Using an IRMS-TPD (temperature programmed desorption) of ammonia, we studied the nature, strength, crystallographic location, and distribution of acid sites of mordenite. In this method, infrared spectroscopy (IR) and mass spectroscopy (MS) work together to follow the thermal behavior of adsorbed and desorbed ammonia, respectively; therefore, adsorbed species were identified, and their thermal behavior was directly connected with the desorption of ammonia during an elevation of temperature. IR-measured TPD of the NH4(+) cation was similar to MS-measured TPD, thus showing the nature of Brønsted acidity. From the behavior of OH bands, it was found that the Brønsted acid sites consisted of two kinds of OH bands at high and low wavenumbers, ascribable to OH bands situated on 12- and 8-member rings (MR) of mordenite structure, respectively. The amount and strength of these Brønsted hydroxyls were measured quantitatively based on a theoretical equation using a curve fitting method. Up to ca. 30% of the exchange degree, NH4(+) was exchanged with Na+ on the 12-MR to arrive at saturation; therefore, in this region, the Brønsted acid site was situated on the large pore of 12-MR. The NH4(+) cation was then exchanged with Na+ on 8-MR, and finally exceeded the amount on 12-MR. In the 99% NH4-mordenite, Brønsted acid sites were located predominantly on the 8-MR more than on the 12-MR. Irrespective of the NH4(+) exchange degree, the strengths deltaH of Brønsted OH were 145 and 153 kJ mol(-1) on the 12- and 8-MR, respectively; that is, the strength of Brønsted acid site on the 8-MR was larger than that on the 12-MR. A density functional theory (DFT) calculation supported the difference in the strengths of the acid sites. Catalytic cracking activity of the Brønsted acid sites on the 8-MR declined rapidly, while that on the 12-MR was remarkably kept. The difference in strength and/or steric capacity may cause such a difference in the life of a catalyst.