A method for determining the concentration of a reduced (or oxidised) form of a
redox species in an
electrochemical cell of the kind comprising a
working electrode and a counter
electrode spaced from the
working electrode by a predetermined distance, said method comprising the steps of: (1) applying an
electric potential difference between the electrodes; (2) selecting the potential of the
working electrode such that the rate of electro-oxidation of the reduced form (or electro-reduction of the oxidised form) of the species is
diffusion controlled, (3) selecting the spacing between the working
electrode and the counter
electrode so that reaction products from the counter electrode arrive at the working electrode; (4) determining current as a function of time after application of the potential and prior to achievement of a
steady state; (5) estimating the magnitude of the
steady state current, and (6) obtaining from the change in current with time and the magnitude of the
steady state current, a value indicative of the
diffusion coefficient and / or of the concentration of the reduced form (or the oxidised form) of the species. Also disclosed is an apparatus for determining the concentration of a
redox species in an
electrochemical cell comprising: an
electrochemical cell having a working electrode and a counter (or counter / reference) electrode, means for applying and
electric potential difference between said electrodes, means for measuring the change in current with time, and characterised in that the working electrode is spaced from the counter electrode by less than 500 mum.