Reference electrode permeability

In principle the ISO-NOP sensor works as follows. The sensor is immersed in a solution containing NO and a positive potential of —860 mV (vs Ag/AgCl reference electrode) is applied. NO diffuses across the gas permeable/NO-selective membrane and is oxidized at the working electrode surface producing a redox current. This oxidation proceeds via an electrochemical reaction followed by a chemical reaction. The electrochemical reaction is a one-electron transfer from the NO molecule to the electrode, resulting in the formation of the nitrosonium cation ... 

The concentration of gases such as C02, NH3, S02 andN02 in aqueous solutions can be measured with an electrode consisting of a glass electrode/reference electrode pair inside a plastic tube which is sealed with a thin gas-permeable membrane and containing an appropriate electrolyte solution (Figure 6.5). 

In a further development, an ADH-MB-NAD/polypyrrole electrode, a platinum counter electrode and an Ag/AgCl reference electrode were assembled and covered with a gas-permeable polymer membrane to form an gaseous ethanol sensor. This appears to be the first time that a complete enzyme sensor for gaseous ethanol has been fabricated in such a manner with NAD incorporated in immobilized form. 

The schematic diagram of a gas-sensing electrode is illustrated in Figure 16.8, that comprises of essentially a reference electrode (E), a specific-ion electrode (B), and an internal electrolyte solution (F) contained in a cylindrical plastic tube (G). One end of the plastic tubing is provided with a thin, replaceable, gas-permeable membrane that separates the internal electrolyte solution from the external solution containing gaseous analyte. However, the exact composition and specifications of this gas-permeable membrane is usually described by its respective manufacturers. It is normally made up of a thin microporous film fabricated from a hydrophobic plastic material. 

The dissolved oxygen content of a solution can be determined by measuring the diffusion current that results at a selected voltage. The Clark electrode was developed for this purpose and various modifications have subsequently been introduced. It consists basically of a platinum electrode separated from the sample by a membrane which is permeable to oxygen, e.g. Teflon or polyethylene. A reference electrode of silver/silver chloride in potassium chloride is used to complete the system (Figure 4.21). When a voltage that is sufficient to give the... 

Figure 18.2—Measurement of pH. The concentration of H+ ions can be determined from the potential difference between the reference electrode and the glass electrode. Details of the membrane, which is permeable to the H1 ion, are shown. When an H+ ion forms a silanol bond, a sodium ion moves into the solution to preserve electroneutrality. A cross-section of the membrane showing this exchange reaction is presented (IUPAC conventions are not followed to improve clarity in the diagram). Prior to its use, the pH meter is calibrated with a buffer solution of known pH.

New polymer membrane-based ISEs for nitrate and carbonate exhibit detection limits and selectivities that may be applicable for ocean measurements. In addition, a number of these ISEs can be used as internal transducers for the design of useful potentiometric gas sensors. For example, dissolved C02 can be detected potentiometrically by using either a glass membrane electrode or a polymer-based carbonate ISE, in conjunction with an appropriate reference electrode, behind an outer gas permeable membrane. Novel differential pC02 sensors based on two polymer membrane-type pH sensors have also been developed recently. 

Use an ammonia electrode (Orion Model 95-10, Beckman Model 39565 or equivalent) along with a readout device, such as a pH meter with expanded millivolt scale between -700 mV and +700 mV or a specific ion meter. The electrode assembly consists of a sensor glass electrode and a reference electrode mounted behind a hydrophobic gas-permeable membrane. The membrane separates the aqueous sample from an ammonium chloride internal solution. Before analysis, the sample is treated with caustic soda to convert any NH4+ ion present in the sample into NH3. The dissolved NH3 in the sample diffuses through the membrane until the partial pressure of NH3 in the sample becomes equal to that in the internal solution. The partial pressure of ammonia is proportional to its concentration in the sample. The diffusion of NH3 into the internal solution increases its pH, which is measured by a pH electrode. The chloride level in the internal standard solution remains constant. It is sensed by a chloride ion-selective electrode which serves as the reference electrode. 

