A general method of thermal analysis is presented, whose aim is to reduce at will pressure and temperature gradients inside the sample submitted to thermolysis. The basic idea is to control the sample temperature so as to keep constant a parameter related to the decomposition rate. Attention is specially called on the case when the controlled parameter is pressure, which allows to monitor at the same time two parameters (pressure and decomposition rate). As an example, one apparatus is described, working in the pressure range between 20 and 10−3 torr. This method of Constant Rate Thermal Analysis (CRTA) appears to be specially suited for thermal analysis under controlled vacuum, for the preparation of well defined porous samples, and for the study of decomposition mechanisms.
Sample controlled thermal analysis (SCTA) can be used in several manners with respect to adsorbents. Almost 70% of adsorbent
synthesis procedures involve a thermal step that can be adapted to a sample controlled method. In this respect, SCTA has been
used for the preparation of activated alumina, calcination of zeolites and activation of carbons. The thermodesorption of
adsorbed molecules can also be carried out using a sample controlled method. Here, both the surface area and pore volume of
adsorbents can be assessed. Finally, SCTA can be highly beneficial in the thermal pretreatment of adsorbents prior to adsorption.
A method is described where the simultaneous measurement of a thermal flow (by means of Tian-Calvet type calorimetry) and of a gas flow (by means of constant decomposition rate thermal analysis) allows the knowledge at any time of the instantaneous enthalpy of thermal dissociation. The method is used to study the thermal decomposition of an industrial Al(OH)3 gibbsite sample.
This paper examines the influence of residual pressures in the range from 10−5 to 5 torr on the course of thermal analysis. With the help of examples concerning in particular the thermolysis of gibbsite, A1(OH)3, it is shown that a) the control of residual pressure is of virtually no use unless the rate of decomposition isalso controlled (otherwise, the TG curves represent a composite phenomenon, which is practically unintelligible); b) the influence of residual pressure may be unexpectedly high both on the shape of the TG curves (and therefore on the apparent kinetic parameters) and on the nature (porosity, structure) of the products.
Authors:M. Torralvo, Y. Grillet, F. Rouquerol, and J. Rouquerol
Thermodesorption is here considered for its possibility of giving access to the microporosity of adsorbents. The requirements
of this application (good separation of successive desorption steps, good control of the desorption pressure and temperature
throughout the sample, possibility of a safe kinetic analysis of each step) are here fulfilled by carrying out the thermodesorption
in the Controlled transformation Rate Thermal Analysis (CRTA) mode. The method is applied to 4 zeolites (3A, 4A, 5A and 13X)
and a well characterized charcoal, from −25 to 325°C, after pre-adsorption of water.
Authors:M. Reading, D. Dollimore, J. Rouquerol, and F. Rouquerol
The uncertainty surrounding the significance of the measured kinetic parameters of solid state decomposition reactions is discussed briefly. Some suggestions are made about what precautions should be taken in order to favour the measurement of undistorted results. Some criteria are proposed for deciding whether a measuredE value can be considered to have its usual meaning. The results of a series of experiments aimed at measuring the activation energy of the decomposition of calcium carbonate using a variety of methods, sample sizes and experimental conditions are presented. These results are compared with results found in the literature and it is concluded that it is possible to measure a reproducible value forE and it is tentatively proposed that this value is meaningful in terms of the energy barrier model of chemical reaction kinetics.
Authors:P. Llewellyn, N. Pellenq, Y. Grillet, F. Rouquerol, and J. Rouquerol
Water adsorption at temperatures of 286 and 296 K on silicalite-I, ZSM-5 (Si/Al=16), ZSM-48 (Si/Al=50) and AlPO4-5 is followed by gravimetry with a quasi-equilibrium continuous adsorptive introduction.
The results show that all of these samples are characterized by a continuous distribution of strongly energetic water adsorption
sites (from 60 to 120 kJ·mol−1) for which the adsorption is irreversible at the experimental temperature. This probably justifies the presence of hysteresis
on desorption at very low relative pressure values. Adsorption of water in these systems firstly occurs by site. This is then
followed by cluster formation and it is suggested that it is the ability of the adsorbent to build up these clusters within
the microporous structure which determines intracrystalline uptake. It is put forward that the zeolites, silicalite-I and
ZSM-5, do not accommodate cluster formation within its microporous network. However, an external flexible microporous structure,
containing Lewis sites, may be present for large crystals. This flexible secondary structure may then be able to opened (swelled)
at high relative pressures.
On the other hand, for the aluminophosphate AlPO4-5, it is believed that a change in the aluminium coordination on the formation of a crystal hydrate together with capillary
condensation results in a large step in the adsorption isotherm, which is itself preceded by a smaller step, revealing a brutal
densification of the adsorbed phase.