Isosteric heats of adsorption and adsorption isotherms have been measured simultaneously in a calorimeter for a series of gases of increasing size and magnitude of quadrupole moment (Ar, O2, N2, CH4, C2H6, SF6, CO2) on adsorbents of varying pore structure and ion type (NaX, H-ZSM-5, Na-ZSM-5). Adsorption isotherms have been checked for reversibility by desorption experiments. The average experimental error in loading is ±0.6%; the average uncertainty in the isosteric heat of adsorption is ±0.5 kJ/mol. Heats of adsorption of nonpolar molecules (CH4, C2H6, SF6) increase in the order NaX, silicalite, H-ZSM-5, Na-ZSM-5 at low coverage. Heats of adsorption of nonpolar molecules are almost identical on silicalite, H-ZSM-5, and Na-ZSM-5 at high coverage. Heats of adsorption of the quadrupolar molecule CO2 increase in the order silicalite, H-ZSM-5, Na-ZSM-5, NaX. The electric field adjacent to Na+ sites is 6.2 V/nm, on the basis of the difference between the heat of adsorption of CO2 in Na-ZSM-5 and the heat of adsorption of CO2 in silicalite.

A Tian−Calvet type calorimeter is applied to the simultaneous determination of adsorption isotherms and heats of adsorption. This is the first of a series of studies of the effect of adsorbate size and polarity on the energetics of adsorption in zeolites. The adsorbate gases used in this study are quadrupolar (N2 and CO2) and nonpolar (Ar, O2, CH4, C2H6, and SF6). The heats of adsorption of both polar and nonpolar gases are either constant or increase with coverage, so silicalite may be classified as a relatively homogeneous adsorbent compared to X type zeolite. Reversibility was established by comparing adsorption and desorption isotherms. Reproducibility was studied by comparing runs for different samples of the same adsorbent. The average experimental error in loading is ±0.6%. The error in the isosteric heat of adsorption is ±2% for heats larger than 20 kJ/mol and ±5% for heats smaller than 20 kJ/mol.

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Individual heats of adsorption and selectivity of mixtures have been measured simultaneously in a calorimeter. After the weakly adsorbed component was preloaded the dosing of both components to the sample cell was adjusted to hold the loading of the weakly adsorbed component constant. Agreement with ideal adsorbed solution theory is quantitative for mixtures of CH4 and C2H6 at low coverage in an adsorbent with a weak electric field (silicalite). Mixtures of quadrupolar (CO2) and nonpolar (C2H6) gases in an adsorbent with a strong electric field (NaX) exhibit strong negative deviations from ideality. The experimental heats of adsorption are larger than those for an ideal solution, in agreement with the results of molecular simulation.

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