Gas-selective electrodes are a particularly important application of the glass electrode. For example, the carbon dioxide electrode is a self-contained system with a glass electrode and a concentric silver-silver chloride electrode enclosed by a C02 permeable membrane. The latter holds a thin film of bicarbonate solution in contact with the glass membrane, which provides a junction to the silver/silver chloride reference electrode. The electrode, which is illustrated schematically by Figure 2.2, has found extensive application in monitoring C02 levels in blood and probably will find increasing application in other systems that require continuous measurement of C02 partial pressures. The electrode response is based on the reaction... 

An important specialized type of voltammetric system is a self-contained cell for the determination of 02 in the gas or solution phases. This is the so-called Clark electrode,66,67 which consists of a platinum or gold electrode in the end of a support rod that is covered by an 02 permeable membrane (polyethylene or Teflon) such that a thin film of electrolyte is contained between the electrode surface and the membrane. A concentric tube provides the support for the membrane and the means to contain an electrolyte solution in contact with a silver-silver chloride reference electrode. The Clark device has found extensive application to monitor 02 partial pressure in blood, the atmosphere, and in sewage plants. By appropriate adjustment of the applied potential it gives a voltammetric current plateau that is directly proportional to the 02 partial pressure. The membrane material prevents interference from electroactive ions as well as from surface-contaminating biological materials. Figure 3.19 illustrates one configuration for this important device. 

Figure 5.41 Selective-ion electrodes (a) glass membrane (b) liquid ion exchange (c) homogeneous solid membrane (d) heterogeneous solid membrane (e) solid membrane without reference electrode (/) gas-permeable membrane 1, sensing electrode 2, electrolyte, 2(e) ohmic contact, 2(f) gas-permeable membrane 3, membrane sur-port 4, reference electrode, 4(f) outer electrode body, 5(b) liquid ion exchanger 5(f) electrode body 6(b) reference electrode body, 6(f) electrolyte 7, liquid junction.

Gas sensors usually incorporate a conventional ion-selective electrode surrounded by a thin film of an intermediate electrolyte solution and enclosed by a gas-permeable membrane. An internal reference electrode is usually included, so that the sensor represents a complete electrochemical cell. The gas (of interest) in the sample solution diffuses through the membrane and comes to equilibrium with the internal electrolyte solution. In the internal compartment, between the membrane and the ion-selective electrode, the gas undergoes a chemical reaction, consuming or forming an ion to be detected by the ion-selective electrode. (Protonation equilibria in conjunction with a pH electrode are most common.) Since the local activity of this ion is proportional to the amount of gas dissolved in the sample, the electrode response is directly related to the concentration of the gas in the sample. The response is usually linear over a range of typically four orders of magnitude the upper limit is determined by the concentration of the inner electrolyte solution. The permeable membrane is the key to the electrode s gas selectivity. Two types of polymeric material, microporous and homogeneous, are used to form the... 

Potentiometry is the measurement of an electrical potential difference between two electrodes (half-ceUs) in an electrochemical cell (Figure 4-1) when the cell current is zero (galvanic cell). Such a cell consists of two electrodes (electron or metallic conductors) that are connected by an electrolyte solution (ion conductor). An electrode, or half-cell, consists of a single metallic conductor that is in contact with an electrolyte solution. The ion conductors can be composed of one or more phases that are either in direct contact with each other or separated by membranes permeable only to specific cations or anions (see Figure 4-1). One of the electrolyte solutions is the unknown or test solution this solution may be replaced by an appropriate reference solution for calibration purposes. By convention, the cell notation is shown so that the left electrode (Mi,) is the reference electrode the right electrode (Mr) is the indicator (measuring) electrode (see later equation 3). ... 

If the polarizing voltage of the PO2 electrode is reversed, making the platinum electrode positive (anode) relative to the Ag/AgCl reference electrode, and if the gas permeable membrane is replaced with a hydrophilic membrane containing the immobilized enzyme, it is possible to oxidize the H202 produced by the glucose oxidase ... 

Figure 21-17 illustrates the essential features of a potentiometric gas-sensing probe, which consists of a tube containing a reference electrode, a selective ion electrode, and an electrolyte solution. A thin, replaceable, gas-permeable membrane attached to one end of the tube serves as a barrier between the internal and analyte solutions. As can be seen from Figure 21-17, this device is a complete electrochemical cell and is more properly referred to as a probe rather than an electrode, a term that is frequently encountered in advertisements by instrument manufacturers. Gas-sensing probes have found widespread use in the determination of dissolved gases in water and other solvents. 

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