Thermal investigation of the phase composition of poly(ethylene terephthalate). Analysis of different methods of determination of the degree of crystallinity of partially crystalline substances

The literature data on the degree of crystallinity of non-deformed poly(ethylene terephthalate) measured at various temperatures have been subjected to comparative analysis. There is no correlation between the results obtained by the different methods. The reason for this is shown to be the imperfections in the methods of determining the degree of crystallinity, which do not provide the true composition of the crystalline phase. Consideration has been paid to the validity of the main principles involved in the thermal method of determining the degree of crystallinity, so as to eliminate the imperfections in the existing methods and to provide the correct value of the mass of the crystalline phase. The phase composition of PET has been analyzed by the thermal method at different temperatures and conditions of crystallization. A marked difference from the literature data is observed in the range of low temperatures.

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Zusammenfassung Eine vergleichende Analyse der Literaturangaben bezüglich des bei verschiedenen Temperaturen gemessenen Kristallisationsgrades von nicht-deformiertem Poly(äthylen-terephthalat) wurde durchgeführt. Zwischen den mit verschiedenen Methoden erhaltenen Ergebnissen besteht keine Korrelation. Es wurde gezeigt, daß der Grund hierfür in der Unvollkommenheit der Methoden zur Bestimmung des Kristallisationsgrades liegt, da diese nicht die wahre Zusammensetzung der Kristallinen Phase angeben. Die Gültigkeit der wichtigsten Prinzipien, welche die thermische Bestimmung des Kristallisationsgrades unter Ausschaltung der Unvollkommenheit der bestehenden Methoden gewährleisten und den richtigen Wert der Masse der kristallinen Phase angeben, wurden in Erwägung gezogen. Die Analyse der Phasenzusammensetzung von PET wurde durch die thermische Methode bei verschiedenen Temperaturen und Kristallisationsbedingungen durchgeführt. Ein deutlicher Unterschied zu den Literaturangaben kann im Bereich der niedrigen Temperaturen beobachtet werden.

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. , , . , , . , , . . .

     

Modification of catalytic properties of silica-supported rhodium

A sharp change in the catalytic properties of rhodium in benzene hydrogenation, propane hydrogenolysis and n-hexane conversion has been found for catalysts prepared via interaction between Rh(CO)₂Cl₂ and silica modified by Sn, Pb, Mo and W ions.

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, Rh(CO)₂Cl₂ , Sn, Pb, Mo W, , , -.

     

Effect of homogeneous initiator on heterogeneous-homogeneous oxidation of methane

A kinetic method of freezing out free radicals combined with recording ESR spectra was used to study the HCl effect on the partial oxidation of methane over SiO₂. This effect is ascribed to the surface modification of catalyst.

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HCl SiO₂. .

     

Discrimination of the mechanisms of cooxidation of arylalkanes and alkylamines

Numerical analysis of experimental data on the cooxidation of arylalkanes and alkylamines indicates a chain propagation and interruption mechanism with the participation of amine cation radicals. The steps corresponding to the classical cooxidation mechanism are excessive in this experiment.

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. , , .

     

Nature of extended defects of CuO

For the first time, using high-resolution electron microscopy, extended defects (twins, screw dislocations and microdistortions) of disperse CuO have been found. Their structure is described.

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CuO -, .

     

Kinetics of the acid-catalyzed equilibration of methylenecyclohexane and 1-methylcyclohexene

The rates of isomerization of methylenecyclohexane and 1-methylcyclohexene have been measured in acetic acid, usingp-toluenesulfonic acid as a catalyst, at temperatures of 20.30, 24.07, 30.00, 32.30, 39.85 and 40.21 °C. The overall forward and reverse rate constants can be expressed as k ₁ ⁰ =4.41×10⁸ exp (–17.6×10³/RT) s^–1 and k ₂ ⁰ =0.64×10⁸ exp ((–19.5×10³/RT) s^–1. From the difference in the activation energies the heat of isomerization is estimated as 7.9 kJ mol^–1.

