The paper presents possible applications of differential thermal analysis for study of the physicochemical properties of liquid/solid systems, mainly through programmable liquid thermodesorption from the sample under quasi-isothermal conditions. The results prove its applicability in the determination of solid physicochemical properties, and particularly in calculations of adsorption potential distribution, the activation energy of molecules adsorbed on the surface and the surface heterogeneity by means of computer techniques.
Authors:J. Kristóf, E. Horváth, R. Frost, and J. Kloprogge
The thermal behaviour of fully and partially expanded kaolinites intercalated with formamide has been investigated in nitrogen atmosphere under quasi-isothermal heating conditions at a constant, pre-set decomposition rate of 0.20 mg min–1 . With this technique it is possible to distinguish between loosely bonded (surface bonded) and strongly bonded (intercalated) formamide. Loosely bonded formamide is liberated in an equilibrium reaction under quasi-isothermal conditions at 118°C, while the strongly bonded (intercalated) portion is lost in an equilibrium, but non-isothermal process between 130 and 200°C. The presence of water in the intercalation solution can influence the amount of adsorbed formamide, but has no effect on the amount of the intercalated reagent. When the kaolinite is fully expanded, the amount of formamide hydrogen bonded to the inner surface of the mineral is 0.25 mol formamide/mol inner surface OH group. While the amount of surface bonded formamide is decreasing with time, no change can be observed in the amount of the intercalated reagent. With this technique the mass loss stages belonging to adsorbed and intercalated formamide can be resolved thereby providing a complex containing only one type of bonded (intercalated) formamide.
A method was devised to evaluate latent heats of vaporization from quasi-isothermal isobaric analysis data. The procedure
requires the recording of at least two diagrams: one for the investigated liquid, and the other for a standard liquid with
a known latent heat of vaporization. Use of the method to determine the heats of vaporization of some alcohols, with water
as standard liquid, led to results close to those previously reported in the literature.
The main advantage of the procedure consists in the fact that it requires only small amounts of sample (5–10 mg).
Quasi-isothermal thermogravimetry is a new technique in which the programmed heating of a furnace automatically ceases when the rate of a reaction taking place in a sample, which is indicated by the DTG-signal, exceeds a preset limit. In this way reactions can be studied under nearly isothermal conditions. In this paper the data obtained using this method during oxidation and reduction experiments on nonstoichiometric cerium oxides are compared with the data obtained by conventional isothermal thermogravimetry. The kinetics of the composition changes during isothermal reduction and oxidation of CeO2−x are also analyzed. It appears that, with some reservations, the experimental data are best described by the rate equation for a diffusion-controlled reaction. Finally, both the isothermal and the quasi-isothermal data suggest that the CeO2−x phase region in the phase diagram consists of several subphases, each with a characteristic activation energy for the diffusion-controlled reactions.
under quasi-isothermalconditions are capable of reducing the average error down to ±1%. To evaluate the claim, heat capacity measurements were carried out by quasi-isothermal mode on sapphire and ThO 2 . To understand the influence of period and
Authors:P. Staszczuk, M. Płanda-Czyż, M. Błachnio, and V. Kutarov
The new method of diffusion coefficient calculations
from thermogravimetry Q-TG data has been presented. Programmed thermodesorption
of polar and apolar liquids from aluminium oxide and montmorillonite-Na and
-La samples in quasi-isothermal conditions has been made. The result from
above method was compared with literature data and good correlation were obtained.
The author gives a detailed survey on thermogravimetric investigations under quasi-isothermal — quasi-isobaric conditions (Q-TG). According to the principle of the technique the heating of the sample is governed by the transformation itself according to the feed-back principle in a way that the transformations should take place at a strictly constant rate, slower by orders of magnitude than in the case of the conventional techniques. Due to this, the transformations take place under ideal conditions, near to physico-chemical requirements.Based on the obtained advantageous results further methods were elaborated, like thermo-dilatometry (Q-TD), evolved gas analysis (Q-EGA) and microdistillation under quasi-isothermal conditions.The second part of the present review deals with DTA and DSC techniques under quasi-isothermal conditions elaborated recently