desorbed species detected by mass spectroscopy were
alcohol and also their main reaction products, such as
ethers and olefins as well as water and other minor
by-products. The physisorbed methanol or ethanol
is removed at temperatures in the range 120–130◦C,
fairly higher than their corresponding boiling point.
However, alcohol was also found by mass spectroscopy
at much higher temperatures, which is believed
to be due to chemisorbed alcohol forming a
stable alkoxide at temperatures below 250◦C. Beyond
this temperature, chemisorbed alcohol can be removed
by thermal breaking of its oxygen bond. However, alcohol
molecules also can undergo dehydration giving
olefins, if possible, or etherification yielding ethers.
These species were detected for all the alcohol studied
at temperatures above 200–250◦C. The detection
of molecular alcohol at temperatures far away from
its boiling point certainly proves that the alcohol is
not merely physisorbed on the alumina surface.
It must be noted that chemisorbed normal alcohol
are stable at temperatures up to 250◦C, whereas secondary
alcohol desorbe earlier, at around 200◦C. This
behaviour could be explained by steric effects appearing
in the case of secondary alcohol, which make the
alkoxide less stable. However, n-octanol behaves as
secondary alcohol, which again could be related to
its higher molecular volume. In turn, iso-amyl alcohol
(3-methyl butanol) appears to show characteristic
trends from normal alcohol. No rational explanation
has been found in this case. On the other hand, physisorbed
alcohol was undoubtedly identified only
for the methanol and ethanol tests as its desorption
occurred at low temperatures, 120–130◦C. The lack
of physisorbed alcohol for the rest of alcohol could
be attributed to its higher molecular volume, which
could hinder the access to the pores. Thus, the amount
of physisorbed alcohol could be very low. Anyway,
the appearance of olefins and/or ethers during thermal
treatment confirms that chemisorbed species do exist
in all the cases. It must also be pointed out that, beyond
350◦C, no more desorbed species were detected
by mass spectroscopy, which suggests that the alcohol
is completely eliminated from the alumina surface