Non-isothermal differential thermal analysis in the study of the initial state of the thermal decomposition of polynitroaromatic compounds in the condensed state

The activation energies, E, of the decomposition of picramide and its N-methyl-,N-ethyl-,N-n-propyl- and N-n-butyl-derivatives are determined by means of non-isothermal DTA, in its simple form, as well as by the Piloyan method. A relationship is found between the E values of the above-mentioned compounds and the published values of the moments of inertia of the corresponding n-alkyl groups. Taking into account data published previously, which were obtained by application of the Piloyan method in the DTA of polynitroaromates, it is concluded that by suitable selection of DTA measurement conditions, it is possible to record the early part of the exothermal decomposition of the above-mentioned compounds were no autocatalytic influence exists. Attention is also paid to the thermostability of the polynitroaromates due to their contact with the construction materials employed in the course of thermolysis.     

Automated radioanalytical determination of lead and beryllium

The automated modification of the radioanalytical determination of lead and beryllium using AutoAnalyzer modules has been developed. The method for lead determination is based on a two-phase isotope exchange of lead between the sample solution labelled with²¹²Pb and the standard lead diethyldithiocarbamate solution in carbon tetrachloride. For the determination of beryllium a substoichiometric isotope dilution method using⁷Be as tracer and acetylacetone in chloroform as extractant was used. As little as 0.02 μg/ml of lead and 2 μg/ml of beryllium can be determined by the methods above. The flow diagrams of the automated procedures are presented.     

A new principle of activation-analysis separations-X Substoichiometric determination of traces of gallium

A rapid method for the substoichiometric determination of gallium by neutron-activation analysis has been developed. After irradiation and dissolution of the test sample, gallium carrier is added and two preliminary separation steps are performed: the extraction into chloroform of cupferrates from 7N sulphuric acid and of diethyldithiocarbamates from 2-3N sulphuric acid. The pH of the remaining aqueous phase is then adjusted to 5.5, the solution extracted with a substoichiometric amount of 8-hydroxyquinoline in chloroform and the activity of the gallium hydroxyquinolate extract measured. A simultaneously irradiated gallium standard is treated in exactly the same way. From the activities of these two substoichiometric extracts the amount of gallium originally present in the test sample can be calculated. The method has been applied to the determination of 10(-6) to 10(-3)% of gallium in metallic aluminium and transistor-grade silicon.     

Possibilities of applying the Piloyan method of determination of decomposition activation energies in the differential thermal analysis of polynitroaromatic compounds and their derivatives

The Piloyan activation energiesE, as well as the initial exotherm temperaturesT _D, are determined for sixN-monoalkyl- and fiveN,N-dialkyl-2,4,6-trinitroanilines. By comparison withR _f-factors, orR _M-functions of paper chromatography, the molecular-structural dependences ofE andT _D are studied for these compounds. Relationships are also found between the termE · T _D ^–1 and theR _M-functions. The effects are discussed of the introduction of the 6-nitro group into the TV-substituted 2,4-dinitroanilines, and of the introduction of the 4-nitro group into the 2,6-dinitro analogues, upon the thermal stabilities of the resulting 2,4,6-trinitroanilines.

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Zusammenfassung Die AktivierungsenergienE nach Piloyan und die Anfangswerte der ExothermenT _D der sechsN-monoalkyl- und fünfN,N-Dialkyl-2,4,6-trinitroaniline wurden bestimmt. Unter Berücksichtigung des Vergleichs mitR _f-Faktoren oderR _M-Funktionen der Papierchromatographie wurden die molekularstrukturellen AbhÄngigkeiten der WerteE undT _D dieser Verbindungen untersucht. ZusammenhÄnge wurden auch zwischen dem AusdruckE · Tw _D ^–1 und denR _M-Funktionen gefunden. Der Einfluss der Einführung der 6-Nitrogruppe in dieN-substituierten 2,4-Dinitroaniline, sowie der Einfluss der Einführung der 4-Nitrogruppe in 2,6-Nitroanaloge auf die ThermostabilitÄt der resultierenden 2,4,6-Trinitroaniline werden erörtert.

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Résumé On a déterminé les énergies d'activation par la méthode de Piloyan ainsi que les températures initialesT _D de l'effet exothermique de sixN-monoalcoyl- et cinqN,N-dialcoyl-2,4,6-trinitroanilines. En se référant aux facteursR _F ou aux valeurs des fonctionsR _M en Chromatographie sur papier, on a étudié la dépendance entre les valeurs deE et deT _D sur les caractéristiques moléculaires-structurales de ces composés.On a également trouvé des rapports entre le termeE · T _D ^–1 et les fonctionsR _M. On discute l'influence de l'introduction du groupe 6-nitro dans les 2,4-dinitroanilinesN-substituées ainsi que l'influence de l'introduction du groupe 4-nitro dans les 2,6-dinitro analogues sur la stabilité thermique des 2,4,6-trinitroanilines qui en résultent.

