Reference saturated calomel

Lu et al. have described a single sweep voltammetric method for the determination of chlorpromazine at carbon paste electrodes [176]. Powdered tablet was dissolved in and diluted to 100 mL with water, whereupon a 10 mL portion of the solution was mixed with 10 mL of acetate buffer solution (pH 5.3). This solution was then diluted to 100 mL. The solution was analyzed using an electrolytic cell equipped with a carbon paste working electrode, a reference saturated calomel electrode, and a platimun counter-electrode. The voltammogram was recorded by single sweep scanning from 0 to 1 V, with a scanning rate of 10 mV/sec. 

TABLE 12. Half-wave reduction potential of some organic halides (after Reference 117) and halosilanes (after Reference 116) using a reference saturated calomel electrode... 

A three-electrode system with a platinum working (H), a platinum auxiliary (K) and a reference saturated calomel electrode (I was placed in a U-type compartment (M) in an isothermal water bath (E). Two platinum wires jointing with the working and auxiliary electrodes, respectively, straight reached to electrolyte outside and connected to two copper wires which linked with the electrochemical workstation (B). The reference electrode was used to track the change in potential of electrode (H). A thermo-sensitive resistor (L)... 

Figure 16. Current and mass with respect to potential for a Prussian blue film in a KCl solution during a linear potential scan. Experimental conditions were as follows pH 2.8, KCl concentration 0.5 M, scan rate 20 mV s and reference saturated calomel electrode (SCE) (potential limits from +0.6 to —0.2 V and from —0.2 to +0.6 V). From Gabrielli et al. ...

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

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. 

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). 

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. 

Various types of reference electrodes have been considered in Section 20.3, and the potentials of these electrodes and their variation with the activity of the electrolyte are listed in Table 21.7, Chapter 21. It is appropriate, however to point out here that the saturated calomel electrode (S.C.E.), the silver-silver chloride electrode and the copper-copper sulphate electrode are the most widely used in corrosion testing and monitoring. 

The mechanism of the action of metallic copper was investigated by Streicher who determined the potential of a Type 314 stainless steel, the redox potential of the solution (as indicated by a platinised-Pt electrode) and the potential of the copper. The actual measurements were made with a saturated calomel electrode, but the results reported below are with reference to S.H.E. In the absence of copper the corrosion potential of the stainless steel was 0-58 V, whereas the potential of the Pt electrode was... 

A basic circuit is shown schematically in Fig. 19.36(a). The specimen C., or working electrode W.E. is the metal under study, the auxiliary electrode A.E. is usually platinum and R.E. is the reference electrode, for instance a saturated calomel electrode. The desired potential difference between the specimen and the reference electrode is set with the backing circuit B. Any... 

If a controlled-potential determination is to be carried out, additional equipment will be required, namely an electronic voltmeter, a potentiostat and a reference electrode. The latter is most commonly a saturated calomel electrode, the construction of which is described in Chapter 14. 

Apparatus. The source of current is a potentiostat which is used in conjunction with a reference electrode (commonly a saturated calomel electrode) to control the potential of the working electrode. The circuit will be essentially that shown in Fig. 12.2(a) but with the addition of the integrator or of a coulometer. 

Ey and E2 are the indicator electrodes. These may consist of a tungsten pair for a biamperometric end point for an amperometric end point they may both be of platinum foil or one can be platinum and the other a saturated calomel reference electrode. The voltage impressed upon the indicator electrodes is supplied by battery B (ca 1.5 volts) via a variable resistance Rs N records the indicator current. For a potentiometric end point Ey and E2 may consist of either platinum-tungsten bimetallic electrodes, or Ey may be an S.C.E. and E2... 

Apparatus. Use the apparatus of Section 14.7. The generator anode is of pure silver foil (3 cm x 3 cm) the cathode in the isolated compartment is a platinum foil (3 cm x 3 cm) bent into a half-cylinder. For the potentiometric end point detection, use a short length of silver wire as the indicator electrode the electrical connection to the saturated calomel reference electrode is made by means of an agar-potassium nitrate bridge. 

