The compensation effect as a result of integration of theArrhenius equation

Summary It has been shown that joined segments of straight lines are observed upon plotting the logarithm of the rate constant against the reciprocal temperature, exhibiting sharp breaks at so-called critical temperatures indicating sudden changes in activation energy [3, 5–8]. If the integration of the differential form of theArrhenius equation from 0 toT K is taken into account, the compensation effect can easily be explained.

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Der Kompensationseffekt als Ergebnis der Integration derArrhenius-Gleichung

Zusammenfassung Wenn man den Logarithmus der Geschwindigkeitskonstante gegen die reziproke Temperatur aufträgt, erhält man aufeinanderfolgende Teilstücke von Geraden mit scharfen Knicks bei sogenannten kritischen Temperaturen, welche jeweils eine Änderung der Aktivierungsenergie anzeigen [3, 5–8]. Integration derArrhenius-Gleichung zwischen 0 undT K führt zu einer zwanglosen Erklärung des Kompensationseffekts.

     

Complexes of amic acids with polar aprotic solvents. VI. System of hydrogen-bonds in complexes of amic acids and polyamic acids with amide solvents

It has been established through X-ray analysis of complexes of pyromellitedianylic acid with amide solvents that the type of the system of hydrogen-bonds and the solvate structure depend on the nature of these solvents. It is shown for solvates of poly(4,4-oxydiphenylene)pyromellite amic acid that mass spectrometric thermal analysis (MTA) may be used for the investigation of hydrogen-bonds formed in solid polyamic acid films. The MTA data may be employed to establish the mechanism of the effects of additives catalysing the solid-phase cyclodehydration of polyamic acids.

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Zusammenfassung Durch röntgenanalyse von Komplexen von Pyromellit-dianilicsäure mit Amidlösungsmitteln wurde festgestellt, daß der Typs des Systems der Wasserstoffbindungen und die Solvatstruktur von der Natur dieser Lösungsmittel abhängt. Für Solvate der Poly-(4,4-oxydiphenilen) pyromellit-amicsäure wird gezeigt, daß die massenspektrometrische thermische Analyse (MTA) zur Untersuchung von in festen Polyamicsäurefilmen ausgebildeten Wasserstoffbindungen herangezogen werden kann. Die MTA-Daten können zur Ermittlung des Wirkungsmechanismus von die Festphasencyclodehydratisierung von Polyamicsäuren katalisierenden Additionen herangezogen werden.

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, . , (4,4-) , , o , , .

     

Amination of isomeric bromo-1-methylnitropyrazoles

A method was developed for the synthesis of 5-bromo-1-methyl-4-nitropyrazole from 1-methylpyrazole. In the reaction with 25% aqueous ammonia at 180–190 °C, 5-bromo-1-methyl-4-nitropyrazole is readily converted to 5-amino-1-methyl-4-nitropyrazole; the production of 4-amino-1-methyl-5-nitropyrazole from 4-bromo-1-methyl-5-nitropyrazole requires the presence of a copper catalyst; under the same conditions in the amination of 4-bromo-1-methyl-3-nitropyrazole, 4-amino-1-methyl-3-nitro- and 1-methyl-3-nitropyrazoles are formed in a 23 ratio.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1672–1675, December, 1983.     

A matrix approach to grazing-incidence X-ray diffraction in multilayers

A method for computation of X-ray grazing-incidence diffraction (GID) in multilayers and superlattices is presented. The method is based on X-ray dynamical diffraction theory and a matrix from a boundary equations and provides a simple numerical solution of the problem. The application of the method to simulating GID measurements taken from A1As/GaAs superlattice (20 periods of 14.6 nm A1As and 6.8 nm GaAs) demonstrates the principal validity of the theory. A perfect matching between the theory and the experiment requires the real-structure effects of sample to be taken into account.     

On the Discrete Hardy Inequality

Necessary and sufficient conditions for the boundedness of thediscrete Hardy operator of the form , from to when 0 < q < 1 <p , is given.     

Mechanism studies of the conversion of 13C-labeled n-butane on zeolite H-ZSM-5 by using 13C magic angle spinning NMR spectroscopy and GC-MS analysis

By using 13C MAS NMR spectroscopy (MAS = magic angle spinning), the conversion of selectively 13C-labeled n-butane on zeolite H-ZSM-5 at 430-470 K has been demonstrated to proceed through two pathways: 1) scrambling of the selective 13C-label in the n-butane molecule, and 2) oligomerization-cracking and conjunct polymerization. The latter processes (2) produce isobutane and propane simultaneously with alkyl-substituted cyclopentenyl cations and condensed aromatic compounds. In situ 13C MAS NMR and complementary ex situ GC-MS data provided evidence for a monomolecular mechanism of the 13C-label scrambling, whereas both isobutane and propane are formed through intermolecular pathways. According to 13C MAS NMR kinetic measurements, both pathways proceed with nearly the same activation energies (E(a) = 75 kJ mol(-1) for the scrambling and 71 kJ mol(-1) for isobutane and propane formation). This can be rationalized by considering the intermolecular hydride transfer between a primarily initiated carbenium ion and n-butane as being the rate-determining stage of the n-butane conversion on zeolite H-ZSM-5.     

Surface Energy of Low-Index Faces of Single-Crystal Gold in Molten Sodium,Potassium, and Cesium Chlorides

The free energies of formation of gold faces (111) and (100) in molten sodium, potassium, and cesium chlorides are measured by the meniscus weighing method. The effect of the cation size, temperature, and electric potential on the electrocapillary curve and PZC is considered. A mechanism for the anion adsorption at a charged metal surface, based on the participation of valence orbitals of the electrode metal in the formation of surface compounds, is suggested.     

Decarbonylation of N-carbazolylacetyl chloride in the friedel-crafts acylation reaction

Reaction products of N-carbazolylacetyl chloride under Friedel-Crafts reaction conditions include carbon monoxide, the reaction product from carbazole and formaldehyde (CF condensate), and carbazole. It is postulated that decarbonylation of N-carbazolylacetyl chloride involves intermediate formation of a N-carbazolylmethyl cation.