Soluble anode

Anodes. There are two types of anodes soluble and insoluble. Most electroplating baths use one or the other specifically however, a few baths use either or both. Chromic acid plating baths use insoluble anodes alkaline zinc cyanide baths use both noncyanide alkaline zincs may use either. Soluble anodes are designed to dissolve efficiendy with current flow and preferably, not to dissolve when the system is idle. A plating solution having the anode efficiency close to the cathode efficiency provides a balanced process that has fewer control problems and is less cosdy. If the anode efficiency is much greater than the cathode efficiency and there are only small solution losses, the dissolved metal concentration rises until at some time the bath has to be diluted back or the excess metal has to be reduced by some other means. If the anode efficiency is less than the cathode efficiency, the dissolved metal decreases, pH decreases, and eventually metal salt additions and other solution corrections are required. Based on the cost of metal, it is usually considerably more economical to plate from the anode rather than add metal salt. Copper cyanide, for example, costs about twice as much to add than to dissolve a comparable amount of copper anode. Additionally, the anion added with the metal salt may build up in the plating solution. 

Polarization occurs because of ion concentration buildup near the anode and/or cathode. Once the ion concentration reaches saturation, corrosion essentially stops. Polarization can occur when (1) Hydrogen ions concentrate at an active cathode in the absence of a cathodic depolarizer. Dissolved oxygen acts as a cathodic depolarizer. (2) Metal ions saturate the electrolyte around an anode. (Soluble Fe++ may saturate the anode, perhaps as the result of the precipitation of an insoluble iron salt, inhibiting the diffusion of Fe++. For example, insoluble surface compounds such as carbonate scales in a fresh water often occur on carbon steel.)... 

From an electrochemical viewpoint, stable pit growtli is maintained as long as tire local environment witliin tire pit keeps tire pit under active conditions. Thus, tire effective potential at tire pit base must be less anodic tlian tire passivation potential (U ) of tire metal in tire pit electrolyte. This may require tire presence of voltage-drop (IR-drop) elements. In tliis respect the most important factor appears to be tire fonnation of a salt film at tire pit base. (The salt film fonns because tire solubility limit of e.g. FeCl2 is exceeded in tire vicinity of tire dissolving surface in tlie highly Cl -concentrated electrolyte.)... 

Anhydrous silver hexafluorophosphate [26042-63-7] AgPF, as well as other silver fluorosalts, is unusual in that it is soluble in ben2ene, toluene, and xylene and forms 1 2 molecular crystalline complexes with these solvents (91). Olefins form complexes with AgPF and this characteristic has been used in the separation of olefins from paraffins (92). AgPF also is used as a catalyst. Lithium hexafluorophosphate [21324-40-3] LiPF, as well as KPF and other PF g salts, is used as electrolytes in lithium anode batteries (qv). 

Fluorocarbons are made commercially also by the electrolysis of hydrocarbons in anhydrous hydrogen fluoride (Simons process) (14). Nickel anodes and nickel or steel cathodes are used. Special porous anodes improve the yields. This method is limited to starting materials that are appreciably soluble in hydrogen fluoride, and is most useflil for manufacturing perfluoroalkyl carboxyflc and sulfonic acids, and tertiary amines. For volatile materials with tittle solubility in hydrofluoric acid, a complementary method that uses porous carbon anodes and HF 2KF electrolyte (Phillips process) is useflil (14). 

The best known oxoanion of iron is the ferrate(VI) prepared by oxidizing a suspension of hydrous iron(III) oxide in concentrated alkah with potassium hypochlorite or by anodic oxidation of iron in concentrated alkah. Crystals of potassium ferrate [13718-66-6], K FeO, are deep purple, orthorhombic, and contain discrete tetrahedral [FeOJ anions. Barium ferrate [13773-23A] can be precipitated from solutions of soluble ferrate salts. 

Lead Telluride. Lead teUuride [1314-91 -6] PbTe, forms white cubic crystals, mol wt 334.79, sp gr 8.16, and has a hardness of 3 on the Mohs scale. It is very slightly soluble in water, melts at 917°C, and is prepared by melting lead and tellurium together. Lead teUuride has semiconductive and photoconductive properties. It is used in pyrometry, in heat-sensing instmments such as bolometers and infrared spectroscopes (see Infrared technology AND RAMAN SPECTROSCOPY), and in thermoelectric elements to convert heat directly to electricity (33,34,83). Lead teUuride is also used in catalysts for oxygen reduction in fuel ceUs (qv) (84), as cathodes in primary batteries with lithium anodes (85), in electrical contacts for vacuum switches (86), in lead-ion selective electrodes (87), in tunable lasers (qv) (88), and in thermistors (89). 

Metals less noble than copper, such as iron, nickel, and lead, dissolve from the anode. The lead precipitates as lead sulfate in the slimes. Other impurities such as arsenic, antimony, and bismuth remain partiy as insoluble compounds in the slimes and partiy as soluble complexes in the electrolyte. Precious metals, such as gold and silver, remain as metals in the anode slimes. The bulk of the slimes consist of particles of copper falling from the anode, and insoluble sulfides, selenides, or teUurides. These slimes are processed further for the recovery of the various constituents. Metals less noble than copper do not deposit but accumulate in solution. This requires periodic purification of the electrolyte to remove nickel sulfate, arsenic, and other impurities. 

