Some solid acids, including sulfated zirconia and certain industrial i
somerization catalysts, catalyze two types of n-butane isomerizations,
avoiding primary carbenium ions or carbonium ions: (1) an internal re
arrangement of the C atoms in n-butane and (2) skeletal isomerization
of n-butane to iso-butane. No superacid sites are required for these r
eactions. The skeletal isomerization is an intermolecular reaction, in
volving a C-8 intermediate. Easily accessible Bronsted acid sites and
small amounts of olefin are crucial. Spectroscopic examination of the
acid sites on sulfated zirconia shows that they are not stronger than
the acid sites in zeolites such as HY. The butane isomerization rate i
s suppressed by CO, even when no CO is adsorbed on Lewis sites; format
ion of oxocarbenium ions is likely. The decisive role of Bronsted acid
sites is demonstrated by results on deuterated catalysts.