Mercury-mercurous electrode

We will discuss four types of reference electrodes hydrogen, calomel, silver-silver chloride, and mercury-mercurous electrodes. 

The electrode potential of this type of electrode is defined by the concentration (activity) of the anions. They are used in corrosion engineering as standard half-cells or reference electrodes. In corrosion engineering practice they are called secondary reference electrodes to differentiate them from the hydrogen electrode, which is a primary reference electrode. The following electrodes of the second kind are of interest in electrochemical and corrosion studies calomel electrode, silver-silver chloride electrode, and mercury-mercurous electrode. 

Reference Electrodes and Liquid Junctions. The electrical cincuit of the pH ceU is completed through a salt bridge that usually consists of a concentrated solution of potassium chloride [7447-40-7]. The solution makes contact at one end with the test solution and at the other with a reference electrode of constant potential. The Hquid junction is formed at the area of contact between the salt bridge and the test solution. The mercury—mercurous chloride electrode, the calomel electrode, provides a highly reproducible potential in the potassium chloride bridge solution and is the most widely used reference electrode. However, mercurous chloride is converted readily into mercuric ion and mercury when in contact with concentrated potassium chloride solutions above 80°C. This disproportionation reaction causes an unstable potential with calomel electrodes. Therefore, the silver—silver chloride electrode and the thallium amalgam—thallous chloride electrode often are preferred for measurements above 80°C. However, because silver chloride is relatively soluble in concentrated solutions of potassium chloride, the solution in the electrode chamber must be saturated with silver chloride. 

The mercurous sulfate [7783-36-OJ, Hg2S04, mercury reference electrode, (Pt)H2 H2S04(y ) Hg2S04(Hg), is used to accurately measure the half-ceU potentials of the lead—acid battery. The standard potential of the mercury reference electrode is 0.6125 V (14). The potentials of the lead dioxide, lead sulfate, and mercurous sulfate, mercury electrodes versus a hydrogen electrode have been measured (24,25). These data may be used to calculate accurate half-ceU potentials for the lead dioxide, lead sulfate positive electrode from temperatures of 0 to 55°C and acid concentrations of from 0.1 to Sm. 

However, in the case of stress-corrosion cracking of mild steel in some solutions, the potential band within which cracking occurs can be very narrow and an accurately known reference potential is required. A reference half cell of the calomel or mercury/mercurous sulphate type is therefore used with a liquid/liquid junction to separate the half-cell support electrolyte from the process fluid. The connections from the plant equipment and reference electrode are made to an impedance converter which ensures that only tiny currents flow in the circuit, thus causing the minimum polarisation of the reference electrode. The signal is then amplifled and displayed on a digital voltmeter or recorder. 

Fig. 5.6 (Left) Comparison of band energy levels for different II-VI compounds. Note the high-energy levels of ZnSe. Representation is made here for electrodes in contact with 1 M HQO4. The reference is a saturated mercury-mercurous sulfate electrode, denoted as esm (0 V/esm = +0.65 V vs. SHE). (Right) Anodic and cathodic decomposition reactions for ZnSe at their respective potentials (fidp, Fdn) and water redox levels in the electrolytic medium of pH 0. (Adapted from [121])...

Similar designs are used for other REs on the basis of poorly soluble mercury compounds (1) the mercury-mercurous sulfate RE with H2SO4 or K2SO4 solutions saturated with Hg2S04, for which = 0.6151V and (2) the mercury-mercuric oxide RE, for measuring electrode potentials in alkaline solutions, with KOH solution saturated with HgO, for which = 0.098 V and E = 0.920 V. 

In selecting reference electrodes for practical use, one should apply two criteria that of reducing the diffusion potentials and that of a lack of interference of RE components with the system being studied. Thus, mercury-containing REs (calomel or mercury-mercuric oxide) are inappropriate for measurements in conjunction with platinum electrodes, since the mercury ions readily poison platinum surfaces. Calomel REs are also inappropriate for systems sensitive to chloride ions. 

It is also important to understand how the potential gradient between an electrode and the bulk solution is established and controlled. Because the potential difference between the electrode and the bulk solution is not measurable, a second electrode must be employed. Although in general the potential difference between an electrode and solution cannot be determined, the potential difference between two electrodes in that solution can be determined. If the solution electrode potential difference of one of the electrodes is held constant by maintaining a rapid redox couple such as silver-silver chloride or mercury-mercurous chloride (calomel), then the potential... 

Figure 4.4 The saturated calomel electrode. A platinum wire makes electrical contact with an electrode which is composed of a paste of metallic mercury, mercuric chloride (calomel) and potassium chloride. A saturated solution of potassium chloride completes the half-cell and provides electrical contact through a porous plug.

