An investigation was carried out on the kinetics of thermal decomposition of plumbo-jarosite. The kinetic models of dissociation
of the compounds in the ore were identified. The results of the kinetic studies and the mechanism of the process are discussed.
The thermal decomposition of plumbo-jarosite occurs in three stages: the first up to 763, the second up to 1023 and the third
up to 1223 K, the corresponding activation energy values being 62.2, 60.3 and 98.0 kJ mol–1 , respectively.
We study the hyperbolicity of metric spaces in the Gromov sense. We deduce the hyperbolicity of a space from the hyperbolicity
of its “building block components”. These results are valuable since they simplify notably the topology of the space and allow
to obtain global results from local information. We also study how the punctures and the decomposition of a Riemann surface
in Y-pieces and funnels affect the hyperbolicity of the surface.
The excess enthalpy of magnesite accumulated by vibration grinding at low specific grinding energy consumption is due predominantly to an increase in specific surface area; at higher energy supply, it is caused by changes in the X-ray amorphous phase content, and when the supplied energy exceeds ca 2000 kJ kg−1 it is a result of the generation of other kinds of defects. The generated defects are relatively stable below 800 K and are the reason for a broad range of distribution of local molar Gibbs energies. Thus, at low temperatures only the ‘active’ portion of samples is able to decompose. Defects relax above ca 800 K, with rates comparable with the rate of decomposition itself. Accordingly, the efficiency of mechanical activation is impressive only below this temperature.
An isothermal method was applied to measure the thermal
decomposition of reactive solids in a sensitive heat flux reaction calorimeter,
C80. This technique experimentally clarified the decomposition mechanisms
of unstable substances based on the shapes of the heat flow curves, from which
autocatalysis, first-order reaction or pseudo-autocatalytic reaction could
be recognized. Kinetic parameters were derived from the measured data.
Forest fires are a plague for all countries in the world. Many factors can induce them. The organic matter (‘fuel’) in the
plant, is often responsible for the start of the fire. The bio-polymers and mainly the cellulose decompose at about 300C
with flammable evolved gas. This decomposition is first order, and the activation energy is about 180 kJ mol−1 . On the other hand, the degradation of the lignin seems more complex, but we observed on many samples, a linearly decomposition
of the lignin vs. the heating rate (in the interval close to the start of the forest fire, 300 to 3000C h−1 ). The decomposition of the plant during the heat is mainly dependent on the cellulose level. This degradation is also slightly
dependent on the lignin level mainly if the lignin present in this plant is less stable.
Authors:W. de Klerk, C. Popescu, and A. van der Heijden
At TNO Prins Maurits Laboratory the characterisation and application of energetic materials is one of the main research topics.
In this respect, the activities are focussed on using thermal analysis techniques such as TG/DTA and DSC. Standard DSC and
TG/DTA techniques usually apply a linear temperature increase. During this gradual temperature change, the sample may pass
certain phase changes related to different crystal structures, followed by a melting/decomposition of the material. In this
way physicochemical properties like phase change temperatures, melting point, enthalpy of melting, decomposition temperature,
etc. can be determined. By applying different heating rates, an analysis of the decomposition kinetics can be performed as
well, which gives additional information on the decomposition process of the material. In this way the activation energy of
the decomposition process and the 'shelf-life' of the material, when stored at a certain temperature, can be assessed. In
a co-operation with the Technical University of Aachen, two relatively new and promising energetic materials were investigated:
FOX-7 and HNF. FOX-7, or 1,1-diamino-2,2-dinitroethylene, is a less sensitive explosive, which could find application as a
substitute of RDX (less sensitive but with preservation of performance). Hydrazinium nitroformate (HNF) is an oxidiser with
potential use as a high-performance, chlorine-free ingredient in rocket propellants. The results of the TG/DTA and DSC tests,
as well as the results of the analysis of the decomposition kinetics of these two materials, will be reported and discussed
in this paper.
The thermal decomposition of poly(α,α,α′,α′-tetrafluoro-p-xylylene) (parylene AF-4) films with thicknesses of ca. 7.5 and 10 μm has been studied by both dynamic (10°C min−1) and isothermal TG in either nitrogen or oxygen atmospheres.
