Analysis of charge transfer Oxidation reduction reactions are characterized by transfer of electrons Oxidized + n e- reduced Charge transfer occurs

urs between electrode and the electro active species . The relation between electrode potential and equilibriu potential is given by nerst equation ! " !o + #T$% ln & electron acceptor'$&electron donor' where ! is the equilibriu !lectron transfer occurs in (el holtz layer and not on the electrode surface. easure ents potential and !o is the standard electrode potential

)on-steady state

Transient current is li*ely to give better signal to noise ratio than steady state current and hence better resolution and higher li it of detection. +n a pero etric easure ents, usually a electrode will be behind a teflon$ e brane. +t has selective diffusion. +t per its wanted analytes and prevent interfering substances. -electivity ay be due to gas diffusion e brane or an i obilized enzy e . e brane. icro eters/.

Current is proportional to the rate of diffusion. #esponse ti e of electrode is proportional to the square of thic*ness of -o thinner the e brane, faster the response.

Increasing the membrane thickness prevents the concentration gradient from penetrating beyond the outer membrane. The opposing effects must be balanced. Applications of charge transfer measurement: The Oxygen electrode The selectivity for oxygen is achieved through selection of electrode parameters Dissolved oxygen in body fluids Oxygen reduction is a complex process. Based on pH, solvents etc In aprotic media O ! e" #uperoxide In $%ueous media steps of 0 0 O ! e" H O electron transfer occur

O ! & e" H O

'or oxygen assay, & electron tranfer is preferred. #ince it gives higher current. #ince this reaction is irreversible, It leads to depletion of oxygen.

Clarks electrode (lark)s electrode* an electrode behind an oxygen permeable membrane. It also prevents electroactive and suface active substances from the sample +hich can give erroneous results. ,latinum electrode is polari-ed and oxygen is reduced at the electrode surface (urrent is proportional to the oxygen concentration in the sample $ teflon or silicon membrane of less than . micron thickness is secured +ith an O"ring or sleeve to the electrode body

Sources of error Depletion of oxygen* It is assumed that oxygen conc. Is constant at membrane sample interface and not affected by electrode reaction. In unstirred sample this is not true. #tirring can be simulated in a flo+ through cell.$ compromise has to be struck bet+een fast response and sensitivity to flo+ rate.

Oxygen depletion can harm the tissue. It also affects calibration /called li%uid 0 gas difference1. 2ith 3 micron platinum electrode and 4 micron teflon membrane, error can be .5

Interference from other electroactive species #electivity to oxygen is by choice of electrode material and polari-ing voltage #ulphur dioxide does not interfere since its potential is 3.6.3 7 +hich less than that of oxygen H #O8 ! &H! ! e" # ! 8H O If 9itric oxide or chlorine is present in significant %uantities, it could interfere since their redox potential is more anodic than oxygen. 9O ! H! ! e" 9 O ! H O (l ! e" (l" #uitable choice of membrane +hich selectively diffuse oxygen over other gases may be used 2hile measuring blood oxygen, 9itrous oxide or halothane could interfere and make incorrect estimate of patient)s blood oxygen. :esult could be inappropriate medication or fatal Nitrous oxide: 9 O! H O ! e" 9 ! OH" (ommercial oxygen sensors use silver or gold /and not platinum as clark used1. #ilver can reduce 9 O. 2ith gold electrode, after substantial use silver /from reference electrode1 may migrate By using dual voltages/"3.;.7 and "4.&.7 against #(<1 both O and 9 O can be estimated alothane: ,resence of halothane prevents reduction of oxygen causing underestimation of oxygen. By using signals from 3 ms* oxygen diffusion .3 ms O ! halothane diffusion control <lectrode control parameters are used to achieve stability, sensitivity and selectivity.2ith cells>en-ymes, these parameters could alter the output range and selectivity of biosensor time -one such as 3 ms and = .3 ms .