Cadmium acids

The first work published in this area was that of Bigelow mentioned above [116], In 1957, monolayers of long-chain fatty acids were fonned on thin films of silver, copper, iron and cadmium deposited on glass microscope slides [43],... 

Cadmium is a soft metal, which forms a protective coating in air, and burns only on strong heating to give the brown oxide CdO. It dissolves in acids with evolution of hydrogen ... 

In its chemistry, cadmium exhibits exclusively the oxidation state + 2 in both ionic and covalent compounds. The hydroxide is soluble in acids to give cadmium(II) salts, and slightly soluble in concentrated alkali where hydroxocadmiates are probably formed it is therefore slightly amphoteric. It is also soluble in ammonia to give ammines, for example Of the halides, cadmium-... 

Liquid- and vapor-phase processes have been described the latter appear to be advantageous. Supported cadmium, zinc, or mercury salts are used as catalysts. In 1963 it was estimated that 85% of U.S. vinyl acetate capacity was based on acetylene, but it has been completely replaced since about 1982 by newer technology using oxidative addition of acetic acid to ethylene (2) (see Vinyl polymers). In western Europe production of vinyl acetate from acetylene stiU remains a significant commercial route. 

Carbonate is measured by evolution of carbon dioxide on treating the sample with sulfuric acid. The gas train should iaclude a silver acetate absorber to remove hydrogen sulfide, a magnesium perchlorate drying unit, and a CO2-absorption bulb. Sulfide is determined by distilling hydrogen sulfide from an acidified slurry of the sample iato an ammoniacal cadmium chloride solution, and titrating the precipitated cadmium sulfide iodimetrically. 

Medicated Dandruff Shampoos. Dandmff is a scalp condition characterized by the production of excessive cellular material (18). A number of shampoos have been marketed which are designed to control and alleviate this condition, and many additives have been included in shampoo compositions to classify them as treatment products for dandmff. These additives include antimicrobial additives, eg, quaternary ammonium salts keratolytic agents, eg, saUcychc acid and sulfur heavy metals, eg, cadmium sulfide coal tar resorcinol and many others. More recent (ca 1993) systems use selenium sulfide [7488-56-4] or zinc pyrithione [13463-41 -7] as active antidandmff shampoo additives. Both of these additives are classified as dmgs, but can be found in over-the-counter products. A stronger version, incorporating the use of higher levels of selenium sulfide in a shampoo, is available but requires a prescription for purchase. 

Ultimately, as the stabilization reactions continue, the metallic salts or soaps are depleted and the by-product metal chlorides result. These metal chlorides are potential Lewis acid catalysts and can greatiy accelerate the undesired dehydrochlorination of PVC. Both zinc chloride and cadmium chloride are particularly strong Lewis acids compared to the weakly acidic organotin chlorides and lead chlorides. This significant complication is effectively dealt with in commercial practice by the co-addition of alkaline-earth soaps or salts, such as calcium stearate or barium stearate, ie, by the use of mixed metal stabilizers. 

Stabilization Mechanism. Zinc and cadmium salts react with defect sites on PVC to displace the labHe chloride atoms (32). This reaction ultimately leads to the formation of the respective chloride salts which can be very damaging to the polymer. The role of the calcium and/or barium carboxylate is to react with the newly formed zinc—chlorine or cadmium—chlorine bonds by exchanging ligands (33). In effect, this regenerates the active zinc or cadmium stabilizer and delays the formation of significant concentrations of strong Lewis acids. 

Typically, soHd stabilizers utilize natural saturated fatty acid ligands with chain lengths of Cg—C g. Ziac stearate [557-05-1/, ziac neodecanoate [27253-29-8] calcium stearate [1592-23-0] barium stearate [6865-35-6] and cadmium laurate [2605-44-9] are some examples. To complete the package, the soHd products also contain other soHd additives such as polyols, antioxidants, and lubricants. Liquid stabilizers can make use of metal soaps of oleic acid, tall oil acids, 2-ethyl-hexanoic acid, octylphenol, and nonylphenol. Barium bis(nonylphenate) [41157-58-8] ziac 2-ethyIhexanoate [136-53-8], cadmium 2-ethyIhexanoate [2420-98-6], and overbased barium tallate [68855-79-8] are normally used ia the Hquid formulations along with solubilizers such as plasticizers, phosphites, and/or epoxidized oils. The majority of the Hquid barium—cadmium formulations rely on barium nonylphenate as the source of that metal. There are even some mixed metal stabilizers suppHed as pastes. The U.S. FDA approved calcium—zinc stabilizers are good examples because they contain a mixture of calcium stearate and ziac stearate suspended ia epoxidized soya oil. Table 4 shows examples of typical mixed metal stabilizers. 

Vinyl acetate (ethenyl acetate) is produced in the vapor-phase reaction at 180—200°C of acetylene and acetic acid over a cadmium, 2inc, or mercury acetate catalyst. However, the palladium-cataly2ed reaction of ethylene and acetic acid has displaced most of the commercial acetylene-based units (see Acetylene-DERIVED chemicals Vinyl polymers). Current production is dependent on the use of low cost by-product acetylene from ethylene plants or from low cost hydrocarbon feeds. 