Basically, the calomel electrode consists of mercury, mercurous chloride (calomel), and chloride ion. The concentration of potassium chloride is 0.1 M in an aqueous-organic solvent (50 50) of the same nature as that contained in the solution to be investigated. The junction with the test solution is realized either with a capillary or a porous stone. When the capillary is used, a small hydrostatic pressure is maintained inside it in order to avoid any electrode contamination by the test solution. In the main part of our investigation, the porous stone junction was used. Moreover, the calomel electrode is thermostatted at 20°C, and temperature variations of this electrode giving appreciable emf variations involve uncertainty on the pon determination on the order of 0.2-0.3 poH unit/ 10°C. 

Mercury-Mercurous Sulfate Electrode. In this reference electrode the metal is mercury, the sparingly soluble compound is mercurous sulfate (Hg2S04), and the source of S04 anions is sulfuric acid or potassium sulfate. The electrode is made in the same way as a calomel electrode, and it is represented as... 

MetaUInsoluble Salt/Ion Electrodes. Electrode potentials are usually reported relative to normal hydrogen electrode (NHE a(H+) = 1, p(H2) = 1), but they are actually measured with respect to a secondary reference electrode. Frequently used secondary reference electrodes are calomel, silver-silver chloride, and mercury-mercurous sulfate electrodes. These secondary reference electrodes consist of a metal M covered by a layer of its sparingly soluble salt MA immersed in a solution having the same anion Az as the sparingly soluble MA. The generalized reference electrode of this type may be represented as M MA AZ and may be considered to be composed of two interfaces one between the metal electrode M and the metal ions Mz+ in the salt MA... 

The mercury-mercurous chloride (calomel) electrode. The calomel electrode was used extensively as a chloride electrode, but it has been all but abandoned for this purpose in favor of the silver chloride electrode. The fixed-potential saturated or 3.5 M KC1 calomel electrode always has been popular for use with glass electrodes in pH measurements and in polarographic work most of the vast compilations of aqueous polarographic half-wave potentials were referred to the aqueous saturated calomel electrode (SCE). 

The mercury-mercuric oxide electrode. The mercury-mercuric oxide electrode is uniquely well behaved among metal-metal oxide electrodes.32 The potential of the cell... 

The mercury-mercurous sulfate electrode. Several commercial suppliers offer the mercury-mercurous sulfate electrode with a saturated potassium sulfate electrolyte. The potential (E° + E ) of this electrode system is 0.658 V on the hydrogen scale at 22°C.34 The electrode constitutes one-half of the Weston standard cell,35 an international secondary voltage standard, and is outstanding in reproducibility,36 in spite of the slight tendency of mercurous sulfate to hydrolyze and its rather high solubility. 

A mercury/mercurous sulfate (Hg/Hg2S04) reference electrode A voltmeter... 

The hydrogen half-cell is not very convenient for routine laboratory usage—indeed, 1 m H+ (corresponding to a pH of 0 ) and 1 atm H2 (explosive) are dangerous. Hence, secondary standards are used, e.g., mercury/mercurous (calomel) or silver/silver chloride electrodes, which have midpoint redox potentials of 0.244 V and 0.222 V, respectively. 

Halogen Electrodes.—The determination of the standard potentials of the halogens is simple in principle it involves measurement of the potential of a platinum electrode, coated with a thin layer of platinum or iridium black, dipping in a solution of the halogen acid or a halide, and surrounded by the free halogen. The uncertainty due to liquid junction can be avoided by employing the appropriate silver-silver halide or mercury-mercurous halide electrode as reference electrode. In practice, however, difficulties arise because of the possibility of the reactions... 

If chloride ions must be avoided, a mercury mercurous sulfate electrode [Hg/ Hg2S04(s), K2S04(s) E = 0.621 V versus NHE] may be employed. In alkaline solution a mercury mercuric oxide electrode (E = 0.098 versus NHE) may be useful. 

Anodic stripping voltammetry (ASV) with the tubular mercury graphite electrode (TMGE) possesses adequate sensitivity and precision under repeated use to characterize zinc in San Diego Bay water. The TMGE, made by electrolysis of a mercuric nitrate solution to form a thin mercury film inside a graphite tube, is described elsewhere (I). 

Another way of developing1 equation (5) is as follows. The calomel electrode is essentially a mercury-mercurous ion Hg Hg+ electrode and its potential follows the relation... 

The peak around —0.38 V versus mercury/mercurous sulfate reference electrode (MSE), during the negative sweep, is associated to gold species whereas the one at —0.8 V versus MSE corresponds to platinum species. For pure catalysts, with an upper potential limit of +0.25 V versus MSE, the charge values of 493 and 543 pC cm-2 were obtained for platinum and gold, respectively (Figure 21.7).43,44 The atomic content of the Pt-Au nanoparticles can be deduced as follows ... 

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