Carbon monoxide acidity measurement

Direct measurements on metals such as iron, nickel and stainless steel have shown that adsorption occurs from acid solutions of inhibitors such as iodide ions, carbon monoxide and organic compounds such as amines , thioureas , sulphoxides , sulphidesand mer-captans. These studies have shown that the efficiency of inhibition (expressed as the relative reduction in corrosion rate) can be qualitatively related to the amount of adsorbed inhibitor on the metal surface. However, no detailed quantitative correlation has yet been achieved between these parameters. There is some evidence that adsorption of inhibitor species at low surface coverage d (for complete surface coverage 0=1) may be more effective in producing inhibition than adsorption at high surface coverage. In particular, the adsorption of polyvinyl pyridine on iron in hydrochloric acid at 0 < 0 -1 monolayer has been found to produce an 80% reduction in corrosion rate . 

Temperature control during pressure hydrogenation of cis- or tram-isomers is essential, since at 155°C violent decomposition to carbon, hydrogen and carbon monoxide with development of over 1 kbar pressure will occur. The material should not be heated above 100°C, particularly if acid or base is present, to avoid exothermic polymerisation [1], The m-isomer is readily cyclised to 2,3-dimethylfuran, which promotes lire and explosion hazards. These were measured for the cis- and tram-isomers, and for fram-3-methyl-l-penten-4-yn-3-ol [2],... 

Figure 12. Top, carbon dioxide and carbon monoxide emitted in flue gases from batchwise commercial heat treatment of Asplund board at 165 C versus time. In some plants the emission decreased more with time than here. Bottom, laboratory scale measurements at two temperatures. Data of emitted CO and total acids as weight % on dry hardboard. All data according to Nordenskjold and Ostman (3). (Reproduced with permission from ref. 10. Copyright 1989 De Gruyter.)...

Solutions of Ru3(CO)i2 in carboxylic acids are active catalysts for hydrogenation of carbon monoxide at low pressures (below 340 atm). Methanol is the major product (obtained as its ester), and smaller amounts of ethylene glycol diester are also formed. At 340 atm and 260°C a combined rate to these products of 8.3 x 10 3 turnovers s-1 was observed in acetic acid solvent. Similar rates to methanol are obtainable in other polar solvents, but ethylene glycol is not observed under these conditions except in the presence of carboxylic acids. Studies of this reaction, including infrared measurements under reaction conditions, were carried out to determine the nature of the catalyst and the mechanism of glycol formation. A reaction scheme is proposed in which the function of the carboxylic acid is to assist in converting a coordinated formaldehyde intermediate into a glycol precursor. 

Since decarboxylation is a primary reaction of the aliphatic carboxylic acids, it is interesting to compare the radical yield measured at 77 K (3) with the yield of carbon monoxide plus carbon dioxide. These values are compared in Table III. The results suggest that there is a correlation between the loss of the carboxyl group and the formation of radicals in the carboxylic acids. 

POLYCARBOXYLIC ACIDS The gamma radiolysis of the homopolymers of acrylic, methacrylic and itaconic acids have been investigated in the solid state at 303 K, and in each case the yields of carbon monoxide, carbon dioxide and of radical intermediates have been measured. These are reported in Tables VII and VIII respectively. 

Particularly important compounds have been studied by flame combustion calorimetry. Methane [92-94], ethanol [95], diethyl ether [96], carbon monoxide [92,93,97], hydrochloric acid [98], and water [93,97,99] are representative examples. With a few exceptions (HC1, H2O, D2O [100], SO2 [101], cyanogen [102,103], and some lower chloroalkanes [104,105]), measurements by flame combustion calorimetry have been limited to substances of general formula CaHbOc. 

Elemental composition Ni 34.38%, C 28.13%, O 37.48%. The compound may be identified and measured quantitatively by GC/MS. An appropriately diluted solution in benzene, acetone, or a suitable organic solvent may be analyzed. Alternatively, nickel tetracarbonyl may be decomposed thermally at 200°C, the liberated carbon monoxide purged with an inert gas, and transported onto the cryogenically cooled injector port of a GC followed by analysis with GC-TCD on a temperature-programmed column. Nickel may be analyzed by various instrumental techniques following digestion of the compound with nitric acid and diluting appropriately (See Nickel). 

Reductive decarboxylation of (20) yields C02, H+, and a Co(I) species at a measurable rate (94). In the presence of CO, the starting cobalt complex is regenerated, and a catalytic system for the oxidation of CO by ferricyanide is established. It is significant that in this system the metal-carbonyl bond is formed when the cobalt is in a reduced state. It is the subsequent oxidation of the cobalt by electron transfer that activated the carbonyl to attack by water or hydroxide. That this activation results in a weaker metal-carbonyl bond is evident since the Co(III)-carbonyl may be hydrolyzed in acidic solution with loss of the carbon monoxide ligand (94). 

In January and March of 1988, Radian Corporation made a comprehensive series of performance measurements on the air pollution control system at Modesto (47). As shown in Table 12, the measurements included chlorinated dibenzo-p-dioxins (CDD), chlorinated dibenzofurans (CDF), polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenols (PCB), total hydrocarbons (THC), ammonia, NOx, sulfur trioxide, sulfur dioxide, hydrochloric acid, carbon monoxide, and particulate matter. 

The fire toxicity of each material has been measured under different fire conditions. The influence of polymer nanocomposite formation and fire retardants on the yields of toxic products from fire is studied using the ISO 19700 steady-state tube furnace, and it is found that under early stages of burning more carbon monoxide may be formed in the presence of nanofillers and fire retardants, but under the more toxic under-ventilated conditions, less toxic products are formed. Carbon monoxide yields were measured, together with HCN, nitric acid (NO), and nitrogen dioxide (NO2) yields for PA6 materials, for a series of characteristic fire types from well-ventilated to large vitiated. The yields are all expressed on a mass loss basis. 

The temperature and density structure of the troposphere, along with the concentrations of major constituents, are well documented and altitude profiles have been measured over a wide range of seasons and latitudes for the minor species water, carbon dioxide, and ozone. A few profiles are available for carbon monoxide, nitrous oxide, methane, and molecular hydrogen, while only surface or low-altitude measurements have been made for nitric oxide, nitrogen dioxide, ammonia, sulfur dioxide, hydrogen sulfide, and nonmethane hydrocarbons. No direct measurements of nitric acid and formaldehyde are available, though indirect information does exist. The concentrations of a number of other important species, such as peroxides and oxy and peroxy radicals, have never been determined. Therefore, while considerable information concerning trace constituent concentrations is available, the picture is far from complete. 

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