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1- , - 20,30, 24,07, 30,00, 32,30, 39,85 40,21 °C. k ₁ ⁰ =4.41×10⁸ exp (–17.6×10³/RT) ^–1 k ₂ ⁰ =0.64×10⁸ exp (–19.5×10³/RT) ^–1. 7,9 /.

     

Thermal studies of some divalent metal chelates of croconic acid

The thermal properties of chelates of croconic acid and squaric acid with divalent copper, cobalt, nickel and zinc have been investigated by TG and DTA. The decreasing order of thermal stability for the decomposition of the croconate chelates was Ni > > Zn > Co=Cu and for the squarate complexes, Zn > Co=Cu > Ni. The copper croconate TG showed water loss in two distinct steps. This was rationalized on the basis of the already known Jahn-Teller effect for this molecule. The nickel squarate was thought to have a different structure than the other squarate chelates. Activation energies were calculated for the croconate chelates from their DTA curves.

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Zusammenfassung Die thermischen Eigenschaften der Chelate der Crocon- und Squarsäure mit zweiwertigem Kupfer, Cobalt, Nickel und Zink wurden durch TG und DTA untersucht. Die Abnahme der thermischen Stabilität bei der Zersetzung der Croconat-Chelate verlief von Ni>Zn>Co=Cu und der Squarat-Komplexe von Zn>Co=Cu>Ni. Die TG der Kupfercroconate wies eine Wasserabgabe in zwei deutlichen Stufen auf. Diese erklärt sich aufgrund des bereits bekannten Jahn-Teller Effekts für dieses Molekül. Für Nickelsquarat wurde eine andere Struktur angenommen als für die anderen Squaratkomplexe. Die Aktivierungsenergien für die Croconatchelate wurden aus ihren DTA-Kurven berechnet.

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Résumé Les propriétés thermiques des chélates formés par les acides croconique et squarique avec le cuivre, le cobalt, le nickel et le zinc ont été étudiées par TG et ATD. La stabilité thermique des chélates de l'acide croconique décroît dans l'ordre Ni>Zn>Co=Cu et pour l'acide squarique Zn>Co=Cu>Ni. L'étude TG du croconate de cuivre révèle une perte d'eau en deux étapes distinctes. Ceci s'explique par l'effet Jahn-Teller, déjà connu pour cette molécule. Le squarate de nickel possède sans dute une structure différente de celle des autres chélates de l'acide squarique. Les énergies d'activation des chélates de l'acide croconiqus ont été calculées à partir des courbes ATD.

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TGA DTA , , . Ni > > Zn > =u, — Zn > =Cu > Ni. TGA , . — . , , . DTA .

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Taken in part from a thesis submitted by D. A. L. to the Graduate School of the University of Notre Dame in partial fulfillment for the requirements of the Ph. D. degree.     

Reasons for different activities of various type catalysts in reactions of oxidation of inorganic substances

The dual role of catalysts in the interaction between an inorganic molecule AB and adsorbed oxygen ZO, as an electron donor (in the oxidative addition of AB) and as an electron acceptor (in subsequent ZO reduction), permits to interpret the orders of activities of various optimal catalysts and their dependence on the AB structure.

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AB ZO — ( AB) ( ZO). AB.

     

Influence of oxygen compound structural elements of stretching vibration frequency of surface hydroxy groups

Stretching vibration frequencies of OH groups ( OH) in acidic oxygen compounds are determined by the electrostatic characteristics (E_p) of the polyhedron containing this group. Empirical dependence of OH various hydroxy groups on the number and nature of their binding cations is suggested.

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, OH- ( OH) (). .

     

Quantum yields of the mercury photosensitized cis-trans isomerization of 1,3-pentadiene

The quantum yields of thecis trans andtrans cis Hg 6(³P₁) photosensitized isomerizations of 1,3-pentadiene at 100 Torr and 22°C are 0.54±0.02 and 0.42±0.02, respectively. The steady state ratio ([trans]/[cis])_ss is 1.27±0.05 which is almost identical with the ratio of the quantum yields, (ct)/(tc)=1.29±0.10. Thecistrans isomerization is suggested as a useful actinometer for mercury sensitized reactions.

