Liquid-Based Ion-Selective Electrodes

Another class of ion-selective electrodes uses a hydrophobic membrane that contains a liquid
organic complexing agent that reacts selectively with the analyte. Three types of organic
complexing agents have been used: cation exchangers, anion exchangers, and neutral ionophores.
A membrane potential exists if the analyte’s activity is different on the two sides of the
membrane. Current is carried through the membrane by the analyte. One example of a liquid-
based ion-selective electrode is that for Ca2+, which uses a porous plastic membrane saturated
with the cation exchanger di-(n-decyl)phosphate. As shown in Figure 1, the membrane is placed
at the end of a non-conducting cylindrical tube and is in contact with two reservoirs. The outer
reservoir contains di-(n-decyl)phosphate in di-n-octylphenylphosphonate, which soaks into the
porous membrane. The inner reservoir contains a standard aqueous solution of Ca2+ and a
Ag/AgCl reference electrode. Calcium ion-selective electrodes also are available in which the di-
(n-decyl)phosphate is immobilized in a polyvinyl chloride (PVC) membrane that eliminates the
need for the outer reservoir. The membrane potential for the Ca2+ ISE develops as the result of a
difference in the extent of the complexation reaction:
-
Ca++ (aq) + 2(C10H21O)2PO2 (mem) ===== Ca[(C10H21O)2PO2]2 (mem)
on the two sides of the membrane, where (mem) indicates a species that is present in the
membrane. The cell potential for the Ca2+ ion-selective electrode is.
Ecell = K + 0.05916 log aCa++ / 2

Figure 1: Schematic diagram showing a liquid-based ion-

selective electrode for Ca2+. The structure of the cation
exchanger, di-(n-decyl) phosphate, is shown in red.
The selectivity of this electrode for Ca2+ is very good, with only Zn2+ showing greater selectivity.
An electrode using a liquid reservoir can be stored in a dilute solution of analyte and needs no
additional conditioning before use. The lifetime of an electrode with a PVC membrane, however,
is proportional to its exposure to aqueous solutions. For this reason these electrodes are best
stored by covering the membrane with a cap along with a small amount of wetted gauze to
maintain a humid environment. Before using the electrode it is conditioned in a solution of
analyte for 30–60 minutes.

Gas-Sensing Electrodes

A number of membrane electrodes respond to the concentration of a dissolved gas. The basic
design of a gas-sensing electrode, as shown in Figure 2, consists of a thin membrane that
separates the sample from an inner solution that contains an ion-selective electrode. The
membrane is permeable to the gaseous analyte, but impermeable to nonvolatile components in
the sample’s matrix. The gaseous analyte passes through the membrane where it reacts with the
inner solution, producing a species whose concentration is monitored by the ion-selective
electrode. For example, in a CO2 electrode, CO2 diffuses across the membrane where it reacts in
the inner solution to produce H3O+.
-
CO2 (aq ) + 2H2O (liq) ===== HCO3 + H3O+ (aq) ------------- (1)

Ecell = K + 0.0592 log aH+ ----------------------------------- (2)

The change in the activity of H3O+ in the inner solution is monitored with a pH electrode, for
which the cell potential is given by equation 2. To find the relationship between the activity of
H3O+ in the inner solution and the activity of CO2 in the inner solution we rearrange the
equilibrium constant expression for reaction above; thus a

------------------- (3)
-
Where; Ka is the equilibrium constant. If the activity of HCO3 in the internal solution is
sufficiently large, then its activity is not affected by the small amount of CO2 that passes through
the membrane. Substituting equation 3 into equation 2 gives:
Ecell = K′ + 0. 05916 log aCO
2

Where; K′ is a constant that includes the constant for the pH electrode, the equilibrium constant
-
for reaction 1 and the activity of HCO3 in the inner solution. Table 4 lists the properties of
several gas-sensing electrodes. The composition of the inner solution changes with use, and both
the inner solution and the membrane must be replaced periodically. Gas-sensing electrodes are
stored in a solution similar to the internal solution to minimize their exposure to atmospheric
gases.
Potentiometric Biosensors:

The approach for developing gas-sensing electrodes can be modified to create potentiometric
electrodes that respond to a biochemically important species. The most common class of
potentiometric biosensors are enzyme electrodes, in which we trap or immobilize an enzyme at
the surface of a potentiometric electrode. The analyte’s reaction with the enzyme produces a
product whose concentration is monitored by the potentiometric electrode. Potentiometric
biosensors also have been designed around other biologically active species, including
antibodies, bacterial particles, tissues, and hormone receptors. One example of an enzyme
electrode is the urea electrode, which is based on the catalytic hydrolysis of urea by urease.
-
CO(NH2)2 (aq) + 2H2O (liq ) ======== 2NH4+ ( aq) + CO3 (aq)

Figure A shows one version of the urea electrode, which modifies a gas sensing NH3 electrode
by adding a dialysis membrane that traps a pH 7.0 buffered solution of urease between the
dialysis membrane and the gas permeable membrane. When immersed in the sample, urea
diffuses through the dialysis membrane where it reacts with the enzyme urease to form the
ammonium ion, NH4+, which is in equilibrium with NH3.

2NH4+ ( aq) + 2H2O (liq ) ========= H2O (aq) + NH3 (aq)

The NH3, in turn, diffuses through the gas permeable membrane where a pH electrode measures
the resulting change in pH. The electrode’s response to the concentration of urea is:

Ecell = K - 0.05916 log aurea

Another version of the urea electrode (Figure B) immobilizes the enzyme urease in a polymer
membrane formed directly on the tip of a glass pH electrode. In this case the response of the
electrode is:
pH = K . aurea
Few potentiometric biosensors are available commercially. As shown in Figure A and Figure B,
however, it is possible to convert an ion selective electrode or a gas-sensing electrode into a
biosensor. Several representative examples are described in Table below:
Figure A: Schematic diagram showing an enzyme-based Figure B: Schematic diagram of an enzyme-based
potentiometric biosensor for urea. A solution of the potentiometric biosensor for urea in which urease is
enzyme urease is trapped between a dialysis membrane immobilized in a polymer membrane coated onto the pH-
and a gas permeable membrane. Urea diffuses across sensitive glass membrane of a pH electrode.
the dialysis membrane and reacts with urease,
producing NH3 that diffuses across the gas permeable
membrane. The resulting change in the internal
solution’s pH is measured with the pH electrode.