Carbon monoxide surface

The electrochemical performance of carbon monoxide adsorbed on platinum basal planes has been extensively studied with the help of various physical techniques such as LEED, AES, and in situ infrared spectroscopy of the surface species [68,69]. The common feature of these studies is the use of a non-adsorbing anion electrolyte such as perchloric acid. The problem arises from the coincident potential region for adsorbed carbon monoxide oxidation and desorption that only on carbon monoxide surface saturation, we can neglect the influence of the hydrogen-adsorbed states. 

Substituting Equation 5.167 into the expressions for the hydrogen and carbon monoxide surface concentrations, and combining the resulting expressions with Equation 5.166 leads to... 

There has been a general updating of the material in all the chapters the treatment of films at the liquid-air and liquid-solid interfaces has been expanded, particularly in the area of contemporary techniques and that of macromolecular films. The scanning microscopies (tunneling and atomic force) now contribute more prominently. The topic of heterogeneous catalysis has been expanded to include the well-studied case of oxidation of carbon monoxide on metals, and there is now more emphasis on the flexible surface, that is, the restructuring of surfaces when adsorption occurs. New calculational methods are discussed. 

The dynamics of fast processes such as electron and energy transfers and vibrational and electronic deexcitations can be probed by using short-pulsed lasers. The experimental developments that have made possible the direct probing of molecular dissociation steps and other ultrafast processes in real time (in the femtosecond time range) have, in a few cases, been extended to the study of surface phenomena. For instance, two-photon photoemission has been used to study the dynamics of electrons at interfaces [ ]. Vibrational relaxation times have also been measured for a number of modes such as the 0-Fl stretching m silica and the C-0 stretching in carbon monoxide adsorbed on transition metals [ ]. Pump-probe laser experiments such as these are difficult, but the field is still in its infancy, and much is expected in this direction m the near fiitiire. 

The saturation coverage during chemisorption on a clean transition-metal surface is controlled by the fonnation of a chemical bond at a specific site [5] and not necessarily by the area of the molecule. In addition, in this case, the heat of chemisorption of the first monolayer is substantially higher than for the second and subsequent layers where adsorption is via weaker van der Waals interactions. Chemisorption is often usefLil for measuring the area of a specific component of a multi-component surface, for example, the area of small metal particles adsorbed onto a high-surface-area support [6], but not for measuring the total area of the sample. Surface areas measured using this method are specific to the molecule that chemisorbs on the surface. Carbon monoxide titration is therefore often used to define the number of sites available on a supported metal catalyst. In order to measure the total surface area, adsorbates must be selected that interact relatively weakly with the substrate so that the area occupied by each adsorbent is dominated by intennolecular interactions and the area occupied by each molecule is approximately defined by van der Waals radii. This... 

Yates J T and Garland C 1961 Infrared studies of carbon monoxide chemisorbed on nickel surfaces J. Catal. 65 617-24... 

Whereas ATR spectroscopy is most commonly applied in obtaining infrared absorption spectra of opaque materials, reflection-absorption infrared spectroscopy (RAIRS) is usually used to obtain the absorption spectrum of a thin layer of material adsorbed on an opaque metal surface. An example would be carbon monoxide adsorbed on copper. The metal surface may be either in the form of a film or, of greaf imporfance in fhe sfudy of cafalysfs, one of fhe parficular crysfal faces of fhe mefal. 

Because the synthesis reactions are exothermic with a net decrease in molar volume, equiUbrium conversions of the carbon oxides to methanol by reactions 1 and 2 are favored by high pressure and low temperature, as shown for the indicated reformed natural gas composition in Figure 1. The mechanism of methanol synthesis on the copper—zinc—alumina catalyst was elucidated as recentiy as 1990 (7). For a pure H2—CO mixture, carbon monoxide is adsorbed on the copper surface where it is hydrogenated to methanol. When CO2 is added to the reacting mixture, the copper surface becomes partially covered by adsorbed oxygen by the reaction C02 CO + O (ads). This results in a change in mechanism where CO reacts with the adsorbed oxygen to form CO2, which becomes the primary source of carbon for methanol. 

Ma.nufa.cture. Nickel carbonyl can be prepared by the direct combination of carbon monoxide and metallic nickel (77). The presence of sulfur, the surface area, and the surface activity of the nickel affect the formation of nickel carbonyl (78). The thermodynamics of formation and reaction are documented (79). Two commercial processes are used for large-scale production (80). An atmospheric method, whereby carbon monoxide is passed over nickel sulfide and freshly reduced nickel metal, is used in the United Kingdom to produce pure nickel carbonyl (81). The second method, used in Canada, involves high pressure CO in the formation of iron and nickel carbonyls the two are separated by distillation (81). Very high pressure CO is required for the formation of cobalt carbonyl and a method has been described where the mixed carbonyls are scmbbed with ammonia or an amine and the cobalt is extracted as the ammine carbonyl (82). A discontinued commercial process in the United States involved the reaction of carbon monoxide with nickel sulfate solution. 

Thermal cracking tends to deposit carbon on the catalyst surface which can be removed by steaming. Carbon deposition by this mechanism tends to occur near the entrance of the catalyst tubes before sufficient hydrogen has been produced by the reforming reactions to suppress the right hand side of the reaction. Promoters, such as potash, are used to help suppress cracking in natural gas feedstocks containing heavier hydrocarbons. Carbon may also be formed by both the disproportionation and the reduction of carbon monoxide... 