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Hg 6(³P₁) 1,3- 100 22°C 0,54±0,02 0,42±0,02, . ([]/[]) 1,27±0,05, ( )/( )=1,29±0,10. , .

     

Determination of basic sites on the surface of metal oxide catalysts by desorption of benzoic acid

A method has been developed for the determination of the concentration of basic sites on white and deeply colored solid porous materials, which is based on the displacement of adsorbed benzoic acid by acetic acid. The determination is rapid and gives results comparable with those obrained by the titration with benzoic acid using thymolphthalein as indicator.

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. . , , , .

     

Thermal decomposition of peroxypropionyl nitrate: Kinetics of the formation of nitrogenous products

The Arrhenius expression for reaction 1, CH₃CH₂COO₂NO₂CH₃CH₂COO₂+NO₂, has been determined to be k=2×10¹⁵ exp (–12800/T)·s^–1. The free radical mechanism is the exclusive thermal decomposition mechanism of PPN. The main nitrogenous decomposition products of pure PPN are ethyl nitrate, nitrogen dioxide and methyl nitrate. In the presence of NO, ethyl nitrite is the major organitrogen product.

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CH₃CH₂COO₂NO₂CH₃CH₂COO₂+NO₂ : k=2·10¹⁵exp (–12800/T) ^–1. () - . , . NO .

     

Influence of the pyridine methyl substituent position on the chemical changes of the NCS groups in the thermal decomposition of coordination compounds of the type Cu(NCS)2L2

The influence of the position of the CH₃ group in picoline and lutidine ligands on the degree of chemical change of the NCS groups in coordination compounds of the type Cu(NCS)₂L₂ (whereL=2-, 3- and 4-picoline, and 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-lutidine) is dealt with. The most marked effect of the CH₃ group is found to be exerted in position 4. This effect of the methyl group on the degree of chemical change points to the mutual influence of the ligands in coordination compounds of Cu(II).

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Zusammenfassung Der Artikel befaßt sich mit dem Einfluß der Lage der CH₃ Gruppe in Pikolinen und Lutidinen als Liganden auf den Grad der chemischen Änderungen der Gruppen NSC in Koordinationsverbindungen des Typs Cu(NCS)₂L₂ (L=2-, 3- und 4-Pikoline, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- und 3,5-Lutidine). Der ausgeprägteste Effekt der CH₃ Gruppe wurde in der Position 4 beobachtet. Dieser Einfluß der Methylgruppe auf das Ausmaß der chemischen Änderungen deutet auch auf die gegenseitige Wirkung der Liganden in Koordinationsverbindungen von Cu(II).

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Résumé L'article a trait à l'influence de la position du groupe CH₂ dans les picolines et lutidines, en tant que ligands, sur le degré des changements chimiques des groupes SCN dans les composés de coordination du type Cu(SCN)₂L₂ (L=2-, 3 et 4-picoline, 2,3-, 2,4-,2,5-, 2,6-, 3,4- et 3,6-lutidine). L'effet le plus prononcé du groupe CH₃ s'observe en position 4. Cette influence du groupe méthyle sur le degré des changements chimiques indique aussi l'influence mutuelle des ligands dans les composés de coordination du Cu(II).

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- , , NCS Cu(NCS)₂,L₂, L=2-, 3- 4- , 2.3-, 2.4-, 2.5-, 2.6-, 3.4- 3.5-. , 4. Cu(II).

     

Kinetics and mechanism of elimination of methoxyphenethyl chlorides in the gas phase

The kinetics for the gas phase elimination of o-and m-methoxy-2-phenylethyl chlorides have been investigated over the temperature range of 390-464°C and pressure range of 38–119 Torr. The reactions in seasoned vessels and in the presence of the free radical inhibitor propene, are homogeneous and unimolecular and follow a first-order rate law. The o-anisyl and p-anisyl substituents at the -position of ethyl chloride assist anchimerically the elimination processes. The formation of a cyclic product, benzodihydrofuran, from o-methoxy-2-phenylethyl chloride suggests an intimate ion pair mechanism operating in this reaction.

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- --2- 390–464°C 38–119 . - , , , . - - - . , , --2- , .

