Platinum nitrate

The synthesis and chemistry of platinum nitrates has been recently reviewed.1621 The only homoleptic nitrate complex is K2Pt(N03)6 formed from K tBre and N2Os. Oxidation of the nitrito complex K2Pt(N02)4 gives K2Pt(N02)6> and not the nitrate complex. 

In order to investigate the poisoning mechanism, the FT-IR spectra were measured for the platinum powder before and after exposed to the vapor of HN03 aqueous solution. A sharp peak which belongs to N03 characteristic absorption was observed at 1390 cm 1 as shown in Fig.3. The formation of some platinum nitrate compounds seems quite unlikely under the present experimental condition, We might conclude from these results that the poisoning was caused by the reversible adsorption of HN03 on the Pt catalyst surface. 

Table 1 presents the n-hexane conversion, selectivity to isomers and coke deposited after reaction for catalysts prepared by using two different platinum precursors tetraammine platinum nitrate and hexachloroplatinic acid. Both materials were calcined at different temperatures after platinum addition. For both platinum precursors, run under standard operational conditions, the optimum calcination temperature for catalytic activity was 500 °C. The amount of coke is small and the TPO profiles of the coked samples (not shown) are similar for all catalysts. Coke is completely burnt off at temperatures below that at which the catalyst was calcined after the metal addition. This is an important feature, because regeneration procedures would not affect the metal function. 

Pt precursor (tetraammine platinum nitrate or hexachloroplatinic acid) does not affect significantly the amount and nature of coke. Under the same operational conditions, the presence of platinum decreases the amount of coke and the maximum temperature of coke burning. The absence of platinum Influences the degree of coke polymerization more than the absence of hydrogen in the feed. 

Similar Pt catalysts with three different dispersions as in Section 17.3, supported on silica and alumina and the homolog containing ceria, were prepared by incipient wetness impregnation of tetraammine-platinum nitrate of the support. In the case of the ceria-containing catalysts, a solution of Ce(N03)3-6H20 in 15.5 ml HjO was added to the silica or alumina supports, followed by drying in air overnight and calcinations at 300°C in air. Specific conditions used in the preparation of these materials are reported elsewhere. Table 17.4 summarizes the various catalysts studied in this case as well as their dispersion. 

Adams catalyst, platinum oxide, Pt02 H20. Produced by fusion of H2PtCl6 with sodium nitrate at 500-550 C and leaching of the cooled melt with water. Stable in air, activated by hydrogen. Used as a hydrogenation catalyst for converting alkenes to alkanes at low pressure and temperature. Often used on Si02... 

Method 1. From ammonium chloroplatinate. Place 3 0 g. of ammonium chloroplatinate and 30 g. of A.R. sodium nitrate (1) in Pyrex beaker or porcelain casserole and heat gently at first until the rapid evolution of gas slackens, and then more strongly until a temperature of about 300° is reached. This operation occupies about 15 minutes, and there is no spattering. Maintain the fluid mass at 500-530° for 30 minutes, and allow the mixture to cool. Treat the sohd mass with 50 ml. of water. The brown precipitate of platinum oxide (PtOj.HjO) settles to the bottom. Wash it once or twice by decantation, filter througha hardened filter paper on a Gooch crucible, and wash on the filter until practically free from nitrates. Stop the washing process immediately the precipitate tends to become colloidal (2) traces of sodium nitrate do not affect the efficiency of the catalyst. Dry the oxide in a desiccator, and weigh out portions of the dried material as required. 

Method A. Cool a solution of the nitrate-free dichloride, prepared from or equivalent to 5 0 g. of palladium or platinum, in 50 ml. of water and 5 ml. of concentrated hydrochloric acid in a freezing mixture, and treat it with 50 ml. of formahn (40 per cent, formaldehyde) and 11 g. of the carrier (charcoal or asbestos). Stir the mixture mechanically and add a solution of 50 g. of potassium hydroxide in 50 ml. of water, keeping the temperature below 5°. When the addition is complete, raise the temperature to 60° for 15 minutes. Wash the catalyst thoroughly by decantation with water and finally with dilute acetic acid, collect on a suction filter, and wash with hot water until free from chloride or alkali. Dry at 100° and store in a desiccator. 

Quantitative estimation of cyclohexane in the presence of benzene and aUphatic hydrocarbons may be accompHshed by a nitration-dehydrogenation method described in Reference 61. The mixture is nitrated with mixed acid and under conditions that induce formation of the soluble mononitroaromatic derivative. The original mixture of hydrocarbons then is dehydrogenated over a platinum catalyst and is nitrated again. The mononitro compounds of the original benzene and the benzene formed by dehydrogenation of the cyclohexane dissolve in the mixed acid. The aUphatic compound remains unattacked and undissolved. This reaction may be carried out on a micro scale. 

C. HIO is prepared by oxidation of iodine with perchloric acid, nitric acid, or hydrogen peroxide or oxidation of iodine in aqueous suspension to iodic acid by silver nitrate. Iodic acid is also formed by anodic oxidation at a platinum electrode of iodine dissolved in hydrochloric acid (113,114). 

Nitric acid reacts with all metals except gold, iridium, platinum, rhodium, tantalum, titanium, and certain alloys. It reacts violentiy with sodium and potassium to produce nitrogen. Most metals are converted iato nitrates arsenic, antimony, and tin form oxides. Chrome, iron, and aluminum readily dissolve ia dilute nitric acid but with concentrated acid form a metal oxide layer that passivates the metal, ie, prevents further reaction. 

