A polarographic investigation of the reduction mechanism of certain cobalt (III) complex ions

A series of eight compounds with bis-diamine cores were prepared and their electrochemical behavior was explored polarographically. The behavior of the compounds was studied at the dropping mercury electrode and the rotating platinum electrode. Trans-dinitro-bis-(ethylenediamine) cobalt (III) nitrate shows reversible behavior in well-buffered solutions at the dropping mercury electrode, The mechanism for the reduction is proposed as; rapid, reversible election transfer; decomposition of the reduced species; and, in solutions sufficiently alkaline, the formation of tris-(ethylenediamine) cobalt (II), thereby accounting for the observed second wave. The reduction of cis dithiocyanato-bis-(ethylenediamine) cobalt (III) thiocyanate and oxalato-bis-(ethylenediamine) cobalt (III) chloride both give irreversible waves, thereby complicating any proposal of a mechanism. The observed second reduction wave, though, appears to be caused by the formation of tris-(ethylenediamine) cobalt (II), as in the case of the dinitro compound. A proposal of the mechanism for the other five compounds was not possible as they either reduced at too positive a potential, aquated too rapidly, or both.

Name thesis:degree_name

Master of Science

Level thesis:degree_level

masters

Discipline thesis:degree_discipline

Chemistry

Department dc:contributor.department

Chemistry

Grantor dc:publisher

Virginia Tech

Year dc:date.issued

1962

Author dc:creator

• White, Richard Lee

Statement dc:rights

• In Copyright

Licence dc:rights.uri

• http://rightsstatements.org/vocab/InC/1.0/

Dc Identifier Other

etd-04072010-020112

OAI identifier oai:identifier

oai:vtechworks.lib.vt.edu:10919/41963