Instrumental Analysis (II)

Electrometric Methods of Analysis

Potentiometry 2
4th Lecture 6 Biological PHCM662
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Dr. Raafat Aly

Objectives

Types of ISEs

Solid state electrodes Liquid-based electrodes Compound electrodes

Gas-sensing electrodes Enzyme-substrate electrodes (Biosensors)

Specifications for Potentiometry

Solid-State ISEs

Solid-state ISEs are based on an inorganic solid crystal. e.g. LaF3 doped with EuF2. This creates anion vacancies in the crystal (because Eu2+ has less charge than La3+). Thus, F- ions can diffuse into the crystal and jump from one side to the other across the vacancies, increasing the conductivity of the crystal.

0.1 M NaCl and 0.1 M NaF

analyte

F- ions in the crystal are exchanged with the Fions in the internal and external solution, causing a potential difference to arise across the membrane.

Response of the F- electrode :

E constant (0.05916) log [F- ]Out

 The solid state LaF3 electrode is highly specific for F- and mainly free from interference. The only interfering species is OH- (very high pH). At low pH, F- is converted to HF which tends to form dimers and thus decreases the F- activity in the solution. Another common inorganic crystal electrode uses Ag2Spressed pellet for the membrane. This electrode responds to Ag+ and S2- ions (essentially ISE for Ag+ ).
S2- ions in the analyte solution will decrease the solubility of Ag2S. In this way it will affect the amount of Ag+ exchanged with the membrane and thus in turn the measured potential

Ag 2S 2Ag S 2

common ion effect

S 2 (analyte)

By doping the electrode with AgCl, AgBr, AgI or AgSCN, it is possible to prepare electrodes selective for Cl-, Br-, I- and SCN- anions, respectively.
On the other hand, electrodes selective for cations such as Cu2+, Cd2+ and Pb2+ can be designed by doping Ag2S with solid CuS, CdS and PbS, respectively. 4

Liquid-Based ISEs

Liquid-based ISEs are similar to the solid-state electrodes except that the solid crystal is replaced by a membrane saturated with hydrophobic liquid ion exchanger. The latter acts as a carrier or binder to transport an ion across a membrane. e.g. for the Ca2+-ISE on the left, the membrane contains Ca-Didecylphosphate (phosphate diester) dissolved in hydrophobic organic solvent. Didecylphosphate anion (phosphate diester acts as chelator) binds Ca2+ and exchange it across the membrane Equilibration of Ca2+ with the chelator establishes a voltage at the membrane-solution boundaries related to Ca2+

[( RO ) 2 PO 2 ]2 Ca 2(RO ) 2 PO 2 Ca 2
Didecylphosphate, R=C10H21

Response of the Ca 2 electrode : E constant

0.0591 log [ca 2 ]Out 5 2

Compound ISEs
1- Gas-sensing electrodes

Compound ISEs contain a normal ISE electrode surrounded by a membrane to isolate (or generate) the analyte to which the electrode responds. These electrodes can be used to measure many different gases. In CO2 gas-sensing electrode, CO2 diffuses through the gas-permeable membrane where it lower the pH in the electrolyte compartment. The response of the glass electrode to the change in pH is a direct measure of the CO2 outside the electrode. CO2(aq) + H2O H+ + HCO3-

Other acidic or basic gases, including NH3, SO2, H2S and NOx can be detected in the same manner both in solution and in the gas phase.
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2. Enzyme-substrate electrode (Biosensor) It is a sensor in which an ion-selective electrode

is covered with a coating containing an

immobilized enzyme which reacts with an organic substance (substrate) resulting in a species to which the ion-selective electrode

responds.

The well-known example is the selective detection of blood urea nitrogen

(BUN) using urease as the enzyme catalyst. The ammonium ion generated,
can then be detected by an ammonium ion-selective electrode.

NH2 - CO - NH2 2 H 2O H urease 2 NH4 HCO 3

 Similarly, enzyme reactions generating protons can be followed with glass pH electrode.

There is a multiplicity of enzyme-electrodes that can be made in this way, with substrates including glucose, penicillin and others.
O D glu cose O2 glucose oxidase D glucono 1,5 lactone H2O2 H D gluconate H
2

penicillin pencillinase penicilloi c acid H

Additional selectivity (ISE to determine the enzyme) can be attained by using composite membranes, in which an enzyme present in the outer part of the membrane catalyses a specific chemical reaction to generate product ions. These ions can be detected by an internal ion-selective membrane. Double selectivity of the enzymatic reaction and the ISE response yields a procedure that is free from most interference.
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Specifications for Potentiometry

Advantages

Linear response to analyte

over wide dynamic range Nondestructive

Short response times

Unaffected by color/turbidity (limited matrix effects) Cheap
log a

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