9184sc Theory of Operation
38
It is also important to notice that the dissociation constants are temperature-dependent
(the equipment takes into account this element).
The amperometric sensor consists of:
•
a gold working electrode (cathode) where the main reaction occurs
•
a silver counter-reference electrode (anode)
•
KCl electrolyte
•
a microporous membrane selective to HOCl
The HOCl molecules in the sample diffuse through the membrane to a thin region between
the membrane and the cathode that contains the electrolyte.
A constant potential is applied to the working electrode where HOCl is reduced according
to the reaction:
+
HOCl
H
+
At the silver electrode (anode) the silver is oxidized to Ag
–
2Cl
2Ag
+
The reduction in HOCl at the cathode generates a current that is directly proportional to its
partial pressure in the sample.
The electrochemical reaction and diffusion through the membrane are dependent upon
temperature. Consequently, the measurement cell contains a temperature sensor that
allows for automatic temperature compensation.
In the acidification version an additional analyzer version offers the possibility to measure
samples with a high pH value. The sample pH is kept constant between 5.5 and 6.5 by
continuously adding acid solution. At such pH levels, all ClO
enabling the sensor to measure TFC.
–
–
→
2e
Cl
H
O
+
+
2
+
–
→
2AgCl
2e
+
+
:
–
ions turn into HOCl, thus