A convenient method for assessing the extent of surface oxidation is the measurement of volatile content. This standard method measures the weight loss of the evolved gases on heating up to 950°C in an inert atmosphere. The composition of these gases consists of three principal components hydrogen, carbon monoxide, and carbon dioxide. The volatile content of normal furnace blacks is under 1.5%, and the volatile content of oxidized special grades is 2.0 to 9.5%. 

Oxidation. Carbon monoxide can be oxidized without a catalyst or at a controlled rate with a catalyst (eq. 4) (26). Carbon monoxide oxidation proceeds explosively if the gases are mixed stoichiometticaHy and then ignited. Surface burning will continue at temperatures above 1173 K, but the reaction is slow below 923 K without a catalyst. HopcaUte, a mixture of manganese and copper oxides, catalyzes carbon monoxide oxidation at room temperature it was used in gas masks during World War I to destroy low levels of carbon monoxide. Catalysts prepared from platinum and palladium are particularly effective for carbon monoxide oxidation at 323 K and at space velocities of 50 to 10, 000 h . Such catalysts are used in catalytic converters on automobiles (27) (see Exhaust CONTHOL, automotive). 

Disproportionation. Carbon monoxide readily disproportionates into elemental carbon and carbon dioxide [124-38-9] on a catalyst surface... 

In these processes, a carbon monoxide containing gas is fed to an adsorber bed containing copper, typically dispersed on a high surface area support such as alumina or carbon. The copper is present predominately as Cu", which selectively adsorbs carbon monoxide. The remainder of the gas stream passes through the adsorbent bed. The carbon monoxide is then removed from the adsorbent by lowering the pressure. Figure 6 shows a typical process for a CO-PSA process. Process conditions are typically adsorption pressures of 0.68—204 MPa (6.8—20.4 atm) and temperatures of 313—373 K. Regeneration occurs at reduced pressure or by vacuum. 

Occurrence. Carbon monoxide is a product of incomplete combustion and is not likely to result where a flame bums in an abundant air supply, yet may result when a flame touches a cooler surface than the ignition temperature of the gas. Gas or coal heaters in the home and gas space heaters in industry have been frequent sources of carbon monoxide poisoning when not provided with effective vents. Gas heaters, though properly adjusted when installed, may become hazardous sources of carbon monoxide if maintained improperly. Automobile exhaust gas is perhaps the most familiar source of carbon monoxide exposure. The manufacture and use of synthesis gas, calcium carbide manufacture, distillation of coal or wood, combustion operations, heat treatment of metals, fire fighting, mining, and cigarette smoking represent additional sources of carbon monoxide exposure (105—107). 

CO Oxidation Catalyzed by Palladium. One of the best understood catalytic reactions occurring on a metal surface is the oxidation of carbon monoxide on palladium ... 

In principle, the catalytic converter is a fixed-bed reactor operating at 500—620°C to which is fed 200—3500 Hters per minute of auto engine exhaust containing relatively low concentrations of hydrocarbons, carbon monoxide, and nitrogen oxides that must be reduced significantly. Because the auto emission catalyst must operate in an environment with profound diffusion or mass-transfer limitations (51), it is apparent that only a small fraction of the catalyst s surface area can be used and that a system with the highest possible surface area is required. 

Only recently has a mechanism been proposed for the copper-cataly2ed reaction that is completely satisfactory (58). It had been known for many years that a small amount of carbon dioxide in the feed to the reactor is necessary for optimum yield, but most workers in the field beHeved that the main reaction in the formation of methanol was the hydrogenation of carbon monoxide. Now, convincing evidence has been assembled to indicate that methanol is actually formed with >99% selectivity by the reaction of dissociated, adsorbed hydrogen and carbon dioxide on the metallic copper surface in two steps ... 

The adsorbed oxygen atom on the copper surface is removed by reaction with carbon monoxide and provides a pathway for the formation of the carbon dioxide needed in the main reaction. 

Compound (1) decomposes to form dichloroacetyl chloride, which in the presence of water decomposes to dichloroacetic acid and hydrochloric acid (HCl) with consequent increases in the corrosive action of the solvent on metal surfaces. Compound (2) decomposes to yield phosgene, carbon monoxide, and hydrogen chloride with an increase in the corrosive action on metal surfaces. 

The mechanism of poisoning automobile exhaust catalysts has been identified (71). Upon combustion in the cylinder tetraethyllead (TEL) produces lead oxide which would accumulate in the combustion chamber except that ethylene dibromide [106-93-4] or other similar haUde compounds were added to the gasoline along with TEL to form volatile lead haUde compounds. Thus lead deposits in the cylinder and on the spark plugs are minimized. Volatile lead hahdes (bromides or chlorides) would then exit the combustion chamber, and such volatile compounds would diffuse to catalyst surfaces by the same mechanisms as do carbon monoxide compounds. When adsorbed on the precious metal catalyst site, lead haUde renders the catalytic site inactive. 

The kinetics of this reaction, which can also be regarded as an erosion reaction, shows die effects of adsorption of the reaction product in retarding the reaction rate. The path of this reaction involves the adsorption of an oxygen atom donated by a carbon dioxide molecule on die surface of the coke to leave a carbon monoxide molecule in the gas phase. 

An alternative surface reaction which has been suggested is a reaction between an adsorbed oxygen atom with an adsorbed carbon monoxide molecule to form carbon dioxide which is immediately desorbed. The reaction rate is again given by the equation above. 

Xs are surface fractions (or active centers), free and covered by chemisorbed species of hydrogen, carbon monoxide, and methanol. H, C, and M are activities of hydrogen, carbon monoxide, and methanol. Primes indicate equilibrium values. 

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