Ammonium chloroplatinate often can be used to advantage in place of chloroplatim c acid in the preparation of Adams catalyst. A mixture of 3 g. of ammonium chloroplatinate and 30 g. of sodium nitrate in a casserole or Pyrex beaker is heated gently at first until the rapid evolution of gas slackens and then more strongly until a temperature of 500° is reached. This operation requires about fifteen minutes and there is no spattering. The temperature is held at 500-520° for one-half hour and the mixture is then allowed to cool. The platinum oxide catalyst, collected in the usual way by extracting the soluble salts with water, weighs 1.5 g. and it is comparable in appearance and in activity to the material prepared from chloroplatinic acid. 

This procedure is particularly time-saving when scrap platinum or spent catalyst is used for the preparation of platinum oxide, for after conversion to chloroplatinic acid a purification is conveniently effected by precipitating the ammonium salt, and the direct fusion of this with sodium nitrate eliminates the tedious process of reconversion to chloroplatinic acid. Furthermore ammonium chloroplatinate is not hygroscopic and can he accurately weighed. The amount of catalyst obtained is almost exactly half the weight of the ammonium salt employed. 

It is available commercially from several routes including as a product from the manufacture of sodium nitrate from sodium chloride and nitric acid, and from a process involving the passage of ammonia and air over heated platinum and treating the nitric oxide so formed with oxygen. 

Gold is stable in most strong reducing acids, whereas iron corrodes rapidly, yet finely divided gold can be quickly dissolved in oxygenated cyanide solutions which may be contained in steel tanks. A mixture of caustic soda and sodium nitrate can be fused in an iron or nickel crucible, whereas this melt would have a disastrous effect on a platinum crucible. 

The behaviour of iridium is closely analogous to that of rhodium its corrosion diagram is very similar and it is, with rhodium, one of the least corrodible of metals. It is unattacked by alkalis, acids or oxidising agents in aqueous solution, although a fused mixture of caustic potash and potassium nitrate will attack it. The metal has an excellent resistance to fused lead oxide, silicates, molten copper and iron at temperatures up to 1 500°C. Additions of iridium to platinum considerably raise the corrosion resistance of the latter to a very wide range of reagents. 

Arylamines are usually prepared by nitration of an aromatic starting material, followed by reduction of the nitro group (Section 16.2). The reduction step can be carried out in many different ways, depending on the circumstances. Catalytic hydrogenation over platinum works well but is often incompatible with... 

If only platinum metal is available this is dissolved in aqua regia and evaporated to dryness several times with hydrochloric acid, until free from nitrates (Note 9) and the product purified according lo the method of Wichers. 

Naturally, the flux employed will depend upon the nature of the insoluble substance. Thus acidic materials are attacked by basic fluxes (carbonates, hydroxides, metaborates), whilst basic materials are attacked by acidic fluxes (pyroborates, pyrosulphates, and acid fluorides). In some instances an oxidising medium is useful, in which case sodium peroxide or sodium carbonate mixed with sodium peroxide or potassium nitrate may be used. The vessel in which fusion is effected must be carefully chosen platinum crucibles are employed for... 

C and weighed. The precipitate is almost insoluble in hot water, but dissolves readily in ammonia and cyanide solutions. Gold is reduced to the metal by the reagent, and platinum (if present in appreciable quantity) is partially precipitated either as a greenish complex compound or as the metal, upon boiling the solution. The precipitation of palladium is not complete in the presence of nitrates. 

Zirconium ( > 100 mg in ca /. M sulphuric acid solution). Add freshly prepared 10 per cent aqueous diammonium hydrogenphosphate solution in 50-100-fold excess. Dilute to 300 mL, boil for a few minutes, allow to digest on a water bath for 15-30 minutes and cool to about 60 °C. Filter through a quantitative filter paper, wash first with 150 mL of 1M sulphuric acid containing 2.5 g diammonium hydrogenphosphate and then with cold 5 per cent ammonium nitrate solution until the filtrate is sulphate-free. Dry the filter paper and precipitate at 110°C, place in a platinum crucible and carefully burn off the filter paper. Finally heat at 1000 °C for 1-3 hours and weigh as ZrP207 (Section 11.51). 

The solution should be free from the following, which either interfere or lead to an unsatisfactory deposit silver, mercury, bismuth, selenium, tellurium, arsenic, antimony, tin, molybdenum, gold and the platinum metals, thiocyanate, chloride, oxidising agents such as oxides of nitrogen, or excessive amounts of iron(III), nitrate or nitric acid. Chloride ion is avoided because Cu( I) is stabilised as a chloro-complex and remains in solution to be re-oxidised at the anode unless hydrazinium chloride is added as depolariser. 

Apparatus. Use the apparatus shown in Figs. 14.2(a) and (b). The generator cathode (isolated auxiliary electrode) consists of platinum foil (4 cm x 2.5 cm, bent into a half cylinder) and the generator anode (working electrode) is a rectangular platinum foil (4 cm x 2.5 cm). For potentiometric end point detection, use a platinum-foil electrode 1.25 cm x 1.25 cm (or a silver-rod electrode) in combination with an S.C.E. connected to the cell by a potassium chloride- or potassium nitrate-agar bridge. 

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