Abstract: Electrochemically reacting a lanthanide or actinide in solvent at a working electrode; wherein the solvent comprises an organic solvent such as acetonitrile which have a dielectric constant of at least three; wherein the solvent system further comprises an electrolyte; wherein the working electrode comprises an ionically conducting or permeable film such as a fluorosulfonate film; wherein at least one ligand such as triflate distinct from the ionically conducting or permeable film is present; wherein the ligand is chemically similar to a structure in the ionically conducting or ionically permeable film; and optionally wherein the electrochemical oxidation or reduction is carried out under the influence of a magnetic field which favorably enhances the reaction. Improved electrochemical methods, identification, and separation can be achieved.