Chemisorption Of Alcohols On Alumina ? Introduction

In several previous studies from this laboratory (1-4) the autophobicity concept of Zisman and co-workers (5, 6) has been extended to gas phase adsorption processes. Low molecular weight alcohols adsorb on silica or alumina to yield novel isotherms in that monolayer adsorption occurs at low relative pressures indicative of strong bonding, but subsequently multilayer adsorption is quite sparse and diminishes with molecular weight of the alcohol. Such isotherms fit no standard classification scheme, however, in the vacinity of monolayer coverage alcohol isotherms give an excellent fit to the Langmuir or B. E. T. , Type I model (7). Monolayer adsorption is relatively irreversible and it is thus possible to prepare these chemisorbed layers and perform subsequent adsorption studies thereon. All indications are that the adsorptive properties on such films is radically different from that on the underlying alumina (4, 8) and in one study finite contact angles for hydrocarbon fluids were observed. One perennial conceptual difficulty is that there is no observed upper bound to the adsorption isotherm which would be necessary for autophobic adsorption to occur. The cause for this has been studied, and it is currently believed that adsorption is complicated by reversible capillary condensation at contact points between powder particles. The evidence for this is that large particle powders give less "apparent" adsorption at high relative pressures and in one very tedious study adsorption on planar sheets, oxidized aluminum displayed similar reduced uptake at high relative pressures when compared with high specific surface area powders (3).