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Abstract  

Pooling lauroyl peroxide (LPO) with nitric acid, we used differential scanning calorimetry (DSC) to assess the thermokinetic parameters, such as exothermic onset temperature (T 0), heat of decomposition (ΔH d), frequency factor (A), and the other safety parameters. When LPO was contaminated with nitric acid (HNO3), we found the exploder 1-nitrododecane. Obvious products were sensitive and hazardous chemicals. Concentration reaching 1–12 N HNO3 emitted a large amount of heat. This study combined with curve-fitting method to elucidate its unsafe characteristics and thermally sensitive structure to help prevent runaway reactions, fires and explosions in the process environment. According to the findings and the concept of inherently safer design, LPO runaway reactions could be adequately prevented in the relevant plants.

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Abstract

With two active O–O peroxide groups, 1,1-bis(tert-butylperoxy)cyclohexane (BTBPC) has a certain degree of thermal instability. It is usually used as an initiator in chemical processes, and therefore reckless operation may result in serious thermal accidents. This study focused on the runaway reactions of BTBPC alone and mixed with various concentrations of nitric acid (1, 2, 4, and 8 N). The essential thermokinetic parameters, such as exothermic onset temperature (T o), activation energy (E a), frequency factor (A), time to maximum rate under adiabatic condition (TMRad) and time to conversion limit (TCL), were evaluated by differential scanning calorimetry at the heating rate of 4 °C min−1, and a kinetics-based curve fitting method was used to assess the thermokinetic parameters. All the results indicated that BTBPC mixed with one more than 4 N nitric acid dramatically increased the degree of thermal hazard in the exothermic peak and became more dangerous. However, it was relatively safe for BTBPC mixed with less than 1 N nitric acid under 34.5 °C.

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Abstract  

We have developed a laser flash apparatus for simultaneous measurements of thermal diffusivity and specific heat capacity of solid materials by introducing recent technical progress: uniform heating by a homogenized laser beam using an optical fiber with a mode mixer, measuring transient temperature of a specimen with a calibrated radiation thermometer, analyzing a transient temperature curve with a curve fitting method, to achieve differential laser flash calorimetry. Thermal diffusivity, specific heat capacity and thermal conductivity of glassy carbon and molybdenum were measured in the temperature range from 300 to 1100 K.

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Summary Relaxation behavior of GeySe100-y (y=8 and 10) glasses related to the viscosity behavior was studied by dilatometry. The method of two consecutive temperature jumps was applied to study the volume relaxation. The relaxation response can be described by Tool-Narayanaswamy-Moynihan model and the parameters of this model ?h*, ß, x, A were determined using curve fitting method and characteristic times method. Viscosities of studied materials in the range of 108-1013 Pas were measured by penetration method. The calculated values of activation energies of viscous flow E? are close to the values of effective activation energies of relaxation ?h* for studied chalcogenide materials.

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Summary  

A new acquisition and evaluation procedure has been introduced for the measurement of time-dependent processes in gamma-ray spectrometry, in order to extract more information, including half-lives, from the data recorded during acquisition and to enable a more comprehensive analysis of the results. These advanced, off-line data evaluation techniques improve the selectivity and the background subtraction and make it possible to estimate the important analytical parameters (e.g., half-lives) more accurately than with the usual decay curve fitting method.

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Abstract  

A new and simple method for selective spectrophotometric determination of uranium(VI) with 4-(2-pyridylazo)resorcinol (PAR) and N-octylacetamide into benzene over pH 7.0–9.0 is described. The molar absorptivity of the complex with 9 different amides is in the range of (0.40–3.2)·104 1·mol–1·cm–1 at the absorption maximum. Out of these, the most sensitive compound N-octylacetamide (OAA) was chosen for detailed studies in the present investigation. The detection limit of the method is 0.008 g U·ml–1. The system obeys Beer's law in the range of 0–5 g U·ml–1. The method is free from interferences of most of the common metal ions except vanadium(V) and copper(II), which are masked by proper masking agents. The composition of the complex is determined by curve-fitting method. The method has been applied for the recovery of the metal from rock samples and synthetic mixtures.

