Platinum special

Although many catalysts have now been found, some with special utility for certain reagents, most research is still devoted to the use of platinum and platinum compounds. No other catalysts have the wide utility and industrial efficiency of platinum. Special uses for platinum and other transition metals are disclosed in numerous patents. A competent review of these is beyond the scope of this chaptei. 

Thanks are due to NSERC for financial support and Johnson-Matthey Ltd. for the generous loan of platinum. Special thanks go to Lj. Manojlovic-Muir and K. W. Muir and their coworkers who have completed the X-ray structure determinations, K. R. Seddon whose help with spectroscopic studies was invaluable and the able research students whose names are given in the references. 

It U better to employ the special palladium catalyst which is incorporated in the Deoxo catalytic gas purifier (obtainable from Baker Platinum Limited, 52 High Holbom. London, W.C. 1). 1 his functions at the laboratory tamperature and will remove up to 1 per cent of oxygen. The water vapour formed is carried away in the gas stream and is separated by any of the common desiccants. 

Common catalyst compositions contain oxides or ionic forms of platinum, nickel, copper, cobalt, or palladium which are often present as mixtures of more than one metal. Metal hydrides, such as lithium aluminum hydride [16853-85-3] or sodium borohydride [16940-66-2] can also be used to reduce aldehydes. Depending on additional functionahties that may be present in the aldehyde molecule, specialized reducing reagents such as trimethoxyalurninum hydride or alkylboranes (less reactive and more selective) may be used. Other less industrially significant reduction procedures such as the Clemmensen reduction or the modified Wolff-Kishner reduction exist as well. 

Dual-Pressure Process. Dual-pressure processes have a medium pressure (ca 0.3—0.6 MPa) front end for ammonia oxidation and a high pressure (1.1—1.5 MPa) tail end for absorption. Some older plants still use atmospheric pressure for ammonia conversion. Compared to high monopressure plants, the lower oxidation pressure improves ammonia yield and catalyst performance. Platinum losses are significantiy lower and production mns are extended by a longer catalyst life. Reduced pressure also results in weaker nitric acid condensate from the cooler condenser, which helps to improve absorber performance. Due to the spHt in operating conditions, the dual-pressure process requires a specialized stainless steel NO compressor. 

The Platinum Group Metal Reviews is a specialized review series focusiag on the new developments and uses of PGMs. Each issue also provides a brief description of recent patents issued ia the field. 

Color. Many water samples have a yellow to brownish-yeUow color which is caused by natural substances, eg, leaves, bark, humus, and peat material. Turbidity in a sample can make the measurement of color uncertain and is usually removed by centrifiigation prior to analysis. The color is usually measured by comparison of the sample with known concentrations of colored solutions. A platinum—cobalt solution is used as the standard, and the unit of color is that produced by 1 mg/L platinum as chloroplatinate ion. The standard is prepared from potassium chloroplatinate (K PtCl ) and cobalt chloride (C0CI26H2O). The sample may also be compared to suitably caUbrated special glass color disks. 

Electroplated Metals and Alloys. The metals electroplated on a commercial scale from specially formulated aqueous solutions iaclude cadmium, chromium, cobalt, copper, gold, iadium, iron, lead, nickel, platinum-group metals, silver, tin, and ziac. Although it is possible to electroplate some metals, such as aluminum, from nonaqueous solutions as well as some from molten salt baths, these processes appear to have achieved Httie commercial significance. 

Phosphoric Acid Fuel Cell This type of fuel cell was developed in response to the industiy s desire to expand the natural-gas market. The electrolyte is 93 to 98 percent phosphoric acid contained in a matrix of silicon carbide. The electrodes consist of finely divided platinum or platinum alloys supported on carbon black and bonded with PTFE latex. The latter provides enough hydrophobicity to the electrodes to prevent flooding of the structure by the electrolyte. The carbon support of the air elec trode is specially formulated for oxidation resistance at 473 K (392°F) in air and positive potentials. 

Fluorinated polymers stand out sharply against other construction materials for their excellent corrosion resistance and high-temperature stability. In this respect they are not only superior to other plastics but also to platinum, gold, glass, enamel and special alloys. The fluorinated plastics used in process plants are polytetrafluorethylene (PTFE), fluorinated ethylene/ propylene (FEP), polytrifiuoromonochlorethylene (PTFCE) and polyvinyl fluoride (PVF). They are much more expensive than other polymers and so are only economical in special situations [59]. 

The so-called standard instrument is used for interpolation between the fixed points and for the calibration of other thermometers lower in the metrological hierarchy. The standard instrument in the moderate temperature range is a special platinum resistance probe, as it has to fulfill set requirements. It is important in all calibration that traceability to a primary normal, here the fixed-point ITS-90 scale, exists. 

