Calibration of coated wire electrode

Coated wire electrodes are usually calibrated by the conventional methods and preferably progressed
from concentrated to dilute solutions like other electrodes. As precautionary measure, the electrode must
be rinse after removing from solution and dip it into the deionized water for 15-20 minutes before
calibration. Reference electrode must be selected restrictly.There must not be any interference of
electrolytic solution used in salt bridge to the ions under examine.in case of any interference a double
junction can reduce the problem. In order to get more reliable results in potentiometric, two standard
solutions which includes the range of unknown, should be measure at same time. This method increases
the reliability 1-2%.

Calibration curve for CWE is following;

0.5057 Z2a I 12
−l 0 gδa=
1+3.3 ×107 a A I 12

In the equation I is the ionic strength, ZA is ionic charge and a A represents size of calibration solution.

Mechanism of coated wire electrodes (CWE) behavior

These are the basically ion selective electrodes designed by coating of polymer membrane which contains
an ionosphere (electro-active specie) to increase the efficacy against variety of ions. In general
mechanism, the lipophilic ionosphere selectively complexes with the ion under test and dissolves in
polymeric film. The ionosphere should be hydrophobic (lipophilic), otherwise they will be leaked from
membrane after contact with aqueous solution.

Fig1:Schematic diagrams sowing typical solid- contact and liquid -contact ion selective
electrodes

Freiser, H. (1986). Coated wire ion-selective electrodes. Principles and practice. 

The exact mechanism of CWEs is quite puzzling from the start and have not be studied deeply
studied like pH glass electrode. One series of studies was conducted to observe the electrical
conduction through the polymeric film. These studies show the high temperature co-efficient of
salt-polymer (polymer-dispersed salt).Some studies relate the mechanism of CWEs with the
general electrodes. The ions under the test are either present in the active membrane (as complex
or precipitate) or electrode must have to dip in solution of ions of interest, in both cases, the ions
of interest are selectively bound to the reagent present in membrane just like pH electrode. When
the electrode is immersed in solution, a boundary potential is generated at membrane-external
solution junction (interface).Again like pH electrode, the reason behind potential is migration of
ions. The ionosphere show the affinity to specific ion which is basically ion of interest.

The more significant example of CWE is potassium-ion selective electrode combined with
valinomycin ionophore. Valinomycin is antibiotic consists of crown ethers with the cage of
oxygen which selectively can make complex with potassium ions. The selectivity ratio of this
electrode for potassium is 104 than that of sodium ions.

Reference

i. James, H. J., Carmack, G., & Freiser, H. (1972). Coated wire ion-selective electrodes. Analytical
chemistry, 44(4), 856-857.
ii. Analytical chemistry,7th edition by Gary Christian
iii. Freiser, H. (1986). Coated wire ion-selective electrodes. Principles and practice. Journal of the
Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, 82(4),
1217-1221.