Electrochemical reduction of 2,4,6-trinitro diphenylamine in buffered and unbuffered methanolic solutions

✍ Scribed by V. John Koshy; C.S. Venkatachalam; C. Kalidas

• Publisher: Elsevier Science
• Year: 1981
• Tongue: English
• Weight: 463 KB
• Volume: 26
• Category: Article
• ISSN: 0013-4686
• DOI: 10.1016/0013-4686(81)85174-2

✦ Synopsis

The pohuographic reduction of 2,4,6trinitro diphenylamine was found to give three waves of nearly equal height in all pH regions in buffered solutions and also in unbuffered methanol-water mixtures. The waves were shown to be diffusion-controlled and irreversible on the basis of the usual criteria. Controlled-potential electrolysis at the limiting region of the third wsve gave nWr, _= 16 and thus it was shown that rlapp = 6 for each of the waves. It was concluded that each of the nitrogroups in thecompound is reduced to the corresponding ammo group, the nitro groups ortho to the -NH group in the parent compound being reduced timt followed by the other. Cyclic voltammetric experiments in unbuffered solutions gave evidena for a new redox system which was attributed to amine-qninonc diiminc intermtdjate couple. It was inferred that each of the nitro groups in the compound is reduced to the amino function viu this intermediate. * pH values pertain to the particular solvent composition as the standard state. + Half-wave potentials, accurate to f 2 mV. * Summit potentials, accurate to * 4 mV. * Difference in half-wave potentials between second and first waves. ** Difference in half-wave potentials between third and second waves,