The most widely used reference electrode, due to its ease of preparation and constancy of potential, is the calomel electrode. A calomel half-cell is one in which mercury and calomel [mercury(I) chloride] are covered with potassium chloride solution of definite concentration this may be 0.1 M, 1M, or saturated. These electrodes are referred to as the decimolar, the molar and the saturated calomel electrode (S.C.E.) and have the potentials, relative to the standard hydrogen electrode at 25 °C, of 0.3358,0.2824 and 0.2444 volt. Of these electrodes the S.C.E. is most commonly used, largely because of the suppressive effect of saturated potassium chloride solution on liquid junction potentials. However, this electrode suffers from the drawback that its potential varies rapidly with alteration in temperature owing to changes in the solubility of potassium chloride, and restoration of a stable potential may be slow owing to the disturbance of the calomel-potassium chloride equilibrium. The potentials of the decimolar and molar electrodes are less affected by change in temperature and are to be preferred in cases where accurate values of electrode potentials are required. The electrode reaction is... 

To measure the hydrogen ion concentration of a solution the glass electrode must be combined with a reference electrode, for which purpose the saturated calomel electrode is most commonly used, thus giving the cell ... 

So-called combination electrodes may be purchased in which the glass electrode and the saturated calomel reference electrode are combined into a single unit, thus giving a more robust piece of equipment, and the convenience of having to insert and support a single probe in the test solution instead of the two separate components. 

Prepare an approximately 0.1 M silver nitrate solution. Place 0.1169 g of dry sodium chloride in the beaker, add 100 mL of water, and stir until dissolved. Use a silver wire electrode (or a silver-plated platinum wire), and a silver-silver chloride or a saturated calomel reference electrode separated from the solution by a potassium nitrate-agar bridge (see below). Titrate the sodium chloride solution with the silver nitrate solution following the general procedure described in Experiment 1 it is important to have efficient stirring and to wait long enough after each addition of titrant for the e.m.f. to become steady. Continue the titration 5 mL beyond the end point. Determine the end point and thence the molarity of the silver nitrate solution. 

Place the prepared copper acetate solution in the beaker and add 10 mL of 20 per cent potassium iodide solution. Set the stirrer in motion and add distilled water, if necessary, until the platinum plate electrode is fully immersed. Use a saturated calomel reference electrode, and carry out the normal potentiometric titration procedure using a standard sodium thiosulphate solution as titrant. 

Titration assembly. The electrode system consists of a mercury electrode and a saturated calomel [or, in some cases, a mercury-mercury(I) sulphate] reference electrode, both supported in a 250 mL Pyrex beaker. Provision is made for magnetic stirring and the potential is followed by means of an electronic millivoltmeter or an auto-titrator. 

The H-type cell devised by Lingane and Laitinen and shown in Fig. 16.9 will be found satisfactory for many purposes a particular feature is the built-in reference electrode. Usually a saturated calomel electrode is employed, but if the presence of chloride ion is harmful a mercury(I) sulphate electrode (Hg/Hg2 S04 in potassium sulphate solution potential ca + 0.40 volts vs S.C.E.) may be used. It is usually designed to contain 10-50 mL of the sample solution in the left-hand compartment, but it can be constructed to accommodate a smaller volume down to 1 -2 mL. To avoid polarisation of the reference electrode the latter should be made of tubing at least 20 mm in diameter, but the dimensions of the solution compartment can be varied over wide limits. The compartments are separated by a cross-member filled with a 4 per cent agar-saturated potassium chloride gel, which is held in position by a medium-porosity sintered Pyrex glass disc (diameter at least 10 mm) placed as near the solution compartment as possible in order to facilitate de-aeration of the test solution. By clamping the cell so that the cross-member is vertical, the molten... 

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. 

Data are also available with a-acetylenic aliphatic sulphones, which involve only two steps i.e., saturation of the triple bond without subsequent cleavage of the Caliphalic—S bond, since it is not reactive. However, the introduction of an aromatic ring to the S02 group does not lead, contrary to what is observed with enones, to a potential shift toward less reducing potential values. Thus, the aromatic moiety introduced apparently does not bring any additional conjugation effect but even seems to decrease the activation of the unsaturated bond, as shown by data in Tables 6 and 7 where most of the potentials refer to the same saturated calomel electrode under similar experimental conditions. 

In these reactions, (2) is the process taking place at the reference electrode which therefore determines the potential scale. In practice other reference electrodes, such as the saturated calomel electrode are frequently used but the data are normally expressed on the hydrogen scale. 

All potentials refer to a standard hydrogen electrode in the used solvent. Exemptions are stated explicitly. Potential reported versus a saturated calomel electrode, converted assuming iiscE=-0-241 V vs. SHE. 

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