Dual site population

Due to the presence of low-temperature desorption peak a new desorption site was included to phenomenological model of TPD experiments previously used for the description of the Cu-Na-FER samples [5], The fit of experimental TPD curves was performed in order to obtain adsorption energies and populations for individual site types sites denoted A (A1 pair), B (sites in P channel (A1 at T1 or T2)), C (sites in the M channel and intersection (A1 at T3 or T4)) [3] and D (newly introduced site). The new four-site model was able to reproduce experimental TPD curves (Figure 1). The desorption energy of site D is cu. 82 kJ.mol"1. This value is rather close to desorption energy of 84 kJ.mol"1 found for the site B , however, the desorption entropy obtained for sites B and D are rather different -70 J.K. mol 1 and -130 J.K. mol"1 for sites B and D , respectively. We propose that the desorption site D can be attributed to so-called heterogeneous dual-cation site, where the CO molecule is bonded between monovalent copper ion and potassium cation. The sum of the calculated populations of sites B and D (Figure 2) fits well previously published population of B site for the Cu-Na-FER zeolite [3], Because the population of C type sites was... 

In the dual-mode sorption and transport model the pressure-dependence of a (= C/p), P and 0 in gas-glassy polymer systems arises from the pressure-dependent distribution of the sorbed gas molecules between Langmuir sites and Henry s law dissolution. Although k, Dg and are assumed to be constant, the average or effective solubility and diffusion coefficients of the entire ensemble of gas molecules change with pressure as the ratio of Henry s to Langmuir s population, C /C, changes continuously with pressure [eq. (14)]. 

According to the dual-sorption model, gas sorption in a polymer (cm) occurs in two types of sites. The first type is filled by gas molecules dissolved in the equilibrium free volume portion of material (concentration cH). In rubbery polymers this is the only population of dissolved gas molecules, but in glassy polymers a second type of site exists. This population of dissolved molecules (concentration cD) is dissolved in the excess free volume of the glassy polymer. The total sorption in a glassy polymer is then... 

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