Carbon kinetic data

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). 

Table 3.6 Kinetic Data for Reactions of Carbon-Centered Radicals...

Much detailed information concerning the decompositions of carbonates is to be found in the review by Stem and Weise [733] and selected kinetic data are summarized in Table 14. 

There is no clear reason to prefer either of these mechanisms, since stereochemical and kinetic data are lacking. Solvent effects also give no suggestion about the problem. It is possible that the carbon-carbon bond is weakened by an increasing number of phenyl substituents, resulting in more carbon-carbon bond cleavage products, as is indeed found experimentally. All these reductive reactions of thiirane dioxides with metal hydrides are accompanied by the formation of the corresponding alkenes via the usual elimination of sulfur dioxide. 

Although Pb(IV) is sufficiently strong an oxidant to oxidise halides, no kinetic data are available. Complexes of Pt(IV) and Au(III) oxidise iodide and thiocyanate ions but the other oxidants are weaker and form stable halo-complexes. However, some simple molecules such as hypophosphorous acid, carbon monoxide and molecular hydrogen are oxidised by the weaker members. 

Table 12 reports the characterization of the resulting materials. In order to comment the subsequent kinetic data, XPS data were collected in order to confirm the presence of the 4f peak of metal gold at 84.0 eV and also for deriving the amount of exposed gold at the carbon surface. In Table 13 the comparison between 2 and 500 g scale preparations is reported. 

CO3 species was formed and the X-ray structure solved. It is thought that the carbonate species forms on reaction with water, which was problematic in the selected strategy, as water was produced in the formation of the dialkyl carbonates. Other problems included compound solubility and the stability of the monoalkyl carbonate complex. Van Eldik and co-workers also carried out a detailed kinetic study of the hydration of carbon dioxide and the dehydration of bicarbonate both in the presence and absence of the zinc complex of 1,5,9-triazacyclododecane (12[ane]N3). The zinc hydroxo form is shown to catalyze the hydration reaction and only the aquo complex catalyzes the dehydration of bicarbonate. Kinetic data including second order rate constants were discussed in reference to other model systems and the enzyme carbonic anhy-drase.459 The zinc complex of the tetraamine 1,4,7,10-tetraazacyclododecane (cyclen) was also studied as a catalyst for these reactions in aqueous solution and comparison of activity suggests formation of a bidentate bicarbonate intermediate inhibits the catalytic activity. Van Eldik concludes that a unidentate bicarbonate intermediate is most likely to the active species in the enzyme carbonic anhydrase.460... 

Furthermore, protonation results in a significant distortion of the coordination polyhedron, i.e., the metal ion is displaced from the plane formed by the four cyano ligand carbon atoms toward the oxo along the M = 0 axis by as much as 0.34 A, which represents about 20% of the total metal-oxo bond length. In spite of this distortion stronger metal-cyano bonds are observed crystallographically, suggesting a better n back-donation by the metal center to the cyano carbons since d-ff overlap is increased. This observation is in line with both the 13C and 15N chemical shift and kinetic data (Section V) for the protonated complexes (8). 

The competitive decomposition of phenyl silver and p-tolyl silver in pyridine solution45 gives (C6H5)2, (C6H4CH3)2 and (C6H5C6H4CH3) in yields consistent with simple metal-carbon bond rupture. Kinetic data is not available. 

Relatively few kinetic data are available for the carbon-carbon bond forming reactions of alkene radical cations. Nevertheless, rate constants for the cyclization illustrated in Scheme 9, with generation of the alkene radical cation by the fragmentation method, have been measured. These cyclization rate constants are significantly faster than those of the corresponding neutral radicals [89]. 

The kinetic data for reactions of carbon-centered radicals with various silanes and the silanthrane derivatives 1-6 are numerous as shown in... 

As with silicon hydrides, the reaction of atoms or radicals with germanium hydrides is the key step for the majority of reactions forming germyl radicals. However, kinetic data for the reactions of organic radicals with germanium hydrides in solution are limited to carbon- and oxygen-centered radicals. 

In the first set of measurements the rate of carbon build-up on a Ni(lOO) surface was measured at various temperatures as follows (1) surface cleanliness was established by AES (2) the sample was retracted into the reaction chamber and exposed to several torr of CO for various times at a given temperature (3) after evacuation the sample was transferred to the analysis chamber and (4) the AES spectra of C and Ni were measured. Two features of this study are noteworthy. First, two kinds of carbon forms are evident - a carbidic type which occurs at temperatures < 650 K and a graphite type at temperatures > 650 K. The carbide form saturates at 0.5 monolayers. Second, the carbon formation data from CO disproportionation indicates a rate equivalent to that observed for methane formation in a H2/CO mixture. Therefore, the surface carbon route to product is sufficiently rapid to account for methane production with the assumption that kinetic limitations are not imposed by the hydrogenation of this surface carbon. 

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