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30 years of research in thermal analysis and calorimetry
A personal review
Abstract
The research in thermal analysis and calorimetry, conducted by the author over the period 1964 to 1993, is summarised and concisely reviewed. The major investigations have focussed on thermal analysis studies of coordination compounds, particularly the metal dithiocarbamate complexes. A significant solution calorimetric study of some metal dithiocarbamate complexes has also been undertaken. DSC has been applied to determine the sublimation enthalpies of many metal dithiocarbamate and metal pentane-2,4-dionate complexes and solution calorimetry has been applied to study the thermochemistry of the latter group of complexes. Thermal analysis investigations of several inorganic molten salt systems have been initiated. Thermometric titrimetry has been applied to study metal-macrocyclic ligand systems in aqueous media and particularly those systems of environmental significance. Temperature calibration standards for TMA have been proposed and TMA has been applied to study the mechanical properties of several common inorganic compounds. DTA has been applied to study a wide variety of phenols and has subsequently been applied as an analytical technique to determine the components of solid state phenol mixtures. Thermometric titrimetry has been applied to determine the phenolic content of wines. A comprehensive thermal analysis study of Australian brown coal has been undertaken, involving the DSC determination of coal specific energy, a TG/DTA study of the coal pyrolysis and combustion processes and a TG/DTA and EGA study of the cation catalytic effect on the coal pyrolysis process. Thermal analysis and calorimetric techniques have been extensively publicised and promoted by the publication of specialist reviews, the presentation of symposia review papers and the oral presentation of short courses, particularly in the SE Asian region. This review essentially reveals the diversity of possible application of thermal analysis and calorimetric techniques and the primary significance of thermodynamic data in the fundamental rationalisation of chemical phenomena.
The use of thermal analytical procedures to obtain both thermodynamic and kinetic parameters is outlined. The advantage of DTA techniques in establishing thermodynamic data is demonstrated. Kinetic data calculated from TG data is demonstrated. Kinetic data calculated from TG data leads to plots of the logarithm of the specific reaction rate constant against 1/T (whereT is the temperature in degrees Kelvin) and from this point onwards the calculation is the same to establish the kinetic parameters no matter whether the data was obtained from TG or isothermal studies. Information on changes in the density and surface area of solid residues in the decomposition process leads to the conclusion that the number of particles present changes significantly during the decomposition and it is pointed out that this factor is largely ignored in setting up kinetic models for the decomposition of solid materials.
irradiation. Besides enabling extrapolation of measured thermodynamic data to other temperature ranges, heat capacity data of the Mark-I and Mark-II fuels are also required to derive the thermal conductivity from the measured thermal diffusivity data. In the
to a number of copper units. Reactions of formation were then written as in Table 1 . Table 1 Thermodynamic data for some Cu compounds [ 14
, x 3 correspond to the mole fraction of components in investigated ternary system. Basic thermodynamic data on the constituent binary subsystems Ga–In, In–Sb and Sb–Ga, needed for calculation of thermodynamic properties in the investigated Ga
enables the understanding of the adsorbate–adsorbent interaction, from which the thermodynamic data can be determined [ 7 , 8 ]. Low-cost adsorbents such as sawdust, chitosans, clays, zeolites, soils, coals, natural oxides, humic substances, and
optimization procedure, we first imposed the conditions d 2 G /d x 2 > 0 for modeling the liquid phase using the phase boundary data reported by Massalski [ 5 ] and thermodynamic data. The optimization procedure was the following steps. The thermodynamic
range of 430–510 °C has been carried out. No other experimental determination of enthalpy of antlerite formation have been performed. However, the literature contains thermodynamic data for antlerite (Δ f G m o (298.15 K), Δ f H m o (298.15 K), and S
stable and metastable states of pure elements [ 3 ] was used. Thermodynamic data for the Al–Ge system were taken from Ref. [ 4 ], for the Al–Zn system were published in Ref. [ 5 ], and thermodynamic data for the system Ge–Zn were taken from Ref
concentration. Further step in the investigation of In–Sn behavior was a comparative thermodynamic analysis, in order to compare obtained experimental results by Oelsen calorimetric method with the literature thermodynamic data, taken from COST531