     

Exchange of deuterium with OH groups of HY zeolites

The exchange reaction of D₂ with OH groups of HY zeolites was followed both in the solid and gas phase by IR and MS. The rates of D₂–OH and D₂–H₂ exchange increase considerably with dehydroxylation of the sample. The active centers are probably vacancies formed by removal of oxygen from the lattice, they catalyze the dissociation of D₂. Dehydroxylation of the sample is accompanied by the formation of 3 740 cm^–1 hydroxyls, whose exchange with D₂ is slower than that with other OH groups and which affect the kinetics in the gas phase.

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D₂ OH HY - O₂–OH O₂–H₂ . , , , O₂. OH, 3740 ^–1, , OH .

     

Mechanism of the liquid-phase oxidation of diethyl sulfide catalyzed by heteropoly acids

It has been established that in the oxidation of diethyl sulfide by¹⁸O₂ in CH₃C¹⁶O₂H–H₂ ¹⁶O solution at 369 K catalyzed by heteropoly acids, sulfoxide and sulfone with 44–54%¹⁸O enrichment are formed. The process is accompanied by isotope exchange of molecular oxygen.

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, ¹⁸O₂ CH₃C¹⁶O₂H–H₂ ¹⁶O 369 ¹⁸O 44–54%, .

     

Infrared study of the bonding of adsorbed nitriles to metals

The ability of the surface of Pt, Pd, Ru, Rh and Ni to form coordinate and covalent bonds with adsorbed molecules has been studied.

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Pt, Pd, Rh, Ru Ni .

     

Investigation of thermal decomposition of solids

Practical aspects of the studies of stages of thermal dissociation of solids, of the kinetics of the stages, and of utilization of general regularities of the process for verification of kinetic studies are discussed.

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Zusammenfassung Die praktischen Aspekte der Untersuchungen über die Stufen der thermischen Dissoziation von Festkörpern und ihrer Kinetik weiterhin über die Anwendungsmöglichkeiten der RegelmÄssigkeiten der Verifikation der kinetischen Untersuchungen werden erörtert.

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, .

     

The kinetic study of thermal dehydration of oxalic acid dihydrate

The thermal dehydration kinetics of crystalline powders of (COOH)₂ · 2 H₂O was examined by thermogravimetry both at constant and linearly increasing temperatures. An Avrami-Erofeyev law is found to hold with a possibility that a phase-boundary controlled reaction proceeds simultaneously. This is supported by the particle size effect on the rate constant. The activation energyE for the dehydration is estimated as around 80 kJ mol^–1. It is likely that the effects of particle size and temperature onE are compensated by those on the frequency factorA.

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Zusammenfassung Die Kinetik der thermischen Dehydratisierung von kristallinen Pulvern von (COOH)₂ · 2 H₂O wurde thermogravimetrisch bei konstanter und linear ansteigender Temperatur untersucht. Es wurde festgestellt, da\ das Avrami-Erofeyev-Gesetz gefolgt wird und die Möglichkeit besteht, da\ gleichzeitig eine phasen grenzflÄchen-kontrollierte Reaktion verlÄuft. Dies wird durch die Beeinflussung der Geschwindigkeitskonstante durch die Partikelgrö\e unterstützt. Die AktivierungsenergieE für die Dehydratisierung wurde zu etwa 80 kJ mol^–1 gefunden. Es ist wahrscheinlich, da\ die Effekte von Partikelgrö\e und Temperatur aufE durch den des HÄufigkeitsfaktorsA kompensiert werden.

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, . , — , - . . E 80 · ^–1. , E A.

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This work was partly supported by a Grant-in-Aid for Scientific Research from the Ministry of Education, Science, and Culture. The author wishes to thank Mr. K. Kawabata for his assistance in the experimental part of this work.     

Mechanism of o-xylene conversion on magnesium modifications of Y zeolite

o-Xylene conversions has been investigated in the presence of MgNaY zeolites with different Si/Al ratios and degrees of exchange. Disproportionation proceeds to a higher degree than does isomerization. The distribution of reaction products is attributed to geometric factors. The results are in agreement with a monomolecular mechanism of isomerization.

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- MgNaY Si/Al . , , . . .