Sensing electrode response

In contrast to direct potentiometry, the potentiometric titration technique offers the advantage of high accuracy and precision, although at the cost of increased time and increased consumption of titrants. Another advantage is that the potential break at the titration endpoint must be well defined, but the slope of the sensing electrode response need be neither reproducible nor Nernstian, and the actual potential values at the endpoint are of secondary interest. In many cases, this allows for the use of simplified sensors. 

Most suitable would be the use of a perfectly NH4+ ion-selective glass electrode however, a disadvantage of this type of enzyme electrode is the time required for the establishment of equilibrium (several minutes) moreover, the normal Nernst response of 59 mV per decade (at 25° C) is practically never reached. Nevertheless, in biochemical investigations these electrodes offer special possibilities, especially because they can also be used in the reverse way as an enzyme-sensing electrode, i.e., by testing an enzyme with a substrate layer around the bulb of the glass electrode. 

Orion Model 95-64). In practice, one simply determines E ntot by calibration with a standard solution without the necessity of knowing the various constants mentioned. The S02 electrode allows the determination of concentrations down to 10 8 Af with a response time of a few minutes. From the above it appears that the gas-sensing electrodes show Nemstian behaviour provided that the concentrations to be measured are not high there is little or no interference by other components in the sample solution. 

It is clear from the Nemst equation that the temperature of the solution affects the response slope (2.303A7//0 of the calibration curve. The electrode voltage changes linearly in relationship to changes in temperature at a given pH therefore, the pH of any solution is a function of its temperature. For example, the electrode response slope increases from 59.2mV/pH at 25°C to 61.5 mV/pH at a body temperature of 37°C. For modem pH sensing systems, a temperature probe is normally combined with the pH electrode. The pH meter with an automatic temperature compensation (ATC) function automatically corrects the pH value based on the temperature of the solution detected with the temperature probe. 

Gas-sensing electrodes differ from ion-selective electrodes in that no species in solution can interfere with the electrode response as only gases can diffuse through the membrane. However, it should be noted that any gas which causes a pH change in the internal electrolyte solution will affect electrode response. 

Tissue electrodes [2, 3, 4, 5, 45,57], In these biosensors, a thin layer of tissue is attached to the internal sensor. The enzymic reactions taking place in the tissue liberate products sensed by the internal sensor. In the glutamine electrode [5, 45], a thick layer (about 0.05 mm) of porcine liver is used and in the adenosine-5 -monophosphate electrode [4], a layer of rabbit muscle tissue. In both cases, the ammonia gas probe is the indicator electrode. Various types of enzyme, bacterial and tissue electrodes were compared [2]. In an adenosine electrode a mixture of cells obtained from the outer (mucosal) side of a mouse small intestine was used [3j. The stability of all these electrodes increases in the presence of sodium azide in the solution that prevents bacterial decomposition of the tissue. In an electrode specific for the antidiuretic hormone [57], toad bladder is placed over the membrane of a sodium-sensitive glass electrode. In the presence of the antidiuretic hormone, sodium ions are transported through the bladder and the sodium electrode response depends on the hormone concentration. 

Zirconia solid electrolyte and zinc oxide sensing electrodes were used as a high-temperature NOx sensor [470, 471]. The response of the electrode potential was linear for the logarithm of NOx (NO) concentration from 40 to 450 ppm. 

Electrochemical Reaction/Transport. Electrochemical reactions occur at the electrode/electrolyte interface when gas is brought to the electrode surface using a small pump. Gas diffuses through the electrode structure to the electrode/electrolyte interface, where it is electrochemically reacted. Some parasitic chemical reactions can also occur on the electrocatalytic surface between the reactant gas and air. To achieve maximum response and reproducibility, the chemical combination must be minimized and controlled by proper selection of catalyst sensor potential and cell configuration. For CO, water is required to complete the anodic reaction at the sensing electrode according to the following reaction ... 

The reactant gas must diffuse through the electrode structure which contains air (02, N2) and any products of reaction (CO2, N02, NO, H2O vapor, etc.). Response characteristics are dependent on electrode material, Teflon content, electrode porosity, thickness and diffusion/reaction kinetics of the reactant gas on the catalytic surface. By optimizing catalytic activity for a given reaction and controlling the potentiostatic voltage on the sensing electrode, the concentration of reactant gas can be maintained at essentially zero at the electrode/electrolyte interface. All reactant species arriving at the electrode/electrolyte interface will be readily reacted. Under these conditions, the rate of diffusion is proportional to C, where... 

