The Oxygen Electrode

Consider the electrode physically made up as O2(g),Pt/H2O. The half-reaction for this electrode is
O2(g) + 4H+ + 4e- --> 2H2O,
and for it:

E = Eo - 0.05915/z log (a(red)/a(ox))

E = +1.2288 - 0.05915/4 log (a2(H2O)/a(O2(g))a4(H+))

E = +1.2288 + 0.0148 log a(O2(g)) + 0.05915 log a(H+)

E= +1.2288 + 0.0148 log p(O2(g)) - 0.05915 pH

The actual potential of the oxygen electrode will then vary with two factors: the partial pressure of the oxygen gas, and the acidity of the solution in which the electrode is operating. Each exerts its influence on the potential independently of the other, and the observed electrode potential is a result of both influences. This is true in general of all multiple influences on potential which arise from the Nernst relationship -- they can be considered to act independently.
[http://www.chem.ualberta.ca/courses/plambeck/p102/p02104.htm]


Polarographic Oxygen Monitoring

How does your polarographic dissolved oxygen system work? The Clark type polarographic electrode was developed by Dr. Leland Clark.  When a potential of about 0.7V is applied between the anode and the cathode, dissolved gaseous oxygen is reduced at the platinum cathode. This produces a current and consumes the oxygen in the immediate vicinity of the exposed platinum cathode. Oxygen in the sample volume diffuses through the membrane to the oxygen-poor region between the membrane and the electrode. When a steady-state is reached (which usually happens in less than 4 seconds), the electrode current is proportional to the rate of arrival of oxygen molecules at the cathode, which is in turn proportional to the concentration of oxygen outside the membrane.
[http://www.instechlabs.com/oxygen.html]