6.5 REDUCTION- OXIDATION POTENTIAL (ELECTRODE METHOD)

REDOX —3REDUCTION- 6.5OXIDATION POTENTIAL(ELECTRODE METHOD)In contrast to other field measurements, the determination ofthe reduction-oxidation potential of water (referred to as redox)should not be considered a routine determination. Measurementof redox potential, describedhere as Eh measurement,is not recommendedin general because of thedifficulties inherent in itstheoretical concept and itspractical measurement (see“Interferences and Limitations,”section 6.5.3.A). Eh measurement mayshow qualitative trendsbut generally cannot beinterpreted as equilibriumvalues.Reduction-oxidationpotential (as Eh): ameasure of theequilibrium potential,relative to thestandard hydrogenelectrode, developed atthe interface betweena noble metalelectrode and anaqueous solutioncontainingelectroactive redoxspecies. Determinations of redoxusing the platinum(or other noble metal)electrode method (Eh)are valid only when redoxspecies are (a) electroactive,and (b) present in the solution at concentrationsof about 10 -5 molal and higher. Redox species in natural watersgenerally do not reach equilibrium with metal electrodes.Procedures for equipment calibration (test procedures) and Ehmeasurement are described in this section for the platinum electrodeonly. Although the general guidance given here applies toother types of redox electrodes (such as gold and glassy carbonelectrodes), it is necessary to consult the manufacturer’s instructionsfor correct use of the specific electrode selected. Concentrationsof redox species can be determined by direct chemicalanalysis instead of using the electrode method (Baedecker andCozzarelli, 1992).U.S. Geological Survey TWRI Book 9 4/98Reduction-Oxidation Potential (Electrode Method)