Carbon monoxide, bond dissociation energy

Carbon monoxide has a larger bond dissociation energy (1072 kJ/mol) than molecular nitrogen (945 kJ/mol). Suggest an explanation. 

Because the thermolysis of the cobalt-cobalt bond in Co2(CO)8 changes the magnetic susceptibility of the solution due to the production of Co(CO)4 radicals, the extent of this homolysis was determined by measuring the temperature dependence of the volumetric susceptibility of a gas-phase solution of Co2(CO)8 in carbon monoxide in the temperature range 120-225°C. From the temperature dependence of the equilibrium constant, AH = (81.1 8.5) kJ/mol and AS = (123.8 17.1) J/(mol K) have been calculated (147). The bond dissociation energy based on thermochemical calculations has been given as D298[(CO)4Co-Co(CO)4] = 83 29 kJ/mol (235). 

Step through the sequence of structures representing dissociation oiketene to methylene and carbon monoxide. Plot energy (vertical axis) vs. carbon-carbon bond distance (horizontal axis). Would you describe ketene as a weak complex between singlet methylene and carbon monoxide Explain. (A table of CC and CO bond lengths is found at left.) Is there an energy barrier to the dissociation ... 

Carbon Monoxide. There are close similarities between carbon monoxide and nitrogen. The molecules are isoelectronic, and the bond lengths and dissociation energies are quite comparable. The phase diagrams of the two compounds show the same trends in the moderate pressure range with a variety of phase transitions between essentially alike crystal structures [333], when allowance is made for the lack of the inversion center and the presence of a weak electric dipole moment in carbon monoxide. However, the behavior and stability at higher... 

Figure 2.16. Calculated dissociative nitrogen ( ), carbon monoxide ( ), and oxygen ( ) chemisorption energies over different 3d transition metals plotted as a function of the center of the transition metal rf-bands. A more negative adsorption energy indicates a stronger adsorbate-metal bond. Reproduced from [32].

The idea that catalyst surfaces possess a distribution of sites of different energies has been around since the 1920s, but it has not been possible until fairly recently to show that adsorption sites on terraces, steps, and kinks differ in energy. For example, hydrogen shows stronger bonding to steps and kinks on platinum than on the 111 terraces. In addition, the activation energy for H2 dissociation is about zero on the step face and about 8.4 kJ mole-1 on the terrace plane. In addition, carbon monoxide is adsorbed with dissociation on the kinks of Pt, but in the molecular form on the steps and terraces. 

A second type of cluster emission involves molecular species which can be as simple as carbon monoxide or as complicated as the dodecanucleotide mentioned above. In the first case, the CO bond strength is 11 eV, but the interaction with the surface is only about 1 eV. Calculations indicate that this energy difference is sufficient to allow ejection of CO molecules, although 15 percent of them can be dissociated by the ion beam or by energetic metal atoms (6). For such molecular systems it is easy to infer the original atomic configurations of the molecule and to determine the... 

In reaction (3) two carbon-carbon bonds are broken and at first sight one would expect this dissociation to absorb 140,000 calories but, as in equation (1), 64,000 calories is evolved in going from the > CO radical to carbon monoxide. The sum total of energy absorbed then is 76,000 calories. 

Transition metal catalysts, specifically those composed of iron nanoparticles, are widely employed in industrial chemical production and pollution abatement applications [67], Iron also plays a cracial role in many important biological processes. Iron oxides are economical alternatives to more costly catalysts and show activity for the oxidation of methane [68], conversion of carbon monoxide to carbon dioxide [58], and the transformation of various hydrocarbons [69,70]. In addition, iron oxides have good catalytic lifetimes and are resistant to high concentrations of moisture and CO which often poison other catalysts [71]. Li et al. have observed that nanosized iron oxides are highly active for CO oxidation at low tanperatures [58]. Iron is unique and more active than other catalyst and support materials because it is easily reduced and provides a large number of potential active sites because of its highly disordered and defect rich structure [72, 73]. Previous gas-phase smdies of cationic iron clusters have included determination of the thermochemistry and bond energies of iron cluster oxides and iron carbonyl complexes by Armentrout and co-workers [74, 75], and a classification of the dissociation patterns of small iron oxide cluster cations by Schwarz et al. [76]. 

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