Response Time. The response-time curve for oxidation of CO with an SPE sensor cell having a platinoid sensing electrode is shown in Figure 8. Similar curves for the oxidation of N0 and reduction of N02 with an SPE cell having a graphite sensing electrode are also shown in Figure 8. All measurements were made at 25°C at gas flow of 60 cc/min. The current-time response can be estimated from the relationship... 

Table II is a list of gases which could potentially interfere with an N0 analysis along with the concentrations of these gases which produce a signal equivalent to 1 ppm N0. Only H2S had an effect on sensor cell performance and was found to decrease the response level by 0.2 a/ppm. H2S, SO2 and NO2 were effectively filtered from the gas stream by use of triethanolamine (TEA) as shown in Table II. To prevent TEA vapors from reaching (and thus poisoning) the sensing electrode surface, a short column of a cation exchange bead was placed after the filter.

Sensing performance for H-,. Sensing performance of the amperometric sensor was examined for the detection of H2 in air. Figure 3 shows the response curve for 2000 ppm H2 in air at room temperature. The response was studied by changing the atmosphere of the sensing electrode from an air flow to the sample gas flow. With air the short circuit current between two electrodes was zero. On contact with the sample gas flow, the current increased rapidly. The 90% response time was about 10 seconds and the stationary current value was 10yUA. When the air flow was resumed, the current returned to zero within about 20 seconds. 

Step 2 is usually limited by the permeability of the membrane. In certain sensor designs, the membrane is eliminated to avoid this step. Step 4 refers to the diffusion of the solvated gas in the electrolyte to the electrode-electrolyte interface. Diffusion in liquids is often considerably slower than diffusion across a membrane. If the sensing electrode is flooded with electrolyte, the response is slow because the gas must diffuse through the electrolyte before reaching the reaction surface. 

CO sensor allows detection of CO in the presence of hydrocarbons and other adsorbable contaminants. The membrane Is usually chosen for Its ability to protect the sensing electrode. However, If It has low permeability to air, the sensor will have a slower response time. The electrolyte and counter electrode have also been reported as Influencing selectivity and device performance In the determination of hydrazines (5) and NO2 (9), respectively. Finally, materials of construction are typically Teflon and high-density plastics like polypropylene because such materials must be compatible with reactive gases and corrosive electrolytes. 

A potentiometric L-lhreonine selective sensor for determining L-threonine in biological fluids and foods utilizes threonine deaminase in conjunction with an NH3 gas-sensing electrode. The biosensor exhibits a linear response to l-threonine concentration over the 0.1-200 mM range (292). Comparing l-tryptophan bacteria and immobilized enzyme electrodes shows that the enzyme probe is stable for less than 5 days but that the bacterial probe functions for approximately 3 weeks (293). 

An electrode for the determination of L-aspaitate is constructed by chemical immobilization of L-aspartase on an ammonia gas-sensing probe. The electrode response is linear in the concentration range 0.7-20 mM with aslope of—59 mV/ decade. The biosensor is stable for more than 20 days (299). 

This type of bulk property detector monitors the conductivity of the eluent. All ions from the analyte and from the buffer contribute to produce a signal. Detector response is linear over a wide range. Cell resistance is inversely proportional to electrolyte concentration. Since AC voltages must be used to avoid polarization of the sensing electrodes, the physical quantity measured is impedance, not resistance. 

White et al. synthesized nanometric La2Cu04 through three techniques auto-ignition, Pechini method, and coprecipitation (White et al., 2008). The NPs were used to fabricate sensing electrodes for NO, and the effect of electrode microstructure on the sensitivity and response time was studied. The response times of the sensors were exponentially dependent on electrode grain size. Sensors with fine-grained electrodes were able to produce a steady-state and consistent voltage at lower temperatures, which improved their response sensitivity. 

Figure 22. (A) The assembly of a nitrate-sensing electrode by the cross-linking of an affinity complex formed between nitrate reductase (cytochrome-dependent, EC 1.9.6.1), NR and an Fe(III)-protoporphyrin reconstituted de novo four-helix-bundle protein. (B) Cyclic voltammograms of the NR-two heme-reconstituted de novo protein-layered Au electrode at nitrate concentrations of (a) 0, (b) 12, (c) 24, (d) 46 and (e) 68 mM. Inset calibration curve for the amperometric response of the electrode at different nitrate concentrations (at E = —0.48 V vs. SCE). Potential scan rate, 5 mV s" 0.1 M phosphate buffer, pH 7.0, under argon electrode roughness factor, ca. 20.

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