Liquid-Membrane

Electrode
Liquid-Membrane Electrode
 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 Concentration range Recommended pH Selectively coefficients
material (M) range

NH4+ Nonactin/monactin 10-1 – 10-5 5–8 K+ = 0.12 ; Na+ = 0.002; Li+ =

0.0042; Mg2+ = 2 x 10-4

Ca2+ Calcium di(n-decyl)- 100 – 10-6 6 – 10 Zn2+ = 3.2; Fe2+ = 0.8; Mg2+ =
phosphate 0.14; Na+ = 0.003

Ca2+ + Mg2+ Similar to that for Ca2+ 10-2 – 10-5 6 – 10 Zn2+ = 3.5; Fe2= = 3.5; Cu2+ =
(divalent electrode 3.1; Na+ = 0.015
cation)

K+ Valinomcin 100 – 10-6 3 – 10 NH4+ = 0.013; H+ = 0.01; Na+

= 6 x 10-5; Li+ = 2 x 10-4

Cl- Dimethyldioctadecyl- 100 – 10-5 3 – 10 I- = 17; NO3- = 4.2; Br- = 1.6;

ammonium chloride HCO3- = 0.19; F- = 0.10; SO4-
= 0.14
ClO4- Tris(substituted 1, 10- 100 – 10-5 4 – 10 I- = 0.012; NO3- = 0.0015; Br-
phenanthroline)iron(II) = 0.00056; Cl- = 0.00022;
perchlorate OH- = 1
NO3- Tridodecylhexadecyl- 100 – 10-5 3–8 I- = 17; Br- = 0.1; NO2- = 0.07;
ammonium nitrate Cl- = 0.005; SO4- < 10-5; ClO4-
 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:
Example Problem 1
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
Example Problem 2
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
Example Problem 3
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
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Thank you for
listening. Till
next time… 