On thermodynamic equilibrium of carbon deposition from gaseous C-H-O mixtures: updating for nanotubes

Extensive literature information on experimental thermodynamic data and theoretical analysis for depositing carbon in various crystallographic forms is examined, and a new three-phase diagram for carbon is proposed. The published methods of quantitative description of gas-solid carbon equilibrium conditions are critically evaluated for filamentous carbon. The standard chemical potential values are accepted only for purified single-walled and multi-walled carbon nanotubes (CNT). Series of C-H-O ternary diagrams are constructed with plots of boundary lines for carbon deposition either as graphite or nanotubes. The lines are computed for nine temperature levels from 200 degrees C to 1000 degrees C and for the total pressure of 1 bar and 10 bar. The diagram for graphite and 1 bar fully conforms to that in (Sasaki K, Teraoka Y. Equilibria in fuel cell gases II. The C-H-O ternary diagrams. J Electrochem Soc 2003b, 150: A885-A888). Allowing for CNTs in carbon deposition leads to significant lowering of the critical carbon content in the reformates in temperatures from 500 degrees C upward with maximum shifting up the deposition boundary O/C values by about 17% and 28%, respectively, at 1 and 10 bar.