The desorption of H2O from a hydroxylated single-crystal alpha-Al2O3(0
001) surface was studied using laser-induced thermal desorption (LITD)
and temperature-programmed desorption (TPD) techniques. alpha-Al2O3(0
001) models the surface of exhaust particles from solid rocket motors.
H2O desorption from alpha-Al2O3(0001) will determine hydroxyl coverag
es that will influence Al2O3 surface chemistry. H2O desorption from th
e hydroxylated alpha-Al2O3(0001) surface occurred over a temperature r
ange from 300 to 500 K. This broad distribution suggests a variety of
hydroxyl surface sites with different binding energies. H2O desorption
results versus hydroxyl coverage prepared by progressively annealing
a fully hydroxylated alpha-Al2O3(0001) surface confirmed a wide range
of hydroxyl binding energies. Additional H2O desorption results versus
hydroxyl coverage prepared by varying the H2O exposure revealed that
H2O dissociative adsorption randomly fills the adsorption sites indepe
ndent of their adsorption energy. These results argued that hydroxyl s
urface diffusion between the various adsorption sites must be negligib
le. Modeling of the desorption results was consistent with hydroxyl de
sorption energies that range from E-d = 23 to E-d = 41 kcal mol(-1). T
he H2O desorption results predict that hydroxyl groups will be stable
on alpha-Al2O3 rocket-exhaust particles under stratospheric conditions
. (C) 1998 Published by Elsevier Science B.V. All rights reserved.