Where E is the potenal, E° is a constant dependent on the electrode/sensor system, R is the gas
constant, T is the absolute temperature, F is Faraday’s constant, (n) is the valence (posive or
negave charge) for the ion being measured, and (a) is the acvity of that ion.
The Nernst equaon can be rewrien as:
E = E° + S log a
Where S replaces the constant term which denes the slope of the sensor. The slope is the
change in millivolts per tenfold change in the acvity of the analyte. For a posively-charged
monovalent ion, the theorecal slope would be 59.1 mV at 25°C.
The second concept is Acvity versus Concentraon where ion-selecve electrodes measure
acvity rather than concentraon. Acvity (a) is related to concentraon (c) through the acvity
coecient (γ). It is wrien as:
a = γc
Note: While ion acvies, which reect free rather than total ion concentraons,
are the physiologically relevant quanty, acvity values are converted to
convenonal concentraon units so that values obtained by direct ISE
measurements can be compared to values obtained from methods that measure
total ion concentraons. The laer includes the indirect methods, which have
acvity coecients close to unity or one, and ame photometric, atomic
absorpon and traon methods.
Amperometric sensors
In amperometric measurements, a potenal is applied to the measuring electrode while current
generated by the resulng oxidaon or reducon reacons in the test system is measured. The
current generated is directly proporonal to the concentraon of the analyte. An enzyme can be
added to a layer on or near an amperometric sensor to produce electroacve species from
analytes of interest that cannot themselves be oxidized or reduced.
Conductometric sensors
In conductometric measurements, an alternang current is applied between two electrodes in
contact with the test soluon and the resulng voltage dierence is measured. The conducvity
of the soluon is proporonal to the magnitude of the voltage dierence. In aqueous soluons,
conducvity is dependent upon the concentraon of electrolytes; an increase in the electrolyte
concentraon causes an increase in conducvity.
Determinaon of analyte concentraon
Potenometric and amperometric sensors are used for the determinaon of analyte concentraon. For
both sensors, the concentraon of the analyte can be calculated using:
1. The known value of the analyte concentraon in the calibrant soluon
2. The measured voltage (potenometric) or current (amperometric) signal generated by the analyte in
the calibrant
3. The measured signal generated by the analyte in the test soluon
For potenometric sensors, the analyte acvity in the sample is calculated from the Nernst equaon
according to:
E
sample
- E
calibrant
= S log (a
sample
/a
calibrant
)
92
i-STAT Alinity — System Operaons Manual Art: 745524-01 Rev. I Rev. Date: 02-Nov-2022