Reaction cell, potentiometric sensors

Besides, potentiometric sensors with ion-selective ionophores in modified poly(vinyl chloride) (PVC) have been used to detect analytes from human serum [128], Cellular respiration and acidification due to the activity of the cells has been measured with CMOS ISFETS [129], Some potentiometric methods employ gas-sensing electrodes for NH3 (for deaminase reactions) and C02 (for decarboxylase reactions). Ion-selective electrodes have also been used to quantitate penicillin, since the penicillinase reaction may be mediated with I or GST. 

This anodic reaction provides sodium ions and electrons to the solid electrolyte and the inert Pt counter electrode, respectively, at the source side. Both the sodium ions and electrons will then travel through the solid electrochemical cell along previously-mentioned ionic and electronic paths to sustain the PEVD cathodic reaction for Na COj product formation at the sink side. Eurthermore, based on anodic reaction 60, the chemical potential of sodium is fixed by the vapor phase at the source side. Under open circuit conditions, this type of source can also serve as the reference electrode for a CO potentiometric sensor. 

Potentiometric sensor is based on a redox reaction that occurs at the electrode-electrolyte interface in an electrochemical cell. If a redox reaction Ox + Ze Red takes place at an electrode surface, it is called a halfcell reaction. In the above reaction. Ox is the oxidant. Red is the reduced product, e in the electron, and Z is the number of electrons transferred in the reaction. At thermodynamic quasiequilibrium conditions, the Nernst equation is applicable and can be expressed as ... 

When a redox reaction. Ox + Ze = Red, takes place at an electrode surface in an electrochemical cell, a potential may develop at the electrode-electrolyte interface. This potential may then be used to quantify the activity (or concentration) of the species involved in the reaction forming the fundamental of potentiometric sensors. 

Potentiometric sensors can be classified based on whether the electrode is inert or active. An inert electrode does not participate in the half-cell reaction and merely provides the surface for the electron transfer or provides a catalytic surface for the reaction. However, an active electrode is either an ion donor or acceptor in the reaction. In general, there are three types of active electrodes the metal/metal ion, the metal/insoluble salt or oxide, and metal/metal chelate electrodes. 

Noble metals such as platinum and gold, graphite, and glassy carbon are commonly used as inert electrodes on which the half-cell reaction of interest takes place. To complete the circuitry for the potentiometric sensor, the other electrode is usually a reference electrode on which a noninterference half-cell reaction occurs. Silver/silver chloride and calomel electrodes are the most commonly used reference electrodes. Calomel consists of Hg/HgClj and is less desirable for biomedical systems in terms of the toxicity of mercury. 

Electrochemistry works using the principles of oxidation-reduction reactions which generate electric currents or, more simply, the conversion of chemical information into an electrical signal. Electrochemical cells or sensors usually contain a working electrode, to which a potential is applied, and a reference electrode. The oxidation-reduction reaction that ensues is then recorded as an electric current which is a measurement of the analyte from the reaction. Electrochemical methods can be further subdivided into amperometric (measures current), potentiometric (measures potential), conductometric (measures the conductive properties of the medium), impedimetric (measures resistance and reactance) or field effect (measures current through charge accumulation at a gate electrode). ... 

In the case of the potentiometric sensor this means the construction of a chain, whose cell reaction does not involve valence changes. This principle led to the CO2 sensors presented in Section 7.2 with open reference electrodes and zero sensitivity to oxygen. 

In the early part of this century, many types of solid electrolyte had already been reported. High conductivity was found in a number of metal halides. One of the first applications of solid electrolytes was to measure the thermodynamic properties of solid compounds at high temperatures. Katayama (1908) and Kiukkola and Wagner (1957) made extensive measurements of free enthalpy changes of chemical reactions at higher temperatures. Similar potentiometric measurements of solid electrolyte cells are still made in the context of electrochemical sensors which are one of the most important technical applications for solid electrolytes. 

The potential profiles in this PEVD system are illustrated in Figure 17. Although there is no driving force due to a difference in the chemical potential of sodium in the current PEVD system, the applied dc potential provides the thermodynamic driving force for the overall cell reaction (62). Consequently, electrical energy is transferred in this particular PEVD system to move Na COj from the anode to the cathode of the solid electrochemical cell by two half-cell electrochemical reactions. In short, this PEVD process can be used to deposit Na CO at the working electrode of a potentiometric CO sensor. 

Amperometric sensing of gases is based on solid ion-conducting materials, as described for potentiometric gas sensors. Solid-state amperometric gas sensors measure the limiting current (ij) flowing across the electrochemical cell upon application of a fixed voltage so that the rate of electrode reaction is controlled by the gas transport across the cell. The diffusion barrier consists of small-hole porous ceramics. The limiting current satisfies the relationship ... 

Electrochemical gas sensors detect gases based on the electromotive force(EMF) or the current of an electrochemical cell due to the electrochemical reaction of a particular gas. Solid electrolyte which a specific ion can selectively permeate is used as a diaphragm. Potentiometric type gas sensors have been most widely adopted. Among them potentiometric oxygen sensors composed of partial stabilized zirconia have already had practical application and heen extensively used for the feedback control of the air-fuel ratio of automobile engines. The oxygen sensor elements are composed of the following electrochemical cell. 

Amperometric sensors In contrast to potentiometric measurements where the monitored parameter, the cell potential, arises from spontaneous reactions, in amperometry the cell reaction is driven by an external fixed potential, and the current is monitored. With these sensors, in the idealized specific sensor case, the signal resulting from a redox reaction is proportional to the concentration of the analyte species. Cells can be either two-electrode (working and reference) or three-electrode (working, counter, and... 

Electrochemical sensors are based on potentiometric, amperometric or conductimetric cells that generate signals from electrochemical reactions of the analyte or in response to the presence of particular chemical species related to it. 

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