Platinum methane

Anhydrous, monomeric formaldehyde is not available commercially. The pure, dry gas is relatively stable at 80—100°C but slowly polymerizes at lower temperatures. Traces of polar impurities such as acids, alkahes, and water greatly accelerate the polymerization. When Hquid formaldehyde is warmed to room temperature in a sealed ampul, it polymerizes rapidly with evolution of heat (63 kj /mol or 15.05 kcal/mol). Uncatalyzed decomposition is very slow below 300°C extrapolation of kinetic data (32) to 400°C indicates that the rate of decomposition is ca 0.44%/min at 101 kPa (1 atm). The main products ate CO and H2. Metals such as platinum (33), copper (34), and chromia and alumina (35) also catalyze the formation of methanol, methyl formate, formic acid, carbon dioxide, and methane. Trace levels of formaldehyde found in urban atmospheres are readily photo-oxidized to carbon dioxide the half-life ranges from 35—50 minutes (36). 

Hydrogenation Reactions. Hydrogen over a nickel, platinum, or paladium catalyst can partially or totally saturate the aromatic ring. Thermal hyrogenolysis of toluene yields benzene, methane, and biphenyl. 

Carbon tetrachloride can be reduced to chloroform using a platinum catalyst (10) or zinc and acid. With potassium amalgam and water, carbon tetrachloride can be totally reduced to methane. It is widely employed as an initiator in the dehydrochlorination of chloroethanes at 400—600°C ... 

Two synthesis processes account for most of the hydrogen cyanide produced. The dominant commercial process for direct production of hydrogen cyanide is based on classic technology (23—32) involving the reaction of ammonia, methane (natural gas), and air over a platinum catalyst it is called the Andmssow process. The second process involves the reaction of ammonia and methane and is called the BlausAure-Methan-Ammoniak (BMA) process (30,33—35) it was developed by Degussa in Germany. Hydrogen cyanide is also obtained as a by-product in the manufacture of acrylonitrile (qv) by the ammoxidation of propjiene (Sohio process). 

In one patent (31), a filtered, heated mixture of air, methane, and ammonia ia a volume ratio of 5 1 1 was passed over a 90% platinum—10% rhodium gauze catalyst at 200 kPa (2 atm). The unreacted ammonia was absorbed from the off-gas ia a phosphate solution that was subsequently stripped and refined to 90% ammonia—10% water and recycled to the converter. The yield of hydrogen cyanide from ammonia was about 80%. On the basis of these data, the converter off-gas mol % composition can be estimated nitrogen, 49.9% water, 21.7% hydrogen, 13.5% hydrogen cyanide, 8.1% carbon monoxide, 3.7% carbon dioxide, 0.2% methane, 0.6% and ammonia, 2.3%. 

In a typical PAFC system, methane passes through a reformer with steam from the coolant loop of the water-cooled fuel cell. Heat for the reforming reaction is generated by combusting the depleted fuel. The reformed natural gas contains typically 60 percent H9, 20 percent CO, and 20 percent H9O. Because the platinum catalyst in the PAFC can tolerate only about 0.5 percent CO, this fuel mixture is passed through a water gas shift reactor before being fed to the fuel cell. 

A device based on flame ionization measures the total concentration of hydrocarbons. By using a catalyst, such as a heated platinum wire, hydrocarbons other than methane can be removed from the sample gas. With a platinum catalyst, these hydrocarbons are oxidized at a lower temperature than methane. Hence, the total concentration of hydrocarbons, methane, and hydrocarbons other than methane can be determined. 

Organonickel derivatives also offer cases of the -coordination of the substituted hydrotrisfpyrazol- l-yl)borate ligand. For the palladium and platinum complexes, the M(II) M(IV) (M = Pd, Pt) transformation is facile. Organopalla-dium chemistry offers anew type of agostic interactions, C—H - - - Pd, where the C—H bond belongs to one of the pyrazolate rings. Cyclopalladation of various pyrazol-l-ylborates and -methanes does not modify their structure. 

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). 

The Degussa process, on the other hand, reacts ammonia with methane in absence of air using a platinum, aluminum-ruthenium ahoy as a catalyst at approximately 1200°C. The reaction produces hydrogen cyanide and hydrogen, and the yield is over 90%. The reaction is endothermic and requires 251 KJ/mol. 

Catalysts. The methanation of CO and C02 is catalyzed by metals of Group VIII, by molybdenum (Group VI), and by silver (Group I). These catalysts were identified by Fischer, Tropsch, and Dilthey (18) who studied the methanation properties of various metals at temperatures up to 800°C. They found that methanation activity varied with the metal as follows ruthenium > iridium > rhodium > nickel > cobalt > osmium > platinum > iron > molybdenum > palladium > silver. 

