A new method of theoretical analysis for
temperature-programmed desorption (TPD) of ammonia to
determine
the acid amount and strength and its distribution from a one-time
experiment is proposed on the basis of the
equilibrium between gaseous and adsorbed ammonia, i.e., free
readsorption of ammonia. The entropy change
was assumed to consist of the constant phase-transformation term and
the gaseous mixing term as a function
of gaseous concentration of ammonia. The enthalpy change, namely
adsorption heat, was assumed to have
several kilojoules per mole of the distribution. Thus a simulated
TPD curve could be fitted well with the
experimental data observed on mordenite and ZSM-5 zeolites. From
the parameter set that gave the best
fitted curve, the acidic properties of zeolite were determined.
The determined acid amount was close to the
difference between the aluminum and sodium contents, [Al] − [Na],
in most cases. This confirms a simple
principle that one acid site is generated by isomorphous substitution
of one aluminum atom into the silicate
matrix, and one sodium atom blocks one acid site. On the other
hand, the mordenite and ZSM-5 had the acid
strength, ca. 145 and 130 kJ
mol-1, of the adsorption heat of ammonia,
respectively, with several kilojoules
per mole of the distribution, irrespective of the acid amount.
Another simple principle is therefore proposed:
the acid strength of zeolite is determined by the crystal
structure.
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