Calcium carbonate (calcite) scale formation in hard water can be prevented by the addition of a small amount of soluble polyphosphate in a process known as threshold treatment. The polyphosphate sorbs to the face of the calcite nuclei and further growth is blocked. Polyphosphates can also inhibit the corrosion of metals by the sorption of the phosphate onto a thin calcite film that deposits onto the metal surface. When the polyphosphate is present, a protective anodic polarization results. 

Production and Economic Aspects. Thallium is obtained commercially as a by-product in the roasting of zinc, copper, and lead ores. The thallium is collected in the flue dust in the form of oxide or sulfate with other by-product metals, eg, cadmium, indium, germanium, selenium, and tellurium. The thallium content of the flue dust is low and further enrichment steps are required. If the thallium compounds present are soluble, ie, as oxides or sulfates, direct leaching with water or dilute acid separates them from the other insoluble metals. Otherwise, the thallium compound is solubilized with oxidizing roasts, by sulfatization, or by treatment with alkaU. The thallium precipitates from these solutions as thaUium(I) chloride [7791 -12-0]. Electrolysis of the thaUium(I) sulfate [7446-18-6] solution affords thallium metal in high purity (5,6). The sulfate solution must be acidified with sulfuric acid to avoid cathodic separation of zinc and anodic deposition of thaUium(III) oxide [1314-32-5]. The metal deposited on the cathode is removed, kneaded into lumps, and dried. It is then compressed into blocks, melted under hydrogen, and cast into sticks. 

Cd(OH)2 is much more basic than Zn(OH)2 and is soluble ia 5 NaOH at 1.3 g/L as the anionic complex tetrahydroxocadmate [26214-93-7] Cd(OH) 4. Technical-grade Cd(OH)2 sold for 74/kg ia 1991 and its most important utihty is as the active anode ia rechargeable Ni—Cd and Ag—Cd storage batteries. The chemical reaction responsible for the charge—discharge of the batteries is (35) ... 

Soluble anode materials are not always a pure metal. In acid, low chloride nickel solutions, pure nickel does not corrode well, and small amounts of specific impurities are added to make the nickel more active, allowing more efficient dissolution. For example, since the early 1960s, nickel anode material containing a small amount of nickel sulfide [16812-54-7] NiS, has been commercially available and important in nickel sulfamate [13770-85-3] Ni(H2N02S)2, plating baths. These anodes corrode at a lower potential then pure nickel or other nickel anode materials (see Nickel and nickel alloys). 

Rhodium. Rhodium is the most commonly plated platinum-group metal. In addition to its decorative uses, rhodium has useful properties for engineering appHcations. It has good corrosion resistance, stable electtical contact resistance, wear resistance, heat resistance, and good reflectivity. The use of rhodium for engineering purposes is covered by an ASTM specification (128). Typical formulas are shown in Table 15. The metal content is obtained from prepared solutions available from proptietary plating supply companies. Replenishment is requited because anodes are not soluble. Rhodium for decorative use may be 0.05—0.13 p.m thick for industtial use, it maybe 0.50—5.0 p.m thick. 

Electrochemical Process. Several patents claim that ethylene oxide is produced ia good yields ia addition to faradic quantities of substantially pure hydrogen when water and ethylene react ia an electrochemical cell to form ethylene oxide and hydrogen (206—208). The only raw materials that are utilized ia the ethylene oxide formation are ethylene, water, and electrical energy. The electrolyte is regenerated in situ ie, within the electrolytic cell. The addition of oxygen to the ethylene is activated by a catalyst such as elemental silver or its compounds at the anode or its vicinity (206). The common electrolytes used are water-soluble alkah metal phosphates, borates, sulfates, or chromates at ca 22—25°C (207). The process can be either batch or continuous (see Electrochemicalprocessing). 

Sample pre-treatment. Novel procedures of electrochemical sample treatment have been proposed to decrease the signal interference with native cholinesterase inhibitors present in fruits and vegetables. Polyphenolic compounds were removed by electrolysis with soluble A1 anode followed by the oxidation of thionic pesticides with electrogenerated chlorine. The procedure proposed makes it possible to decrease the background current and the matrix effect by 80-90%. Thus, the detection limits of about 5 ppb of Pai athion-Methyl and Chloropyrifos-Methyl were obtained in spiked grape juice without any additional sepai ation or pre-concentration stages. 

Chemical inhibitors, when added in small amounts, reduce corrosion by affecting cathodic and/or anodic processes. A wide variety of treatments may be used, including soluble hydroxides, chromates, phosphates, silicates, carbonates, zinc salts, molybdates, nitrates, and magnesium salts. The exact amount of inhibitor to be used, once again, depends on system parameters such as temperature, flow, water chemistry, and metal composition. For these reasons, experts in water treatment acknowledge that treatment should be fine tuned for a given system. 

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