A novel parameter of the relative rate of thermal decomposition has been defined on the basis of an analysis of equation relating
the logarithm of the conversion degree on the temperature. The dependence of this parameter on temperature in the dynamic
conditions has been analyzed and discussed. The dependence of the relative rate of thermal decomposition is a linear relationship
involving two coefficients. These coefficients can be related to the enthalpy and activation energy. The parameter developed
has been used for the analysis of a series of consecutive reactions of thermal decomposition of calcium oxalate monohydrate.
The dependence of conversion degree estimated from the (TG) curve of the mass loss on heating of temperature has been analyzed.
It has been shown that dynamic TG curve can be modeled by an equation relating to the logarithm of conversion degree as a
function of temperature. A coefficient in the equation developed provides information on the distance from the equilibrium,
therefore, the coefficient a2=0–50 implies equilibrium, while a2>50 informs about some distance from the equilibrium. Further possibilities for the use of the models of lnα vs. 1/T in the analyses of thermodynamics and kinetics of thermal dissociation of solids has been shown.
It was proved on the basis of Holba-Šesták equation (1972) that the one is very interesting point of view to define the relative
rate of reaction/process. Thereby, the assumption about interconnection between three-parametric equation and thermodynamic
condition determined by equilibrium conversion degree in given temperature, is strengthened. Further considerations, still
based on analysis of the inequality, made possible proposition of thesis about maximal rate of reaction/process in dynamic
conditions in relation to modified van’t Hoff’s isobar (equation).
The idea of the generation of thermokinetic models on the basis of the analysis of kinetic equations (isothermal conditions)
and thermokinetic equations (dynamic conditions) is presented. The method resembles that used in polisothermal conditions,
which consists in analysis of the relation of the equilibrium conversion degree vs. temperature. The interpretation of the
coincidence of mass integrals g(α) in the relation α vs. temperature has been attempted.
We performed the analysis of the thermokinetic equations taking into account Kissinger law. The formulas obtained were verified
by the use of the so-called isokinetic effect. It was shown that the thermokinetic equation, g(α)=(AT/q)exp(-E/RT), appeared to connect both laws analyzed. Moreover, this approach validates equation km=q/Tm which takes a form of Kissinger law, i.e. ln(q/Tm) vs. 1/Tm.
Significant influence of sample preparation on thermal decomposition of polyolefin-technological oil mixtures was proved during
tests. Samples of polymer-oil mixtures were prepared with two methods: reducing size and components mixing and soaking in
temperature 170°C. Soaking causes decreasing thermal stability of the charge. This fact manifests itself in decreasing of
thermal decomposition temperature in laboratory scale, as well as in change of characteristic decomposition temperatures during
thermogravimetric analyses. Data analysis was performed with the use of classic method based on Arrhenius kinetic equation
and three-parameter model. The influence of sample composition and preparation method on values of three-parameter equation
coefficients was observed.
analyses of thermal decomposition (pyrolysis, thermal dissociation and combustion)
of 9 different samples were carried out in dynamic conditions at different
heating rates. The kinetic parameters (E, A and km)
of thermal decomposition were determined and interrelations between the parameters
and heating rate q were analyzed. There
were also relations between Arrhenius and Eyring equations analyzed for thermal
decomposition of solid phase. It was concluded that Eyring theory is an element,
which interconnects used thermokinetic equations containing Arrhenius law
and suggests considering kinetic quantities in way relative to 3 kinetic constants
and km). Analysis
of quantities other than km (i.e. E, A, Δ+H, Δ+S) in relation to heating rate is an incomplete method
and does not lead to unambiguous conclusions. It was ascertained that in ideal
case, assuming constant values of kinetic parameters (E
and A) towards heating rate and satisfying
both Kissinger equations, reaction rate constant km
should take on values intermediate between constants (km)1
determined from these equations. Whereas behavior of parameters E and A towards q were not subjected to any rule, then plotting relation kmvs.q in the background of (km)1
made possible classification of differences between thermal decomposition
processes taking place in oxidizing and oxygen-free atmosphere.
The results of the thermokinetic analysis of the combustion of carbon containing materials in the air and oxygen have been
presented. A thermokinetic model has been developed, which simplifies the current approach assuming the0-th order and zero
activation energy for this process. The interpretation of the results makes possible the identification of the material (carbon
carrier) of the highest reactivity toward oxygen. This material was used as a component of the insulating grease fill for
the continuous slab caster (CSC) process. The application of the fill proves successful in the industrial practice.
Further considerations concerning thermal decomposition of reference material — CaCO3, described by three-parametric equation in version (3), have been presented. It was established that in linear relationship
between coefficients of Eq. (3) a2 is the argument of a1, which reaches minimal value of thermodynamic character (δH/vR) when a2=0 (equilibrium relationship). During thermal decomposition connection between system atmosphere — rich in CO2 or vacuum, caused by fast evacuation of gaseous products — and activation energy value, as well as maximal temperature of
reaction process. Conditions of this kind may be explained by Zawadzki-Bretsznajder law.
The investigations of interactions between polyolefins and test solutes at temperatures 58–122�C were carried out in the work.
The test solutes were intentionally selected as representatives of the most important groups of compounds occurring in technological
oils, which may be used as additives in conditions of industrial decomposition of polyolefins in Poland. For this purpose
both the Flory-Huggins theory and inverse gas chromatography (IGC) were used. On the basis of retention data the values of
both interaction and solubility parameters of analyzed polymers were determined. Solubility parameter δ and interaction parameter
χ are related to some heat quantities e.g. excess free energy of mixing. It was observed influence of molecular mass and existence
of chain branches on the values of the parameters. The obtained values allowed determination of influence of composition change
of typical technological oils on their interactions with polymers and, at the same time, on course of charge preparation in