Aromatics graphitization

Diamond is the prototype of all alijihatic compounds. One would expect on its surface free valences which are capable of surface compound formation. The surface compounds on diamond should differ somewhat in character as compared to the surface compounds on aromatic graphite or microcrystalline carbon. Apart from singly bonded carbon atoms on the edges and corners of diamond crystals... 

The model that emerged [50] is of short sections (< 5 carbon atoms) of sp CH2 chains and statistically distributed CH groups in an sp -sp carbon network with olefinic rather than aromatic (graphitic) carbons. The two environments are separated by regions of non-hydrogenated sp carbons. 

Because they contain many islets of condensed aromatics, the carbon-rich asphaltenes can begin to acquire the spatial organization of graphite layers. 

This becomes more aromatic and carbon-rich as it generates petroleum and evolves toward graphite. In contrast, the solvent-extractable lower molecular weight organic materials called bitumen or extractables increase in hydrogen content and progress through compositions typical of cmde oils to those of gas (10). 

At pressures of 13 GPa many carbonaceous materials decompose when heated and the carbon eventually turns into diamond. The molecular stmcture of the starting material strongly affects this process. Thus condensed aromatic molecules, such as naphthalene or anthracene, first form graphite even though diamond is the stable form. On the other hand, aUphatic substances such as camphor, paraffin wax, or polyethylene lose hydrogen and condense to diamond via soft, white, soHd intermediates with a rudimentary diamond stmcture (29). 

Complex aromatic raw materials such as petroleum resids, decant oils, coal, and coal tars have been employed for many years by the earbon industry and eontinue to be used extensively in the fabneation of eoke, earbon, and artifieial graphite [1], These same feedstoeks also have the potential for use in produeing "advaneed" earbon produets such as carbonaceous mesophase, fibers, and beads 12-4],... 

Zebiihr et al. (29) developed an automated system for determining PAHs, PCBs and PCDD/Fs by using an aminopropyl silica column coupled to a porous graphitic carbon column. This method gives five fractions, i.e. aliphatic and monoaromatic hydrocarbons, polycyclic aromatic hydrocarbons, PCBs with two or more ortho-chlorines, mono-ort/io PCBs, and non-ortho PCBs and PCDD/Fs. This method employed five switching valves and was successfully used with extracts of sediments, biological samples and electrostatic filter precipitates. 

In graphite each carbon atom is bound to three others in the same plane and here the assumption of inversion of a puckered layer is improbable, because of the number of atoms involved. A probable structure is one in which each carbon atom forms two single bonds and one double bond with other atoms. These three bonds should lie in a plane, with angles 109°28 and 125°16,l which are not far from 120°. Two single bonds and a double bond should be nearly as stable as four single bonds (in diamond), and the stability would be increased by the resonance terms arising from the shift of the double bond from one atom to another. But this problem and the closely related problem of the structure of aromatic nuclei demand a detailed discussion, perhaps along the lines indicated, before they can be considered to be solved. 

Values of the diamagnetic anisotropy of benzene and other aromatic hydrocarbon molecules are calculated on the basis of the assumption that the p, electrons (one per aromatic carbon atom) are free to move from carbon atom to adjacent carbon atom under the influence of the impressed fields. When combined with the assumed values for the contributions of the other electrons (-2.0X 10-6 for hydrogen, —4.5 X10 c for aromatic carbon, — 6.0XlO-6 for aliphatic carbon) these lead to principal diamagnetic susceptibilities of molecules in approximate agreement with the available experimental data. The diamagnetic anisotropy of graphite is also discussed. 

Accordingly, the mechanism of conduction in metals is different from that for the ring currents in benzene, other aromatic molecules, and graphite, in which the atoms do not have the metallic orbital.16 16... 

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