Reference electrodes, aqueous solutions

For a two-electrode cell, the net reaction comprises two half-reactions, involving the processes at the two electrodes. As already mentioned, usually only one of these processes is of interest, and this occurs at the working electrode in dynamic electrochemistry experiments or indicator electrode in equilibrium (potentiometric) experiments. The other electrode is made up such that it maintains a constant composition throughout the measurement, thus providing a reference potential. The most common reference for aqueous solution is the saturated calomel electrode (SCE), depicted in Fig. 1, and this provides... 

Figure 3-21 CV of 50mM paranitrobenzoic acid (PNBA) on smooth Ag electrodes. Aqueous solution, 0.1 M NajSO scan rate, 50mV/s. (Adapted from Reference 15.)...

Figure 5. Cyclic voltammetry of cobalt bishistidine (1 mM) in aqueous saline solution containing 0.1 M sodium borate (pH 9). Sweep rate 50 mVs . Reference electrode SCE. Solution degassed with N2.

Experimentally, the aqueous iron(II) is titrated with cerium(IV) in aqueous solution in a burette. The arrangement is shown in Figure 4.6, the platinum indicator electrode changes its potential (with reference to a calomel half-cell as standard) as the solution is titrated. Figure 4.7 shows the graph of the cell e.m.f. against added cerium(IV). At the equivalence point the amount of the added Ce (aq) is equal to the original amount of Fe (aq) hence the amounts of Ce (aq) and Fe (aq) are also equal. Under these conditions the potential of the electrode in the mixture is ( - - f)/2 this, the equivalence point, occurs at the point indicated. 

Reference electrode based on the reduction of Hg2Cl2 to Hg in an aqueous solution saturated with KCl that is,... 

One example of a liquid-based ion-selective electrode is that for Ca +, which uses a porous plastic membrane saturated with di-(n-decyl) phosphate (Figure 11.13). As shown in Figure 11.14, the membrane is placed at the end of a nonconducting cylindrical tube and is in contact with two reservoirs. The outer reservoir contains di-(n-decyl) phosphate in di- -octylphenylphosphonate, which soaks into the porous membrane. The inner reservoir contains a standard aqueous solution of Ca + and a Ag/AgCl reference electrode. Calcium ion-selective electrodes are also available in which the di-(n-decyl) phosphate is immobilized in a polyvinyl chloride... 

Combination silver—silver salt electrodes have been used in electrochemistry. The potential of the common Ag/AgCl (saturated)—KCl (saturated) reference electrode is +0.199 V. Silver phosphate is suitable for the preparation of a reference electrode for the measurement of aqueous phosphate solutions (54). The silver—silver sulfate—sodium sulfate reference electrode has also been described (55). 

When the activity of the ion M"+ is equal to unity (approximately true for a 1M solution), the electrode potential E is equal to the standard potential Ee. Some important standard electrode potentials referred to the standard hydrogen electrode at 25 °C (in aqueous solution) are collected in Table 2.5.5... 

As indicator electrodes glass and antimony electrodes are commonly used, but it must be noted that in benzene-methanol solutions, a glass-antimony electrode pair may be used in which the glass electrode functions as reference electrode. Glass electrodes should not be maintained in non-aqueous solvents for long periods, as the hydration layer of the glass bulb may be impaired and the electrode will then cease to function satisfactorily. 

Both lead ion and dichromate ion yield a diffusion current at an applied potential to a dropping mercury electrode of —1.0 volt against the saturated calomel electrode (S.C.E.). Amperometric titration gives a V-shaped curve [Fig. 16.14 (C)]. The exercise described refers to the determination of lead in lead nitrate the application to the determination of lead in dilute aqueous solutions (10-3 — 10-4lVf) is self-evident. 

Several significant electrode potentials of interest in aqueous batteries are listed in Table 2 these include the oxidation of carbon, and oxygen evolution/reduction reactions in acid and alkaline electrolytes. For example, for the oxidation of carbon in alkaline electrolyte, E° at 25 °C is -0.780 V vs. SHE or -0.682 V (vs. Hg/HgO reference electrode) in 0.1 molL IC0 2 at pH [14]. Based on the standard potentials for carbon in aqueous electrolytes, it is thermodynamically stable in water and other aqueous solutions at a pH less than about 13, provided no oxidizing agents are present. 

Changes in the reference electrode junction potential result from differences in the composition of die sample and standard solutions (e.g., upon switching from whole blood samples to aqueous calibrants). One approach to alleviate this problem is to use an intermediate salt bridge, with a solution (in the bridge) of ions of nearly equal mobility (e.g., concentrated KC1). Standard solutions with an electrolyte composition similar to that of the sample are also desirable. These precautions, however, will not eliminate the problem completely. Other approaches to address this and other changes in the cell constant have been reviewed (13). 

Instead of using an indicator, an ion-sensitive electrode can be used. An aqueous solution is titrated potentiometrically against 0.04 N hyamine 1622 solution using a nitrate ion-selective electrode and a silver/silver chloride reference electrode [106]. 

Thus when using the she scale one chooses as the reference state of electrons (and assigns the zero value to it) the state of an electron at the Fermi level of a metal electrode in equilibrium with an aqueous solution of pH=0 and Ph2=1 atm at 25°C. 

The experimental setup is shown in Figure 9.23. The Pt-black catalyst film also served as the working electrode in a Nafion 117 solid polymer electrolyte cell. The Pt-covered side of the Nafion 117 membrane was exposed to the flowing H2-02 mixture and the other side was in contact with a 0.1 M KOH aqueous solution with an immersed Pt counterelectrode. The Pt catalyst-working electrode potential, Urhe (=Uwr)> was measured with respect to a reversible reference H2 electrode (RHE) via a Luggin capillary in contact with the Pt-free side of the Nafion membrane. 

Table 1.6. Potentials of common reference electrodes in aqueous solution. ...

Photovoltaic response parameters for electrodeposited (polycrystalline) CdTe thin film electrodes in sulfide-polysulfide or alkaline sodium telluride PEC have been reported, primarily with no reference to the stability of the cells [100], In view of the instability of CdTe in aqueous solutions, Bhattacharya and Rajeshwar [101] employed two methods for the characterization of their electrodeposited CdTe-based PEC. In the first one, a coating of Pb02 (-100 nm thick) was deposited on the CdTe film surface by electroless deposition, and the coated films... 

Voltammetric experiments without external solution were carried out using a 0-pipette with one barrel filled with an aqueous solution and the second barrel filled with organic phase. In a two-electrode setup, voltage was applied between Ag/AgCl and Ag/AgTPBCl reference electrodes inserted in two barrels. 

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