Dilead hexacyanokisferrate [14402-61 -0] Pb2[Fe(CN)g], is a white precipitate that forms when lead acetate is added to Ca2[Fe(CN)g]. It is insoluble in water or dilute acids but is soluble in hot ammonium chloride or ammonium succinate solutions. It has been used as a quaUtative analytical reagent in tests for cadmium and chromate. 

Organophosphoms compounds, primarily phosphonic acids, are used as sequestrants, scale inhibitors, deflocculants, or ion-control agents in oil wells, cooling-tower waters, and boiler-feed waters. Organophosphates are also used as plasticizers and flame retardants in plastics and elastomers, which accounted for 22% of PCl consumed. Phosphites, in conjunction with Hquid mixed metals, such as calcium—zinc and barium—cadmium heat stabilizers, function as antioxidants and stabilizer adjutants. In 1992, such phosphoms-based chemicals amounted to slightly more than 6% of all such plastic additives and represented 8500 t of phosphoms. Because PVC production is expected to increase, the use of phosphoms additive should increase 3% aimually through 1999. 

Henkel Rearrangement of Benzoic Acid and Phthalic Anhydride. Henkel technology is based on the conversion of benzenecarboxyhc acids to their potassium salts. The salts are rearranged in the presence of carbon dioxide and a catalyst such as cadmium or zinc oxide to form dipotassium terephthalate, which is converted to terephthahc acid (59—61). Henkel technology is obsolete and is no longer practiced, but it was once commercialized by Teijin Hercules Chemical Co. and Kawasaki Kasei Chemicals Ltd. Both processes foUowed a route starting with oxidation of napthalene to phthahc anhydride. In the Teijin process, the phthaHc anhydride was converted sequentially to monopotassium and then dipotassium o-phthalate by aqueous recycle of monopotassium and dipotassium terephthalate (62). The dipotassium o-phthalate was recovered and isomerized in carbon dioxide at a pressure of 1000—5000 kPa ( 10 50 atm) and at 350—450°C. The product dipotassium terephthalate was dissolved in water and recycled as noted above. Production of monopotassium o-phthalate released terephthahc acid, which was filtered, dried, and stored (63,64). 

Activators. Activators are chemicals that increase the rate of vulcanization by reacting first with the accelerators to form mbber soluble complexes. These complexes then react with the sulfur to achieve vulcanization. The most common activators are combinations of zinc oxide and stearic acid. Other metal oxides have been used for specific purposes, ie, lead, cadmium, etc, and other fatty acids used include lauric, oleic, and propionic acids. Soluble zinc salts of fatty acid such as zinc 2-ethyIhexanoate are also used, and these mbber-soluble activators are effective in natural mbber to produce low set, low creep compounds used in load-bearing appHcations. Weak amines and amino alcohols have also been used as activators in combination with the metal oxides. 

Most commercial sorbic acid is produced by a modification of this route. Catalysts composed of metals (2inc, cadmium, nickel, copper, manganese, and cobalt), metal oxides, or carboxylate salts of bivalent transition metals (2inc isovalerate) produce a condensation adduct with ketene and crotonaldehyde (22—24), which has been identified as (5). 

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. 

LB Films of Long-Chain Fatty Acids. LB films of saturated long-chain fatty acids have been studied since the inception of the LB technique. The most stable films of long-chain fatty acids are formed by cadmium arachidate deposited from a buffered CdCl2 subphase. These films, considered to be standards, have been widely used as spacer layers (23) and for examining new analytical techniques. Whereas the chains are tilted - 25° from the surface normal in the arachidic acid, CH2(CH2) gCOOH, films (24), it is nearly perpendicular to the surface in the cadmium arachidate films (25). 

Metal carboxyiates have been considered as nucleophilic agents capable of removing aHyUc chlorine and thereby affording stabilization (143). Typical PVC stabilizers, eg, tin, lead, or cadmium esters, actually promote the degradation of VDC polymers. The metal cations in these compounds are much too acidic to be used with VDC polymers. An effective carboxylate stabilizer must contain a metal cation sufftcientiy acidic to interact with aHyUc chlorine and to facihtate its displacement by the carboxylate anion, but at the same time not acidic enough to strip chlorine from the polymer main chain (144). 

A second synthesis of cobyric acid (14) involves photochemical ring closure of an A—D secocorrinoid. Thus, the Diels-Alder reaction between butadiene and /n j -3-methyl-4-oxopentenoic acid was used as starting point for all four ring A—D synthons (15—18). These were combined in the order B + C — BC + D — BCD + A — ABCD. The resultant cadmium complex (19) was photocyclized in buffered acetic acid to give the metal-free corrinoid (20). A number of steps were involved in converting this material to cobyric acid (14). 

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