In dynamic studies with nitrogen, gross decomposition occurs between 546.7±1.4 and 589.0±2.6°C, with 26.8±4.4% of the initial
mass remaining at 700°C. With oxygen as the purge gas, the onset of decomposition shifts slightly to 530.8±4.2°C. The end
of the transition at 587.4±2.6°C is within experimental error of the nitrogen value, but no polymer remains above 600°C.
Isothermal data were obtained at 10°C intervals from 420 to 490°C in nitrogen, and from 390 to 450°C in oxygen. Plots of log(Δ%wt/Δt)vs. T−1 are linear throughout the specified range for oxygen and from 420 to 470°C for nitrogen. The calculated activation energies
of (147±16) kJ mol−1 and (150±12) kJ mol−1 in N2 and O2, respectively, are equal within experimental error.
The objects for the studies of this paper are iron sulfates where the iron has second or third valences and where coordination
between iron, sulfur and oxygen is different. DSC technique is used to investigate thermal stability and enthalpy changes
when iron compounds are treated in different gas medium. The main objective is to compare thermal stability and enthalpy of
iron oxy-sulphate, often detected as an intermediate, with commonly known iron sulphates.
DSC curves of samples with equal mass under different gas medium, determining different partial pressure of oxygen in the
gas phase, are the base for comparative study of the sample’s thermal properties. Obtained different values of the enthalpy
and mass losses and kinetic parameters demonstrate that the stability of oxy-sulphate strongly depended on the value of oxygen
partial pressure in the gas phase.
The new evidences from the experimental study help to propose the mechanism of the decomposition and to compare some of the
iron sulphates properties.
The paper describes the synthesis, characterization and thermal decomposition of nickel(II) bis(tartrato) nickelate(II) heptahydrate [Ni2(C4H4O6)2]·7H2O. The complex was characterized by elemental analysis, magnetic moment measurement, infrared, ESR and electronic spectroscopy. The experimental evidences indicate that complex is likely to have metal bonding. The thermal decomposition of the complex produced NiO in air at about 360°C and in nitrogen at about 380°C as the final product. Some of the intermediates produced during the thermolysis were isolated by temperature arrest technique and identified by analytical and spectroscopic methods. A tentative reaction mechanism is proposed for the thermal decomposition of the complex in air and nitrogen.
The thermal behaviour of Ba[Cu(C2O4)2(H2O)]·5H2O in N2 and in O2 has been examined using thermogravimetry (TG) and differential scanning calorimetry (DSC). The dehydration starts at relatively
low temperatures (about 80°C), but continues until the onset of the decomposition (about 280°C). The decomposition takes place
in two major stages (onsets 280 and 390°C). The mass of the intermediate after the first stage corresponded to the formation
of barium oxalate and copper metal and, after the second stage, to the formation of barium carbonate and copper metal. The
enthalpy for the dehydration was found to be 311±30 kJ mol−1 (or 52±5 kJ (mol of H2O)−1). The overall enthalpy change for the decomposition of Ba[Cu(C2O4)2] in N2 was estimated from the combined area of the peaks of the DSC curve as −347 kJ mol−1. The kinetics of the thermal dehydration and decomposition were studied using isothermal TG. The dehydration was strongly
deceleratory and the α-time curves could be described by the three dimensional diffusion (D3) model. The values of the activation
energy and the pre-exponential factor for the dehydration were 125±4 kJ mol−1 and (1.38±0.08)×1015 min−1, respectively. The decomposition was complex, consisting of at least two concurrent processes. The decomposition was analysed
in terms of two overlapping deceleratory processes. One process was fast and could be described by the contracting-geometry
model withn=5. The other process was slow and could also be described by the contracting-geometry model, but withn=2.
The values ofEa andA were 206±23 kJ mol−1 and (2.2±0.5)×1019 min−1, respectively, for the fast process, and 259±37 kJ mol−1 and (6.3±1.8)×1023 min−1, respectively, for the slow process.