A substitute may be prepared thus 0 05 gram palladous chloride is placed in a special shaking flask with 50 c.c, of 50 per cent, alcohol and 1 or 2 c c. of 1 per cent, aqueous solution of gum-arabic, the weight of gum being about one-fourth the weight of the palladous chloride. On shaking this mixture in an atmosphere of hydrogen the chloride is reduced with formation of a black solution of colloidal platinum, which is rendered stable by the small quantity of gum present. 

Many workers (5,6,7,87) have compared various metals for the selective hydrogenation of lower acetylenes to olefins, and it was always found that palladium was by far the most selective. This conclusion concurs with the usual synthetic experience, but under special circumstances other metals, such as platinum, may prove more useful (35,63). The catalyst support may also have an influence (21,65). Carbon, calcium carbonate, and barium sulfate are frequently used supports. Examples of some differences are noted later,... 

Reduction of unsaturated aldehydes seems more influenced by the catalyst than is that of unsaturated ketones, probably because of the less hindered nature of the aldehydic function. A variety of special catalysts, such as unsupported (96), or supported (SJ) platinum-iron-zinc, plalinum-nickel-iron (47), platinum-cobalt (90), nickel-cobalt-iron (42-44), osmium (<55), rhenium heptoxide (74), or iridium-on-carbon (49), have been developed for selective hydrogenation of the carbonyl group in unsaturated aldehydes. None of these catalysts appears to reduce an a,/3-unsaturated ketonic carbonyl selectively. 

A platinum-rhodium ahoy is used as a catalyst at 1100°C. Approximately equal amounts of ammonia and methane with 75 vol % air are introduced to the preheated reactor. The catalyst has several layers of wire gauze with a special mesh size (approximately 100 mesh). 

Although it is attractive to directly convert chemical energy to electricity, PEM fuel cells face significant practical obstacles. Expensive heavy metals like platinum are typically used as catalysts to reduce energy barriers associated with the half-cell reactions. PEM fuel cells also cannot use practical hydrocarbon fuels like diesel without complicated preprocessing steps. Those significantly increase the complexity of the overall system. At this time, it appears likely that PEM fuel cells will be confined to niche applications where high cost and special fuel requirements are tolerable. 

Crucibles and basins required for special purposes are often fabricated from various metals, amongst which platinum holds pride of place by virtue of its general resistance to chemical attack. 

Woodward and Redman 6c have described a specially designed weighing bottle which will accommodate a small platinum crucible when a substance has been ignited in the crucible, the crucible is transferred to the weighing bottle and subsequently weighed in this. This device obviates the need for a desiccator. 

For the preparation of samples for X-ray fluorescence spectroscopy, lithium metaborate is the preferred flux because lithium does not give rise to interfering X-ray emissions. The fusion may be carried out in platinum crucibles or in crucibles made from specially prepared graphite these graphite crucibles can also be used for the vacuum fusion of metal samples for the analysis of occluded gases. 

Gold may also be separated from hydrochloric acid solutions of the platinum metals by extraction with diethyl ether or with ethyl acetate (compare Chapter 6) except in special cases these methods do not offer any special advantages over the reduction to the metal. 

The electrodes are made of platinum gauze as the open construction assists the circulation of the solution. It is possible to use one of the electrodes as stirrer for the solution, but special arrangements must then be made for connection of the electrolysis current to this electrode, and an independent glass-paddle stirrer or a magnetic stirrer offer a simple altemative.Typical electrodes are the Fischer type depicted in Fig. 12.4 a glass tube is slid into... 

A bolometer is essentially a thin blackened platinum strip in an evacuated glass vessel with a window transparent to the infrared rays it is connected as one arm of a Wheatstone bridge, and any radiation absorbed raises the temperature of the strip and changes its resistance. Two identical elements are usually placed in the opposite arms of a bridge one of the elements is in the path of the infrared beam and the other compensates for variations in ambient temperature. Both the above receptors give a very small direct current, which may be amplified by special methods to drive a recorder. 

These fixed points are used to calibrate a different kind of thermometer that is easier to use than a gas thermometer. Over the temperature range from 13.8033 to 1234.93 °A (or K), which is the temperature interval most commonly encountered, the thermometer used for ITS-90 is a platinum resistance thermometer. In this thermometer, the resistance of a specially wound coil of platinum wire is measured and related to temperature. More specifically, temperatures are expressed in terms of W(T9o), the ratio of the resistance R(Ttriple point of water R (273.16 K), as given in equation (1.11)... 

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