The previously obtained results on sulphate‐water interactions both in liquid and solid states in the four measuring systems (high resolution mixing calorimetry, differntial scanning calorimetry, thermomechanical analysis, and dynamic thermal densimetric analysis) are retrieved according to the universal topoenergetic procedure by considering the solute concentration as governing potential. Ontogenic and phylogenic parameters defining the nature, the overall amplitude, the mass of the kinetic entity and the coupling strength of these interactions, allow to establish the composite structure both of pure water and of aqueous solutions. At least two structures exist in these specimens made from the pure water with isolated molecules and polymerized water molecules involving cations which catalyze H‐bond forming in polymeric chains.
The solubility behaviour of several hydrated and anhydrous sulphates has been studied isothermally (26.24-0.06 ~ by using the high-resolution calorimeter previously described. The notion of behaviour recently defined in terms of topoenergetic principles was adopted for these experiments by establishing standard experimental conditions (SEC), mainly covering the geometry of the measuring cell and the figure of merit of the overall calorimetric system. The previously defined parameters from the heat flow recorded at normal and high speed clearly show the oscillatory behaviour generally predicted by the topoenergetic theory. The measuring system used also allows the demonstration of a difference in behaviour for size fractions of the same solute. The overall solubility behaviour finder the same SEC for all values of solute mass can be defined in accordance with the universal topoenergetic procedure applied to a large variety of composite and measuring systems. The resulting data associated with the individual (ontogenic) and the group (phylogenic) behaviour can provide Data Banks for general use. The solubility in two-component systems is a complex problem in terms of classical thermodynamics [1], involving many experimental and theoretical aspects.A new view of this problem is provided by the topoenergetic theory of behaviour of non-equilibrium composite systems, recently developed and applied to a large variety of particular cases [2]. In fact, the notion of system behaviour is actually adopted in classical terms [1], considering that the kinetic aspects of solubility are important in the conversion of the integral heat of solution (E,) as a function of the mass of solute (ms,). However, the experimental data accumulated to date involve an important disadvantage concerning the experimental conditions. It is known that the kinetics of any kind of transformation process depends strongly on the geometry and dimensions of the overall reacting system, no matter how carefully the initial components are examined as regards purity and proportion. The
The temporal relativistic principle, recently established for calorimetric systems in the framework of the theory of the topoenergetic behaviour of composite systems, is extended to general thermal measuring systems. A thermal measuring system is defined as a measuring system in which the conversion of a response function is measured as a result of a stepwise perturbation in temperature. The process of crystallization revealed by different thermal measuring systems is considered for a series of compounds for which the processes are identical in nature, but differ in amplitude, so that an external affine relation E = n K q-m is verified between the activation energy E and the amplitude term K. It results that the polarity of a transformation process is a characteristic proper to the temporal reference system of the considered measuring system and can be expressed by the signs of the parameters E and/or n. Review of topoenergetic conceptsOn the basis of the recently established topoenergetic principles [1,2], it has been concluded that the behaviour of a composite system in a thermal measuring system is univocally defined by the nature and the amplitude of the revealed transformation process [3]. The two characteristics can be quantitatively determined from the parameters (E, K) which generally define the kinetic equations proper to the direct or single measuring system (SMS) and the differential measuring system (DMS), respectively [4], namely:These equations were established by modelling the eqivalent energetic principles, and both impose as the transformation temperature T, to be applied by the stepwise boundary condition [2], starting from an initial value at which the process occurs slowly or is completely inhibited. Thus a thermal measuring system can be defined as any kind of energetic circuit in which the time conversion for a physical value can be measured as a result of the stepwise variation of the external temperature. DTA systems represent a particular case recently considered in topoenergetic terms [1 -6], with a view to determining the behaviour of the processes of crystallization [5], thermooxidation [4,6], curing-polymerization [7] and degradation by molec-
The most important calorimetric methods have been reviewed: the differential thermal analysis (DTA) as basic disposition and the scanning calorimetry (DSC) as well as the adiabatic rate calorimetry (ARC). The thermal circuits of these are expressed by bond diagrams as conceived by topological thermodynamics. It has been stated that the heat flux associated with the process of transformation is virtually (uncompensated) transferred in the DTA system, really transferred (compensated) in the DSC and ARC systems, between the two containers through a transfer medium assumed to be purely dissipative.
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