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N-- N,N--2,4,6- E , T _D. R _f,- R _M — , - E T _D. E.T _D ^–1 R _M-. 6N- 2,4- 4 2,6- 2,4,6- .

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The authors would like to thank Mrs. Anna Colláková for careful DTA measurements, and Dr. Ladislav Smolka for help in the treatment of the measured results with the Wang 600 computer.     

Modelling of Gearbox Vibration and Noise

The paper presents the methodology intended to the vibration and noise analysis of gearboxes or generally of large rotating systems. These systems are considered including their interior rotating shaft system and housing joined together by rollingelement bearings and gear couplings. The new developed bearing model respects real number of rolling bodies and roller contact forces acting between the journals and the outer housing. The model of a complete gearbox is created using the modal synthesis method. Steady state dynamic response of the whole gearbox excited by gear kinematic transmission errors is investigated. A noise radiated by the housing is calculated on the basis of the acoustic power density evaluation. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Eigenvalue sensitivity and parametric optimization of the large rotating systems

The contribution presents the modal synthesis method of the mathematical modelling of the large rotating systems. The condensed mathematical model is used for deriving analytical formula for eigenvalue sensitivity calculation. According to the sensitivity analysis suitable design parameters are chosen and the optimization process for the purpose of steady state response minimization in a certain operating speed area is performed. The theory is applied to a simple test‐gearbox. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A Bayesian Estimate of the Risk of Tick-Borne Diseases

The paper considers the problem of estimating the risk of a tick-borne disease in a given region. A large set of epidemiological data is evaluated, including the point pattern of collected cases, the population map and covariates, i.e. explanatory variables of geographical nature, obtained from GIS.The methodology covers the choice of those covariates which influence the risk of infection most. Generalized linear models are used and AIC criterion yields the decision. Further, an empirical Bayesian approach is used to estimate the parameters of the risk model. Statistical properties of the estimators are investigated. Finally, a comparison with earlier results is discussed from the point of view of statistical disease mapping.     

Possibilities of applying the piloyan method of determination of decomposition activation energies in the differential thermal analysis of polynitroaromatic compounds and their derivatives

Piloyan activation energiesE as well as initals of exothermT _D of sevenN-monoalkyl and fiveN,N-dialkyl-2,4-dinitroanilines were determined. Relationships were found between the T_D values and R_f factors as well asE values and those R_M functions and also theET _D ^–1 term and R_M functions.

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Zusammenfassung Die AktivierungsenergienE nach Piloyan sowie die Anfangswerte der ExothermenT _D wurden für siebenN-Monoalkyl- und fünfN,N-Dialkyl-2,4-dinitroaniline bestimmt. Die Zusammenhänge zwischen denT _D-Werten und den papierchromatographischenR _f-Faktoren der gemessenen Dinitroaniline wurden abgeleitet und erörtert. Desgleichen wurden auch die Zusammenhänge zwischen denE-Werten und denR _M-Funktionen der Papierchromatographie abgeleitet und erörtert. Auch zwischen dem AusdruckE ·T _D ^–1 und denR _M-Funktionen wurde ein Zusammenhang gefunden.

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Résumé On a déterminé les températures initialesT _D de l'effet exothermique ainsi que les énergies d'activationE d'après la méthode de Piloyan, de sept N-mono alcoyl et cinqN,N-dialcoyl-2, 4-dinitroanilines. Une corrélation entre les valeursT _D et les facteursR _f de la Chromatographie sur papier des dinitroanilines étudiées a été trouvée et discutée, ainsi qu'entre les valeursE et les fonctionsR _M de la Chromatographie sur papier. Une relation entre le termeE ·T _D ^–1 et les fonctionsR _M a également été trouvée.

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E T _D N- N,N- -2,4- . _D R _f , E R _M. E. _D ^–1 R _M.

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The authors would like to thank Mrs. Anna Collàkovà for careful DTA measurements, and Dr. Ladislav Smolka for help in treatment of the measured results with the Wang 600 computer.     

Untersuchung von 2.4.6-substituierten s-Triazinen durch Gaschromatographie-Massenspektrometrie

Gas chromatography mass spectrometry was used to examine a large number of 2,4,6-trialkoxy-s-triazines. The fragmentation of these compounds upon electron impact is discussed. This method permits reliable and rapid identification of mixtures of triazines obtained by reaction of 2,4,6-trichloro-s-triazine with mixtures of alcohols.