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Abstract  

Humic substances (HSs) occur throughout the ecosphere in soils, waters and underground systems. The strong complexation of HSs is of importance in the migration of radionuclies in geological media. Renewed interest in stability constants of complexes of radioelements and radionuclides with humic and fulvic acids has been generated by problems associated with the nuclide migration in the environment. Use of the ion exchange method for the determination of conditional stability constants of metal-HS complexes was examined and reviewed. The complexation of HS to metal ions cannot be described in rigorous mathematical terms because of the ill-defined nature of HSs in contrast with the complexation of single ligands. Furthermore, the advantages and disadvantages of Schubert's and, Ardakani-Stevenson's, curve fitting methods were discussed. The great stabilities of HS complexes to rare earths (Yb(III), Tb(III), Eu(III), Gd(III)), americium(III), cobalt(II), uranyl(VI) and thorium(IV) were revealed.

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Abstract

the Retezat Mountains, this study discusses radiocarbon chronology and sediment accumulation rate changes in two sediment profiles in relation to lithostratigraphy, organic content, biogenic silica and major pollenstratigraphic changes. A total of 25 radiocarbon dates were obtained from sediments of two lakes, Lake Brazi (TDB-1; 1740 m a.s.l.) and Lake Gales (Gales-3; 1990 m a.s.l.). Age-depth modeling was performed on TDB-1 using calibrated age ranges from BCal and various curve-fitting methods in psimpoll. Our results suggest that sediment accumulation began between 15,124–15,755 cal yr BP in both lakes and was continuous throughout the Late Glacial and Holocene. We demonstrated that local ecosystem productivity showed delayed response to Late Glacial and Early Holocene climatic changes in the subalpine and alpine zones most likely attributable to the cooling effect of remnant glaciers and meltwater input. However, regional vegetation response was without time lag and indicated forestation and warming at 14,450 and 11,550 cal yr BP, and cooling at ca. 12,800 cal yr BP. In the Holocene one major shift was detected, starting around 6300 cal yr BP and culminating around 5200 cal yr BP. The various proxies suggested summer cooling, shorter duration of the winter ice-cover season and/or increasing size of the water body, probably in response to increasing available moisture.

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Abstract  

Tert-butyl peroxybenzoate (TBPB) is one of the sensitive and hazardous chemicals which have been popularly employed in petrifaction industries in the past. This study attempted to elucidate its unsafe characteristics and thermally sensitive structure so as to help prevent runaway reactions, fires or explosions in the process environment. We employed differential scanning calorimetry (DSC) to assess the kinetic parameters (such as exothermic onset temperature (T 0), heat of reaction (ΔH), frequency factor (A)), and the other safety parameters using four different scanning rates (1, 2, 4 and 10°C min−1) combined with curve-fitting method. The results indicated that TBPB becomes very dangerous during decomposition reactions; the onset temperature and reaction heat were about 100°C and 1300 J g−1, respectively. Through this study, TBPB accidents could be reduced to an accepted level with safety parameters under control. According to the findings in the study and the concept of inherent safety, TBPB runaway reactions could be thoroughly prevented in the relevant plants.

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Kinetic analysis of thermogravimetric data

XIV. Three integral methods and their computer programs

Journal of Thermal Analysis and Calorimetry
Authors: J. Zsakó and J. Zsakó

Computer programs are given in Fortran language for three integral methods of deriving kinetic parameters from TG curves. Method 1 is a computerized variant of Doyle's curve-fitting method and performs the calculation of the exponential integralp(x) by means of author's empirical formula. Methods 2 and 3 are variants of the Coats-Redfern linearization method. Testing of the methods on both theoretical and experimental TG curves shows them to be almost equivalent as far as the results obtained are concerned, but Method 1 needs a ten-fold higher computer time.

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