Magnesium-silver electrode

An electrochemical cell consists of a silver electrode in contact with 346 mL of 0.100 M AgN03 solution and a magnesium electrode in contact with 288 mL of 0.100 M Mg(N03)2 solution, (a) Calculate E for the cell at 25°C. (b) A current is drawn from the cell until 1.20 g of silver have been deposited at the silver electrode. Calculate E for the cell at this stage of operation. 

When metals are arranged in the order of their standard electrode potentials, the so-called electrochemical series of the metals is obtained. The greater the negative value of the potential, the greater is the tendency of the metal to pass into the ionic state. A metal will normally displace any other metal below it in the series from solutions of its salts. Thus magnesium, aluminium, zinc, or iron will displace copper from solutions of its salts lead will displace copper, mercury, or silver copper will displace silver. 

Many other cyclic and noncyclic organic carriers with remarkable ion selectivities have been used successfiilly as active hosts of various liquid membrane electrodes. These include the 14-crown-4-ether for lithium (30) 16-crown-5 derivatives for sodium bis-benzo-18-crown-6 ether for cesium the ionophore ETH 1001 [(R,R)-AA -bisd l-ethoxycarbonyl)undecyl-A,yVl-4,5-tctramcthyl-3,6-dioxaoctancdiamide] for calcium the natural macrocyclics nonactin and monensin for ammonia and sodium (31), respectively the ionophore ETH 1117 for magnesium calixarene derivatives for sodium (32) and macrocyclic thioethers for mercury and silver (33). 

Thus films can be divided into two groups according to their morphology. Discontinuous films are porous, have a low resistance and are formed at potentials close to the equilibrium potential of the corresponding electrode of the second kind. They often have substantial thickness (up to 1 mm). Films of this kind include halide films on copper, silver, lead and mercury, sulphate films on lead, iron and nickel oxide films on cadmium, zinc and magnesium, etc. Because of their low resistance and the reversible electrode reactions of their formation and dissolution, these films are often very important for electrode systems in storage batteries. 

Other commonly employed redox electrodes are metals such as copper, cobalt, silver, zinc, nickel, and other transition metals. Some p-block metals such as tin, lead and indium can also function as redox electrodes. However, s-block metals such as magnesium do not make good redox electrodes since the elemental metal is reactive and forms a layer of oxide coating, which leads to poor reproducibility, poor electronic conductivity and electrode potentials that are difficult to interpret, (see Section 3.3.1). 

Electrical contact between the electrode and connecting wires can be made with solder if the electrode is a refractory metal, while lower-melting-point metals such as lead, and reactive metals such as magnesium, should be joined to a connection lead with commercially available conductive silver paint . Contact to ITO-coated electrodes will similarly require this conductive paint. 

The rate of the reoxidation of Mg deposits is controlled by their morphology, which in turn depends on the substrate material. Smooth and compact deposits were obtained using silver or gold, but not nickel or copper. It was also established that the open circuit potential (OCP) of magnesium electrode (a fresh deposit on a Pt) in concentrated solutions of 5 depends strongly on the solvent used. In THE solutions with c around 1 M at 22 °C under argon atmosphere, the values of OCP for 5a, 5b and 5f were equal to —2.8, —2.73 and —2.77 V vs. Ag+/Ag, respectively-. ... 

Table 5), and several are now being used, or are potentially useful, for measuring key ocean elements. The most common use of direct potentiometry (as compared with potentiometric titrations) is for measurement of pH (Culberson, 1981). Most other cation electrodes are subject to some degree of interference from other major ions. Electrodes for sodium, potassium, calcium, and magnesium have been used successfully. Copper, cadmium, and lead electrodes in seawater have been tested, with variable success. Anion-selective electrodes for chloride, bromide, fluoride, sulfate, sulfide, and silver ions have also been tested but have not yet found wide application. 

The major serum electrolytes—sodium, potassium, calcium, magnesium, chloride, and bicarbonate (CO2)—are fairly easy to determine. The metals are most readily determined by the use of fiame-spectrophotometiic or atomic absorption methods, although colorimetric methods exist for calcium and magnesium. Calcium and, less frequently, magnesium are also titrated with EDTA. Ion-selective electrodes are used for the routine analysis of sodium, potassium, and calcium. Bicarbonate is analyzed also by titration against standard acid (see Experiment 8) in addition to a manometric method. Chloride is widely determined by automatic coulometric titration with electrogenerated silver ion. 

K. Fischbeck and E. Einecke found that the cathodic polarization of ferrous, cuprous, calcium, and magnesium chromites produces chromic acid, whilst the other chromites are unaffected, and natural chrome ironstone behaves in a like manner, but other commercial chromites are reduced on cathodic polarization, and yield chromic acid on anodic polarization. Chromites behave as an intermediate electrode. 0. Unverdorben observed that chromyl fluoride, prepared by heating a mixture of fluorspar, lead chromate, and sulphuric acid, when passed into water, furnishes an aq. soln. of this oxide. The soln. was treated with silver nitrate, and the washed precipitate of silver chromate decomposed by hydrochloric acid. A. Mans said that anhydrous sulphuric acid or fuming sulphuric acid is not suited for the preparation because of its volatilization with the chromyl fluoride. 

Multilayer LBFs are often prepared from cadmium stearate, magnesium stearate, and a-Fe203. Self-organized films of silver stearate (8-14 layers) were formed in hydrophobic layers of stearic acid. The film was transferred to electrodes (n = 25 mN m ) and then electrochemically reduced in a neutral or acidic solution to form 2D Ag clusters (20-30 nm). These films also contained Ag clusters of the sandwich type. Self-organized metal-containing LBF ensembles are often rrsed for... 

More recently, because of their high dielectric constants k > 20 000), lead-based relaxor ferroelectrics have been used as capacitor materials. These ceramics have the general chemical formula Pb(5i, 2)03) vvhere Bi is typically a low-valence cation and B2 is a high-valence cation. Compositions used in capacitor applications are frequently based on lead magnesium niobate, Pb(Mgi/3,Nb2/3)03, and lead zinc niobate, Pb(Zni/3,Nb2/3)03. Other substituents and modifiers are added so that dielectric layers of these materials can be densified at relatively low temperatures ( 900 °C). The low firing temperatures permit the use of relatively inexpensive cofired electrode materials, such as silver. Typically, tape casting is used in the preparation of the dielectric layers. 

The number and variety of ion-specific electrodes is rapidly increasing with no end in sight. At the present writing, it is possible to use such electrodes to determine, either by direct or indirect measurement, ionic concentrations of the following species ammonia, bromide, cadmium, calcium, chloride, cupric, cyanide, fluoride, fluoroborate, iodide, lead, nitrate, perchlorate, potassium, sulfide, sodium, sulfur dioxide, and thiocyanate, all by direct measurement, and by titration methods aluminum, boron, chromium, cobalt, magnesium, mercury, nickel, phosphate, silver, sulfate, and zinc. 

---