Henry constant and isosteric heat at zero-loading for gas adsorption in carbon nanotubes.

The Henry constant and the isosteric heat of adsorption at zero loading in a carbon nanotube bundle are studied with Monte Carlo integration for the adsorption of gases over a range of temperatures. The spacing between nanotubes in a bundle is determined from the minimization of potential energy of interaction between these tubes. We study different tube configurations with bundles of 2, 3, 4 and 7 tubes. Depending on the configuration it is found that the spacing is of between 0.31 to 0.333 nm, and this falls within the range reported in the literature. The Henry constant has been carefully defined so that it will not become negative at high temperatures. This is done with the aid of accessible volume, rather than the usual absolute void volume. We show that linearity of the van't Hoff plot for the Henry constant is not strictly followed. Furthermore the slope of this plot is not equal to the isosteric heat of adsorption at zero loading, which is found to be a strong function of temperature. From the results we find that the Henry constant and the heat of adsorption depend on the tube configuration. In general the adsorption in the cusp interstices is strongest followed by that inside the tube and finally on the outer surface. However for very small tubes adsorption occurs inside the tube first. For molecules with orientation, the behaviour is even more interesting and the shape of the isosteric heat versus temperature depends on the degree of orientation, tube configuration and the domain of adsorption (interstices, inside the tube and on the outer surface).