Palladium arsenate

Palladium Arsenic, carbon, ozonides, sulfur, sodium tetrahydridoborate... 

Palladium Arsenate was reported by Berzelius3 as a pale yellow precipitate formed when sodium orthoarsenate was added to a neutral solution of palladious nitrate. 

Impurities in cmde metal can occur as other metals or nonmetals, either dissolved or in some occluded form. Normally, impurities are detrimental, making the metal less useful and less valuable. Sometimes, as in the case of copper, extremely small impurity concentrations, eg, arsenic, can impart a harmful effect on a given physical property, eg, electrical conductivity. On the other hand, impurities may have commercial value. For example, gold, silver, platinum, and palladium, associated with copper, each has value. In the latter situation, the purity of the metal is usually improved by some refining technique, thereby achieving some value-added and by-product credit. 

Catalytic Oxidation. Catalytic oxidation is used only for gaseous streams because combustion reactions take place on the surface of the catalyst which otherwise would be covered by soHd material. Common catalysts are palladium [7440-05-3] and platinum [7440-06-4]. Because of the catalytic boost, operating temperatures and residence times are much lower which reduce operating costs. Catalysts in any treatment system are susceptible to poisoning (masking of or interference with the active sites). Catalysts can be poisoned or deactivated by sulfur, bismuth [7440-69-9] phosphoms [7723-14-0] arsenic, antimony, mercury, lead, zinc, tin [7440-31-5] or halogens (notably chlorine) platinum catalysts can tolerate sulfur compounds, but can be poisoned by chlorine. 

By-Product Recovery. The anode slime contains gold, silver, platinum, palladium, selenium, and teUurium. The sulfur, selenium, and teUurium in the slimes combine with copper and sUver to give precipitates (30). Some arsenic, antimony, and bismuth can also enter the slime, depending on the concentrations in the electrolyte. Other elements that may precipitate in the electrolytic ceUs are lead and tin, which form lead sulfate and Sn(0H)2S04. 

The reaction is a sensitive one, but is subject to a number of interferences. The solution must be free from large amounts of lead, thallium (I), copper, tin, arsenic, antimony, gold, silver, platinum, and palladium, and from elements in sufficient quantity to colour the solution, e.g. nickel. Metals giving insoluble iodides must be absent, or present in amounts not yielding a precipitate. Substances which liberate iodine from potassium iodide interfere, for example iron(III) the latter should be reduced with sulphurous acid and the excess of gas boiled off, or by a 30 per cent solution of hypophosphorous acid. Chloride ion reduces the intensity of the bismuth colour. Separation of bismuth from copper can be effected by extraction of the bismuth as dithizonate by treatment in ammoniacal potassium cyanide solution with a 0.1 per cent solution of dithizone in chloroform if lead is present, shaking of the chloroform solution of lead and bismuth dithizonates with a buffer solution of pH 3.4 results in the lead alone passing into the aqueous phase. The bismuth complex is soluble in a pentan-l-ol-ethyl acetate mixture, and this fact can be utilised for the determination in the presence of coloured ions, such as nickel, cobalt, chromium, and uranium. 

The magnetic criterion is particularly valuable because it provides a basis for differentiating sharply between essentially ionic and essentially electron-pair bonds Experimental data have as yet been obtained for only a few of the interesting compounds, but these indicate that oxides and fluorides of most metals are ionic. Electron-pair bonds are formed by most of the transition elements with sulfur, selenium, tellurium, phosphorus, arsenic and antimony, as in the sulfide minerals (pyrite, molybdenite, skutterudite, etc.). The halogens other than fluorine form electron-pair bonds with metals of the palladium and platinum groups and sometimes, but not always, with iron-group metals. 

Palladium mixed with arsenic when it is hot causes a violent incandescence of the mixture with a very bright light emission. The same goes for sulphur. 

Mellor, 1940, Vol. 4, 485-486 1942, Vol. 15, 629 1937, Vol. 16,161 Palladium or zinc and arsenic react on heating with evolution of light and heat, and platinum with vivid incandescence. 

Kuroda and Tarui [498] developed a spectrophotometric method for molybdenum based on the fact that MoVI catalyses the reduction of ferric iron by divalent tin ions. The plot of initial reaction rate constant versus molybdenum concentration is rectilinear in the range 0.01-0.3 mg/1 molybdenum. Several elements interfere, namely, titanium, rhenium, palladium, platinum, gold, arsenic, selenium, and tellurium. 

Palladium Paraformaldehyde Paraldehyde Pentaborane-9 Pentacarbonyliron Arsenic, carbon, ozonides, sulfur, sodium tetrahydridoborate Liquid oxygen Alkalies, HCN, iodides, nitric acid, oxidizers Dimethylsulfoxide Acetic acid, nitric oxide, transition metal halides, water, zinc... 

Antimony, arsenic, bismuth, cadmium, calcium, cesium, chromium, cobalt, copper, gold, indium, iridium, iron, lead, lithium, magnesium, manganese, mercury, nickel, palladium, platinum, potassium, rhodium, rubidium, ruthenium, selenium, silver, sodium, tellurium, thallium, zinc... 

The corresponding palladium compound (157) must be formulated as [Pd(TA)Br]+Br. The cation is essentially square-planar, but the bromine atom is displaced 10° out of the arsenic-palladium plane. Such a distortion is very unusual for palladium, and may be due to a steric effect of the alkyl chains in the arsine ligand. This might similarly account for the distortion of the nickel complex from a square pyramidal shape. 

The most active catalyst is platinum applied in finely divided form, for example platinised asbestos. Certain elements, especially arsenic and mercury, have a powerful effect in reducing the activity of the platinum, a quantity of arsenic equal to 0-2 per cent, of the weight of the platinum reducing the activity by 50 per cent.5 These poisons, as they are termed, also include less harmful substances such as antimony, lead, bismuth, etc. The presence of small quantities of rhodium, iridium or osmium in the platinum also causes diminished yields of trioxide, but the presence of palladium or ruthenium has the opposite effect.6... 

These are prepared by the cyclization of either an arsenous chloride (29) (23JCS2489) or an arsenic acid (30) (58JCS1719). These routes have been used to prepare both the 1-methyl-and the 1-phenyl-arsindolines. The arsindolines show the normal properties of tertiary arsines and form addition compounds with alkyl halides or palladium dibromide. Attempts to dehydrogenate arsindolines to the parent arsindoles (31) have not been successful (Scheme 7). 

Iridium Arsenide, IrAs2, has been obtained in a pure form by heating iridium chloride with an excess of arsenic in a current of hydrogen.4 It is also formed when an intimate mixture of the finely divided metal and excess of arsenic is heated in an indifferent atmosphere. The arsenide may be analysed by the method described under palladium arsenide (p. 73). 

Elements determined but sometimes overlooked antimony, arsenic, bismuth, cadmium, coball, gallium, indium, lanthanum, nickel, palladium. rare earlhs (except cerium), rhodium, ruthenium, scandium, silver, tellurium, thallium, tin. and yttrium. 

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