-

employs as the membrane a water-immiscible liquid which will selectively bond the ion being determined. it is similar to the glass pH electrode in that it contains an internal silver-silver chloride electrode and an internal reference solution or fixed composition. has a hydrophobic membrane impregnated with a hydrophobic ion exchanger (called an ionophore) that is selective for analyte ion. develops across the interface between the solution containing the analyte and a liquid-ion exchanger that selectively bonds with the analyte ion.

CHARACTERISTICS OF SELECTED LIQUID-MEMBRANE ELECTRODES

Analyte ion

Active membrane material

Nonactin/monactin

Concentration range (M)

10-1 10-5

Recommended pH range
58

Selectively coefficients

NH4+

K+ = 0.12 ; Na+ = 0.002; Li+ = 0.0042; Mg2+ = 2 x 10-4 Zn2+ = 3.2; Fe2+ = 0.8; Mg2+ = 0.14; Na+ = 0.003

Ca2+

Calcium di(n-decyl)phosphate

100 10-6

6 10

Ca2+ + Mg2+ (divalent cation)

K+

Similar to that for Ca2+ electrode

10-2 10-5

6 10

Zn2+ = 3.5; Fe2= = 3.5; Cu2+ = 3.1; Na+ = 0.015

Valinomcin

100 10-6

3 10

NH4+ = 0.013; H+ = 0.01; Na+ = 6 x 10-5; Li+ = 2 x 10-4 I- = 17; NO3- = 4.2; Br- = 1.6; HCO3- = 0.19; F- = 0.10; SO4= 0.14 I- = 0.012; NO3- = 0.0015; Br= 0.00056; Cl- = 0.00022; OH- = 1 I- = 17; Br- = 0.1; NO2- = 0.07; Cl- = 0.005; SO4- < 10-5; ClO4-

Cl-

Dimethyldioctadecylammonium chloride Tris(substituted 1, 10phenanthroline)iron(II) perchlorate Tridodecylhexadecylammonium nitrate

100 10-5

3 10

ClO4-

100 10-5

4 10

NO3-

100 10-5

38

The membrane consists of liquid calcium di(n-decyl) phosphate, [(CH3(CH2)8CH2O)2PO2]2Ca, immobilized in a thin disk of polyvinyl chloride that cannot be penetrated by water. At each membrane surface, the calcium compound establishes an equlibrium with its ions: [(RO)2PO2]2Ca 2(RO)2PO2- + Ca2+
where r is the n-decyl hydrocarbon chain. It is important to recognize that the didecylphosphate anion is fixed part of the nonaqueous liquid membrane. Since the concentration of calcium ions in the solutions on each of the membrane surface may be different also, giving rise to a potential described by the equation:

Collecting the constants into a single term as was done gives:

A nitrate-ion electrode in 1.64 x 10-4 M KNO3 has an electrode potential of 0.017 V. Enough potassium nitrite is added to the solution to make its concentration 4.76 x 10-2 M without changing the volume. The new electrode potential is -0.049 V. Calculate the selectivity of the electrode for nitrate ions.

the value of Q can be calculated from this equation using the electrode potential measured with no nitrate present:

or

A perchlorate-ion electrode in 2.56 x 10-4 M NaClO4 has an electrode of 0.023 V. Enough sodium perchlorate is added to the solution to make its concentration 5.03 x 10-2 M without changing the volume. The new electrode potential is -0.037 V. Calculate the selectivity of the electrode for perchlorate over chlorate ions.

the value of Q can be calculated from this equation using the electrode potential measured with no perchlorate present:

or

A nitrate-ion electrode in 7.98 x 10-4 M AgNO3 has an electrode potential of 0.056 V. Enough silver nitrate is added to the solution without changing the volume. The new electrode potential is -0.024 V. Calculate the concentration of the nitrite ion after the addition of silver nitrate. The selectivity of nitrate over nitrite ions is 85.

the value of Q can be calculated from this equation using the electrode potential measured with no nitrate present:

or

Thank you for listening. Till next time