Reference calomel

Consider a liquid membrane that exhibits a Nernstian response for ions and is immersed in a solution with a K ion activity of flK (5)- A reference calomel electrode is connected with this solution by a saturated KCl liquid bridge. The whole system is depicted schematically in fig. 4.9. The gate voltage, Vq, is given by... 

Lead in water may he analyzed very precisely at low concentrations hy anodic stripping voltametry using an electrochemical analyzer static or controlled growth mercury drop electrodes, reference calomel or silver-silver chloride electrodes and silica or TEE cells. Copper, silver, gold, and certain organic compounds may interfere in the test. (APHA, AWWA and WEE. 1998. Standard Methods for the Examination of Water and Wastewater, 20 ed. Washington, D.C. American Public Health Association.)... 

A calomel electrode (a), and a glass electrode (b). The pH meter commonSy used in chemical and biological laboratories often employs a glass electrode which is immersed in the unknown solution, and is used with a reference calomel electrode. 

FIGURE 4.8 Laboratory platinum electrode and reference calomel electrode. (1) Platinum wire of 1.024 mm diameter, (2) waterproof epoxy, (3) triple-distilled mercury, (4) glass tubing, (5) silicon sealant covered with heat-shrink tubing, (6) test tube, (7) saturated KCl, (8) calomel-mercury-KCl paste, (9) mercury, (10) saturated KCl, (11) salt bridge, and (12) copper wire. 

Potentiometric measurements for the evaluation of Na" activity coefficients were carried out using a Drion BD1 Analyser with a Orion IMa-electrode in conjunction with a reference calomel electrode and a water JacKeted titration cell. 

The electrolysis vessel, C, la protected from mercury Ions diffusing from the working reference calomel electrode. A, by a medium glass frit between B and C, and a fine frit backed with an agar plug between B and A. Between runs, cell C is kept filled with saturated potassium chloride solution. 

Incidentally, a quantity called the rational potential is defined as E for the mercury-water interface (no added electrolyte) so, in general, = E + 0.480 V if a normal calomel reference electrode is used. 

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. 

Calomel Electrodes Calomel reference electrodes are based on the redox couple between Hg2Cl2 and Hg (calomel is a common name for Hg2Cl2). 

If the copper electrode is the indicator electrode in a potentiometric electrochemical cell that also includes a saturated calomel reference electrode... 

When the potential of an electrode of the first kind responds to the potential of another ion that is in equilibrium with M"+, it is called an electrode of the second kind. Two common electrodes of the second kind are the calomel and silver/silver chloride reference electrodes. Electrodes of the second kind also can be based on complexation reactions. Eor example, an electrode for EDTA is constructed by coupling a Hg +/Hg electrode of the first kind to EDTA by taking advantage of its formation of a stable complex with Hg +. 

Determine the parts per million of F in the tap water, (b) For the analysis of toothpaste a 0.3619-g sample was transferred to a 100-mL volumetric flask along with 50.0 mL of TISAB and diluted to volume with distilled water. Three 20.0-mL aliquots were removed, and the potential was measured with an L ion-selective electrode using a saturated calomel electrode as a reference. Live separate 1.00-mL additions of a 100.0-ppm solution of L were added to each, measuring the potential following each addition. 

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. 

Measuring electrodes for impressed current protection are robust reference electrodes (see Section 3.2 and Table 3-1) which are permanently exposed to seawater and remain unpolarized when a small control current is taken. The otherwise usual silver-silver chloride and calomel reference electrodes are used only for checking (see Section 16.7). All reference electrodes with electrolytes and diaphragms are unsuitable as long-term electrodes for potential-controlled rectifiers. Only metal-medium electrodes which have a sufficiently constant potential can be considered as measuring electrodes. The silver-silver chloride electrode has a potential that depends on the chloride content of the water [see Eq. (2-29)]. This potential deviation can usually be tolerated [3]. The most reliable electrodes are those of pure zinc [3]. They have a constant rest potential, are slightly polarizable and in case of film formation can be regenerated by an anodic current pulse. They last at least 5 years. 

Potential control with zinc reference electrodes presented a problem because deposits of corrosion products are formed on zinc in hot water. This caused changes in the potential of the electrode which could not be tolerated. Other reference electrodes (e.g., calomel and Ag-AgCl reference electrodes) were not yet available for this application. Since then, Ag-AgCl electrodes have been developed which successfully operate at temperatures up to 100°C. The solution in the previous case was the imposition of a fixed current level after reaching stationary operating conditions [27]. 

The electroreductive cyclization of the furanone 118 (R = -(CH2)4CH=CH— COOMe Scheme 36) using a mercury pool cathode, a platinum anode, a saturated calomel reference electrode, and a degassed solution of dry CH3CN containing -Bu4NBr as the electrolyte, gave the spirocyclic lactones 119 and 120 in a ratio 1.0 1.1 (Scheme 37)(91T383). 

The electrolysis is carried out at a reference potential of -2.4 volts vs a standard calomel electrode. An initial current density of 0.0403 amp/cm is obtained which drops to 0.0195 amp/cm at the end of the reduction, which is carried on over a period of 1,682 minutes at 15° to 20°C. The catholyte is filtered, the solid material is washed with water and dried. 430 g of the 2,3-bis-(3-pyridyl)-butane-2,3-diol is recrystallized from water, MP 244° to 245°C. 

These values are roughly constant across a range of electrolyte environments except where noted but the variations between alloys, heat treatment conditions, etc. creates a range for each metal. For some metals such as iron and steel the range is low ( 100 mV), but for lead, nickel, stainless steels a range is given. The corrosion potential is reported with respect to the saturated calomel reference electrode. 

Stainless steel pipes (buried in the ground) and the interiors of stainless steel heat exchangers have been successfully cathodically protected, but CP is rarely used for materials other than steel. The protection potential usually adopted for steel is —850 mV to the saturated calomel reference electrode. This varies with temperature and the presence of other aggressive species in the environment. 

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