Oxidative-coupling reaction of TNT reduction products by manganese oxide.
Abiotic transformation of TNT reduction products via oxidative-coupling reaction was investigated using Mn oxide. In batch experiments, all the reduction products tested were completely transformed by birnessite, one of natural Mn oxides present in soil. Oxidative-coupling was the major transformation pathway, as confirmed by mass spectrometric analysis. Using observed pseudo-first-order rate constants with respect to birnessite loadings, surface area-normalized specific rate constants, ksurf, were determined. As expected, ksurf of diaminonitrotoluenes (DATs) (1.49-1.91L/m2 d) are greater about 2 orders than that of dinitroaminotoluenes (DNTs) (1.15 x 10(-2)-2.09 x 10(-2)L/m2d) due to the increased number of amine group. In addition, by comparing the value of ksurf between DNTs or DATs, amine group on ortho position is likely to be more preferred for the oxidation by birnessite. Although cross-coupling of TNT in the presence of various mediator compounds was found not to be feasible, transformation of TNT by reduction using Fe0 followed by oxidative-coupling using Mn oxide was efficient, as evaluated by UV-visible spectrometry.
Kang
Ki-Hoon
KH
Technology Research Institute, Daelim Industrial Co., Ltd., 146-12 Susongdong, Jongrogu, Seoul 110-732, Republic of Korea. khkang@kaist.ac.kr
Lim
Dong-Min
DM
Shin
Hyunsang
H
D007501:Iron / Q000737:chemistry; D007700:Kinetics; D017895:Manganese Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010087:Oxides / Q000737:chemistry*; D012989:Soil Pollutants; D014303:Trinitrotoluene / Q000737:chemistry*
D017895:Manganese Compounds; D010087:Oxides; D012989:Soil Pollutants; C505018:birnessite; D014303:Trinitrotoluene; C027424:manganese oxide; D007501:Iron