The most successful class of active ingredient for both oxidation and reduction is that of the noble metals silver, gold, ruthenium, rhodium, palladium, osmium, iridium, and platinum. Platinum and palladium readily oxidize carbon monoxide, all the hydrocarbons except methane, and the partially oxygenated organic compounds such as aldehydes and alcohols. Under reducing conditions, platinum can convert NO to N2 and to NH3. Platinum and palladium are used in small quantities as promoters for less active base metal oxide catalysts. Platinum is also a candidate for simultaneous oxidation and reduction when the oxidant/re-ductant ratio is within 1% of stoichiometry. The other four elements of the platinum family are in short supply. Ruthenium produces the least NH3 concentration in NO reduction in comparison with other catalysts, but it forms volatile toxic oxides. 

The fit of these equations to the data is very good, as seen in Fig. 18. These equations are valid to very small values of CO concentrations, where the reaction becomes first order with respect to CO. In a mixture of CO with oxygen, there should be a maximum in reaction rate when the CO concentration is at 0.2%, as shown in Fig. 19. When the oxidation of olefins and aromatics over a platinum loaded monolith is over 99% complete, the conversion of higher paraffins may be around 90% and the conversion of the intractable methane is only 10%. 

The cyanide ion, CN-, is the conjugate base of hydrogen cyanide, HCN. This acid is made by heating ammonia, methane, and air in the presence of a platinum catalyst ... 

The photo-Kolbe reaction is the decarboxylation of carboxylic acids at tow voltage under irradiation at semiconductor anodes (TiO ), that are partially doped with metals, e.g. platinum [343, 344]. On semiconductor powders the dominant product is a hydrocarbon by substitution of the carboxylate group for hydrogen (Eq. 41), whereas on an n-TiOj single crystal in the oxidation of acetic acid the formation of ethane besides methane could be observed [345, 346]. Dependent on the kind of semiconductor, the adsorbed metal, and the pH of the solution the extent of alkyl coupling versus reduction to the hydrocarbon can be controlled to some extent [346]. The intermediacy of alkyl radicals has been demonstrated by ESR-spectroscopy [347], that of the alkyl anion by deuterium incorporation [344]. With vicinal diacids the mono- or bisdecarboxylation can be controlled by the light flux [348]. Adipic acid yielded butane [349] with levulinic acid the products of decarboxylation, methyl ethyl-... 

Catalytic hydrogenation with platinum liberates the hydrocarbon from methylcobalamin (57) and from alkyl-Co-DMG complexes (161), but not from pentacyanides with primary alkyl, vinyl, or benzyl ligands, though the cr-allyl complex yields propylene (109). Sodium sand gives mixtures of hydrocarbons with the alkyl-Co-salen complexes (64). Dithioerythritol will liberate methane from a variety of methyl complexes [cobalamin, DMG, DMG-BF2, G, DPG, CHD, salen, and (DO)(DOH)pn] (156), as will 1,4-butanedithiol from the DMG complex (157), and certain unspecified thiols will reduce DMG complexes with substituted alkyl ligands (e.g., C0-CH2COOH ->CH3C00H) (163, 164). Reaction with thiols can also lead to the formation of thioethers (see Section C,3). 

When tetranuclear platinum complex (35) bridged by tetra(4-ethynylphenyl)-methane was used as the core (Fig. 6), dendrimers having more platinum atoms than those prepared from trinuclear platinum core 30 in the molecule were obtained up to the third generation. GPC analysis of these dendrimers revealed that the dendrimers with a tetraplatinum core have a similar molecular size to those with the triplatinum core 30. 

GP 10] [R 18] The ammonia selectivity of 62% at a p-gauze platinum catalyst is in the range of the technical process (Figure 3.48) the methane selectivity of 30% is only half the industrial performance (70 ml h methane 70 ml h ammonia ... 

For transition-metal catalyzed hydroxylation of alkane C-H bonds, the reactions of alkanes with platinum(II) complexes were the most successful. In an aqueous solution of hexachloroplatinic acid and Na2PtCl4, alkanes were converted into a mixture of isomeric alkyl chlorides, alcohols, and ketones, and the platinum(IV) is reduced to platinum(II).7 The kinetics of the reaction with methane as the alkane have been described in detail.8... 

Relatively, few studies were devoted to the reduction of NO by HC in TW conditions. Platinum seems to be a good reducer of NO by light alkanes, specially the methane [95] ... 

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