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develops across the interface between the solution containing the analyte and a liquid-ion exchanger that selectively bonds with the analyte ion. 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. .- - - - employs as the membrane a water-immiscible liquid which will selectively bond the ion being determined.

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CHARACTERISTICS OF SELECTED LIQUID-MEMBRANE ELECTRODES .

Na+ = 0.6.= 0. Cl.10.1.5.14 I. Na+ = 6 x 10-5. Fe2= = 3. Na+ = 0.00056. SO4.005. ClO4- Cl- Dimethyldioctadecylammonium chloride Tris(substituted 1.= 17.= 17.07. OH. F. 10phenanthroline)iron(II) perchlorate Tridodecylhexadecylammonium nitrate 100 10-5 3 10 ClO4- 100 10-5 4 10 O3- 100 10-5 3 .8. Mg2+ = 0.013.< 10-5.= 0. Li+ = 0.2. NO3. Na+ = 0.01. Cl. Br= 0.0042. Mg2+ = 2 x 10-4 Zn2+ = 3. HCO3.012. Li+ = 2 x 10-4 I.00022.0015.= 1 I.= 0. NO3.= 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+ = 3.015 Valinomcin 100 10-6 3 10 NH4+ = 0.12 .5.Analyte ion Active membrane material Nonactin/monactin Concentration range (M) 10-1 10-5 Recommended pH range 5 8 Selectively coefficients NH4+ K+ = 0.= 0. Fe2+ = 0. H+ = 0.= 1. NO2.= 0.002.14.19. Br.= 0. Cu2+ = 3. Br.1.= 0.= 4. SO4= 0.2.

At each membrane surface. the calcium compound establishes an equlibrium with its ions: [(RO)2PO2]2Ca 2(RO)2PO2. giving rise to a potential described by the equation: . [(CH3(CH2)8CH2O)2PO2]2Ca.The membrane consists of liquid calcium di(n-decyl) phosphate.+ 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. immobilized in a thin disk of polyvinyl chloride that cannot be penetrated by water.

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

049 V.64 x 10-4 M KNO3 has an electrode potential of 0. Enough potassium nitrite is added to the solution to make its concentration 4. Calculate the selectivity of the electrode for nitrate ions.017 V.76 x 10-2 M without changing the volume. The new electrode potential is -0.A nitrate-ion electrode in 1. .

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

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Enough sodium perchlorate is added to the solution to make its concentration 5. .023 V.56 x 10-4 M NaClO4 has an electrode of 0. Calculate the selectivity of the electrode for perchlorate over chlorate ions. The new electrode potential is -0.03 x 10-2 M without changing the volume.A perchlorate-ion electrode in 2.037 V.

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

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98 x 10-4 M AgNO3 has an electrode potential of 0. The new electrode potential is -0. .056 V.A nitrate-ion electrode in 7. The selectivity of nitrate over nitrite ions is 85. Enough silver nitrate is added to the solution without changing the volume. Calculate the concentration of the nitrite ion after the addition of silver nitrate.024 V.

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

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