| Popis: |
The Spheron 6 surface acidity has been investigated by adsorption of ammonia at 70°C and microcalorimetry. The carbon samples are degassed at temperatures up to 950°C. The effects of degassing temperature on the adsorption isotherms of ammonia are shown in Fig. 2. Up to 350°C, the isotherms are characterized by a very slight decrease in the total amount adsorbed. On the contrary, these amounts considerably decrease for higher degassing temperatures. The differential heats of adsorption (Fig. 3), which are initially close to 100 kJ/mole, are shown to decrease with the amount of adsorbed ammonia: the higher the degassing temperature, the greater the decrease. By desorption, the adsorption of ammonia is found partly irreversible. By readsorption it is possible to measure the differential heat of the reversible adsorption and to deduce from it the differential heat of the irreversible adsorption (Fig. 4) as well as the amount irreversibly adsorbed, i.e. chemisorbed. The amounts of chemisorbed ammonia are found to be respectively 0.36 ± 0.01 × 10 −6 mole m 2 at 150°C and 0.29 ± 0.01 × 10 −6 mole m −2 at 350°C. With the surface covering the differential heat of chemisorption of ammonia slightly decreases from 105 to 88 kJ. mole −1 . These values suggest that carboxyl groups are responsible for irreversible adsorption of ammonia. This assumption has been checked by various experiments: the irreversible uptake of ammonia lies in the same range as the number of carboxyl surface groups determined by chemical analysis of functional groups (Table 1); the evolving of H 2 O during the decomposition of the ammonium salt formed by reacting with ammonia has been observed and is probably correlated with the irreversible uptake of ammonia (Fig. 8); moreover it must be pointed out that irreversible adsorption of ammonia disappears after methylation of sample by diazomethane (Figs. 5 and 6). Then, the amounts of carboxyl groups can be determined by measuring the irreversibly adsorbed ammonia. This method has been applied to the study of the thermal stability of functional groups. Carboxyl groups are shown to be quickly decomposed by heat treatment above 500–600°C (Fig. 8). It appears from our experiments that the oxidation at constant temperature followed by a cooling under nitrogen is unable to regenerate functional groups on the surface of carbon after their removal at 950°C. On the contrary, by an oxidation at decreasing temperature it is possible to regenerate functional groups because they are stabilized by the oxidising atmosphere. The groups thus created behave like those initially present on Spheron 6: particularly the graph of the thermal elimination of carbon dioxide presents two peaks (Table 2, Fig. 12). The amount of regenerated carboxyl groups is found to be 0.25 × 10 −6 instead of 0.36 × 10 −6 mole m −2 on untreated Spheron 6. |
