Investigation of mechanisms of oxidation of EDTA and NTA by permanganate at high pH.
Permanganate has been used for oxidation of nuclear wastes containing chelating agents such as ethylenediaminetetraacetic and nitrilotriacetic acids (EDTA and NTA) to improve separation of radionuclides and heavy metals from the wastes, butthe mechanisms of degradation of these and related organic ligands at high pHs have not been studied. EDTA, NTA, and the model compound ethylenediamine (EN) were found to be readily oxidized by permanganate at pH 12-14. The reduction of permangante was accompanied by formation of unstable manganate and dispersed MnO2 particles, which constituted the final product of permanganate reduction. The yields and speciation of EDTA, NTA, and EN breakdown products were affected by the pH and permanganate dose. Iminodiacetic acid (IDA), oxalate, formate, and ammonia were the predominant EDTA and NTA oxidation products. Mineralization of EDTA, NTA, and EN to CO2 was more significant at pH 12. At pH 14 formation of oxalate and deamination to NH3 were the most important reactions. IDA was released upon the oxidation of both EDTA and NTA, but EDTA oxidation yielded no ethylenediaminediacetic acid (EDDA). The speciation of the reaction products indicated that the ethylene group in EDTA was the preferred attack site in oxidations by alkaline permanganate.
Chang
Hyun-Shik
HS
Department of Civil and Environmental Engineering, University of Washington, Seattle 98115-2700, USA.
Korshin
Gregory V
GV
Ferguson
John F
JF
D000475:Alkenes / Q000737:chemistry; D004492:Edetic Acid / Q000031:analogs & derivatives / Q000032:analysis / Q000737:chemistry*; D004784:Environmental Monitoring / Q000379:methods*; D005029:Ethylenediamines / Q000032:analysis*; D006863:Hydrogen-Ion Concentration; D007098:Imino Acids / Q000032:analysis; D017895:Manganese Compounds / Q000737:chemistry*; D008956:Models, Chemical; D009571:Nitrilotriacetic Acid / Q000032:analysis / Q000737:chemistry*; D010087:Oxides / Q000737:chemistry*; D013053:Spectrophotometry; D014874:Water Pollutants, Chemical; D014875:Water Pollutants, Radioactive
D000475:Alkenes; D005029:Ethylenediamines; D007098:Imino Acids; D017895:Manganese Compounds; D010087:Oxides; D014874:Water Pollutants, Chemical; D014875:Water Pollutants, Radioactive; C048856:permanganic acid; C026058:EDDA; C031234:ethylenediamine; D004492:Edetic Acid; D009571:Nitrilotriacetic Acid; C008109:iminodiacetic acid