Ionic compounds sensors

In the discussion so far, the diffusional and electrical fluxes of the ionic and electronic carriers were treated separately. However, as will become amply clear in this section and was briefly touched upon in Sec. 5.6, in the absence of an external circuit such as the one shown in Fig. 7.7, the diffusion of a charged species by itself is very rapidly halted by the electric field it creates and thus cannot lead to steady-state conditions. For steady state, the fluxes of the diffusing species have to be coupled such that electroneutrality is maintained. Hence, in most situations of great practical importance such as creep, sintering, oxidation of metals, efficiency of fuel cells, and solid-state sensors, to name a few, it is the coupled diffusion, or ambipolar diffusion, of two fluxes that is critical. To illustrate, four phenomena that are reasonably well understood and that are related to this coupled diffusion are discussed in some detail in the next subsections. The first deals with the oxidation of metals, the second with ambipolar diffusion in general in a binary oxide, the third with the interdiffusion of two ionic compounds to form a solid solution. The last subsection explores the conditions for which a solid can be used as a potentiometric sensor. 

In the electrochemical community at that period the research on ion selective electrodes (ISE) was very active and the idea to extend the range of sensors to non electrochemical active compounds, and even to non ionic compounds, like glucose, has been very well accepted. We saw at that time the possibility to extend much more the research activity. The groups active in ISE development have been definitively the first to shift to the development of electroanalytical biosensors. 

In the most common method, the solution is irradiated with near-ultraviolet radiation (200-400 nm) to decompose organic matter by means of a radical formation mechanism. Then the generated CO2 is transported toward the detector with a carrier gas. In order to eliminate some ionic compounds that can interfere with the measurement, a membrane is placed before the detector. The detection is carried out either by the measurement of conductivity via a sensor or by a nondispersive infrared analyzer. In this online system, the sample analysis takes aroimd 6 min. Other systems based on the same principle have also been described. In this case the oxidation and detection are produced in the same chamber. In this "batch" apparatus the sample is trapped and analyzed for 3-30 min. With this latter system, some ionic species other than H and HCO3 can interfere with the conductivity readings. Species such as Ti02 [85,90] and persulfate [91,121] have been used as catalysts present as a diluted suspension in water. The TOC is obtained from the difference between the conductivities for the irradiated and nonirradiated samples. 

Indicators can be directly immobilized onto the tip of an optical fiber, or trapped between the fiber and a semi-permeable membrane. Configuration (a) in Figure 4.33 facilitates mass transfer and consequently decreases the response time of the sensor. Configuration (b), however, prevents interference from other substances because of the presence of the semi-permeable membrane. When gaseous compounds are determined, a hydrophobic membrane can prevent the access of ionic compounds to the reactive agent, which increases the sensor selectivity. The membrane can also be tubular (c). In this case, the diameter and thickness of the membrane must be as small as... 

Today, the term solid electrolyte or fast ionic conductor or, sometimes, superionic conductor is used to describe solid materials whose conductivity is wholly due to ionic displacement. Mixed conductors exhibit both ionic and electronic conductivity. Solid electrolytes range from hard, refractory materials, such as 8 mol% Y2C>3-stabilized Zr02(YSZ) or sodium fT-AbCb (NaAluOn), to soft proton-exchange polymeric membranes such as Du Pont s Nafion and include compounds that are stoichiometric (Agl), non-stoichiometric (sodium J3"-A12C>3) or doped (YSZ). The preparation, properties, and some applications of solid electrolytes have been discussed in a number of books2 5 and reviews.6,7 The main commercial application of solid electrolytes is in gas sensors.8,9 Another emerging application is in solid oxide fuel cells.4,5,1, n... 

Interesting systems, mainly with respect to solid-state optoelectronics and chalco-genide glass sensors (due to ionic conductivity effects) are found among the Group IIIB (13) and IVB (14) chalcogenides, such as the p-type semiconductors MSe (M = Ga, In, Sn), SnS, and GeX (X = S, Se, Te). Some of the IIIB compounds. 

The development of a sensor for ionized magnesium turned out to be one of the most difficult challenges of recent years. Several carriers have been designed for this purpose but none have been satisfactory. The first report of a successful measurement of ionized magnesium in an automated clinical analyzer (Thermo, prev. KONE) was published only in 1990 [30]. The ionophore ETH 5520 was used as the active compound. Two other carriers have been used since then ETH 7025 (Roche, former AVL), and a derivative of 1,10-phenenthroline (Nova). All of the magnesium sensors are based on a plastic membrane. Numerical compensations of the influence of calcium ion and the ionic strength are used due to insufficient selectivity of the magnesium sensors. 

Suitably modified fiber optic sensors can also be used for detecting gas vapors, humidity, ions, and organic compounds. Fiber inclusions that show length variation were used to develop humidity sensors, whereas ion-responsive lipid bilayers formed the basis for the detection of inorganic ions. Immobilized neutral and ionic crown ethers in polymeric membranes were designed as sensors for determination of barium and copper (Wolfbeis 2000). 

Solid-state reference electrodes for potentiometric sensors are currently under research. The main problem to be faced in developing this type of electrode lies in connecting the ionic conducting (usually aqueous) solution with an electronic conductor. Since the reference electrode has to maintain a defined potential, the electrochemical reaction with components of the electrolyte has to be avoided. Oxides, mixed oxides, and polyoxometalate salts of transition elements can be proposed for preparing solid-state reference electrodes. Tested compounds include tungsten and molybdenum oxides (Guth et al., 2009). 

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