Rate constants for H abstraction from benzo(a)pyrene and chrysene: a theoretical study.

Density functional B3LYP/6-31G(d) and ab initio G3(MP2,CC) calculations have been carried out to determine thermal rate constants of direct H abstraction reactions from four- and five-ring polycyclic aromatic hydrocarbons (PAH) chrysene and benzo[a]pyrene by various radicals abundant in combustion flames, such as H, CH3, C3H3, and OH, using transition state theory. The results show that the H abstraction reactions with OH have the lowest barriers of ∼4 kcal mol-1, followed by those with H and CH3 with barriers of 16-17 kcal mol-1, and then with propargyl radicals with barriers of 24-26 kcal mol-1. Thus, the OH radical is predicted to be the fastest H abstractor from PAH. Even at 2500 K, the rate constant for H abstraction by H is still 34% lower than the rate constant for H abstraction by OH. The reaction with H is calculated to have rate constants 35-19 times higher than those for the reaction with CH3 due to a more favorable entropic factor. The reactions of H abstraction by C3H3 are predicted to be orders of magnitude slower than the other reactions considered and their equilibrium is strongly shifted toward the reactants, making propargyl an inefficient H abstractor from the aromatics. The calculations showed strong similarity of the reaction energetics in different H abstraction positions of benzo[a]pyrene and chrysene within armchair and zigzag edges in these molecules, but clear distinction between the armchair and zigzag sites. The zigzag sites appear to be more reactive, with H abstraction rate constants by H, CH3, and OH being respectively 37-42%, a factor of 2.1, and factors of 8-9 higher than the corresponding rate constants for the H abstraction reactions from armchair sites. Although the barrier heights for the two types of edges are similar, the entropic factor makes zigzag sites more favorable for H abstraction. Rate expressions have been generated for all studied reactions with the goal to rectify current combustion kinetics mechanisms.

Multiscale modeling catalytic decomposition of hydrocarbons during carbon nanotube growth.

A molecular dynamics simulator coupled to a quantum semiempirical Hamiltonian model was applied to multiscale modeling of the catalytic decomposition of hydrocarbons during carbon nanotube (CNT) and carbon nanofiber (CNF) growth. It was found that catalytic decomposition of acetylene is accompanied by a large energy release and its rate weakly depends on temperature in the range from 20 to 700 degrees C. In contrast, the methane decomposition rate substantially decreases as the iron temperature drops. A comparative analysis of acetylene decomposition on a clean surface and on an oxidized Fe(100) surface showed that the presence of oxygen reduces the decomposition rate by an order of magnitude, but has very little influence on the amount of heat released by the reaction. We also found that oxygen absorbed on the surface of catalyst does not easily diffuse into the catalyst or desorb from the surface. This implies that the surface of the catalyst is quickly covered by oxygen during CNT/CNF growth even at low oxygen flow rates.

A new mechanism for the formation of meteoritic kerogen-like material.

The carbon in ancient carbonaceous chondritic meteorites is mainly in a hydrocarbon composite similar to terrestrial kerogen, a cross-linked structure of aliphatic and aromatic hydrocarbons. Until recently, the composite has been commonly thought to have been produced in the early solar nebula by a Fischer-Tropsch-type process, involving the catalytic synthesis of hydrocarbons from carbon monoxide and hydrogen on grain surfaces. Instead, the aromatic hydrocarbons may form in gas-phase pyrolysis of simple aliphatics like acetylene and methane by a mechanism developed recently to explain formation of soot in combustion and of aromatic molecules in circumstellar envelopes. Nonequilibrium chemical kinetic calculations indicate that this mechanism can produce meteoritic aromatics if the initial concentration of simple hydrocarbons in the solar nebula was sufficiently but not unreasonably high.