochemically. The gel permeation chromatographic behavior of one ligand substitution product showed it to be polymeric with a limiting tripolyphosphate to technetium ratio of 1:1.

• Research Organization: Rensselaer Polytechnic Inst., Troy, NY (USA)
• OSTI ID: 5622116
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
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400702* -- Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
BROMINE
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
CHROMATOGRAPHY
COMPLEXES
DATA
DECOMPOSITION
DISPERSIONS
ELECTROCHEMISTRY
ELECTROLYSIS
ELEMENTS
EXPERIMENTAL DATA
GEL PERMEATION CHROMATOGRAPHY
HALOGENS
HYDROLYSIS
INFORMATION
KINETICS
LIGANDS
LYSIS
MIXTURES
NONMETALS
NUMERICAL DATA
OXYGEN COMPOUNDS
PH VALUE
PHOSPHATES
PHOSPHORUS COMPOUNDS
POLAROGRAPHY
REACTION KINETICS
REFRACTORY METAL COMPOUNDS
SEPARATION PROCESSES
SOLUTIONS
SOLVOLYSIS
STRUCTURAL CHEMICAL ANALYSIS
TECHNETIUM COMPLEXES
TECHNETIUM COMPOUNDS
TECHNETIUM PHOSPHATES
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS