Synthesis gas reactions on Pd-catalysts

Reactions of synthesis gas (CO/H₂) have been followed on a number of Pd-metal and Pd-alloy catalysts. Formation of methanol is sensitive to the choice of the carrier, but as the literature (and some of the data presented) is indicating, it is not proportional to the Pd-metal surface area. Alloying with Ag does not suppress methane formation substantially. It has been inferred from these results that methane is formed, at least partially, from an oxygen containing intermediate and that Pd ions play a role in the formation of these intermediates.

---

, -, CO/H₂, Pd . , , ( ), Pd. . , , - , , , Pd.

     

Kinetics of the catalytic transformation of isobutene into methacrylonitrile with NO on supported nickel oxide aerogel

Kinetic studies of the nitroxidation of isobutene by NO show that the reaction follows a redox mechanism in the temperature range of 300–400°C. This mechanism implies an interaction between dehydrogenated isobutene -allyl radical and atomic nitrogen due to the decomposition of NO by the reduced catalyst, which is then reoxidized.

---

NO , 300–400°C. - , NO , .

     

Modification of the sorption kinetic characteristics of natural zeolite adsorbents used in pressure swinging adsorption operations

The adsorption kinetic characteristics of natural zeolite based adsorbents can be improved significantly by grinding, size fractionation and regranulation. The sorption characteristics of such materials with tridisperse pore-size distributions are discussed here. (Tridisperse structure: the holes of crystallites, the macropore system among crystallites and macropores produced by granulation.)

---

- , . .

     

Differential thermal analysis of potassium perchlorate

A study has been made of the differential thermal analysis of (i) potassium perchlorate in powdered form, (ii) potassium perchlorate in pelletized form, (iii) potassium perchlorate recrystallized from liquid NH₃, and (iv) potassium perchlorate preheated for 24 hours at 375°. Pretreatment of potassium perchlorate leads to a desensitization of both endothermic and exothermic processes. Additionally, the pretreatment tends to convert the symmetric exotherm into an asymmetric exotherm due to merging of the two exotherms. An analysis of the factors causing asymmetry in the exotherm has thrown fresh light on the mechanism of thermal decomposition of potassium perchlorate.

---

Zusammenfassung Eine differentialthermoanalytische Untersuchung wurde an, (i) Kaliumperchlorat in Pulverform, (ii) Kaliumperchlorat in pelletisierter Form, (iii) Kaliumperchlorat, umkristallisiert aus flüssigem Ammoniak und (iv) Kaliumperchlorat, 24 Stunden bei 375° vorgeheizt, durchgeführt. Die Vorbehandlung von Kaliumperchlorat führt zu einer Verdichtung sowohl der endothermen als auch der exotherman Vorgänge. Ausserdem führt die Vorbehandlung zur Umwandlung der symmetrischen Exotherme in eine asymmetrische Exotherme durch Vereinigung der zwei Exothermen. Die Analyse der die Asymetrie der Exothermen verursachenden Faktoren zeigte den Mechanismus der thermischen Zersetzung des Kaliumperchlorats unter neuen Gesichtspunkten.

---

Résumé On a effectué l'étude par analyse thermique différentielle du perchlorate de potassium: (i) en poudre, (ii) sous forme comprimée, (iii) recristallisé dans NH₃ liquide, (iv) préchauffé à 375° pendant 24 heures. Le traitement préalable du perchlorate de potassium entraîne la désensibilisation des processus endothermiques et exothermiques. De plus, le traitement préalable tend à convertir l'exotherme symétrique en un exotherme asymétrique, du fait de la fusion des deux exothermes. Une analyse des facteurs causant l'asymétrie de l'exotherme a donné une vue nouvelle du mécanisme de la décomposition thermique du perchlorate de potassium.

---

, , , 375° 24 . . , , . , , .

---

---

This work has been supported by a grant from the Indian Space Research Organization (I.S.R.O). It also includes financial support to one of the authors (D. S.). This support is gratefully acknowledged.     

Decomposition of alkanethiols to dialkyl sulfides and hydrogen sulfide

Disproportionation of thiol to sulfide and H₂S takes place on catalysts of various composition, the most active being those with paired acid-base centers. On these catalysts at 200–400°C methanethiol is quantitatively converted to dimethyl sulfide. Disproportionation of ethanethiol and particularly of 2-propanethiol is accompanied by the decomposition of sulfides formed and initial thiols to produce olefins and H₂S.

---

H₂S , - . 200–400°C . 2- H₂S.

     

On the thermal analysis of mineral components in clays

The paper deals with the problem of the interactions of the mineral components in clay and argillite samples during the thermal analysis. It is shown that depending on the experimental conditions, the interaction of pyrite and carbonates may cause atypical course of DTA and TG curves. Also the common occurring of sylvine and halite shifts the temperature of their melting to a lower value and this phenomenon occurs in pure salts as well as in the great dilution to some percent in clays.

---

Zusammenfassung Es wird über Zwischenreaktionen der mineralischen Komponenten von Ton und Argillit während der thermischen Analyse berichtet. Von den Versuchsbedingungen abhängend produzieren die Zwischenreaktionen von Pyrit und Karbonat DTA und TG Kurven deren Verlauf nicht charakteristisch ist. Das gemeinsame Vorkommen von Sylvin und Halit verschiebt ihren Schmelzpunkt in Richtung der niedrigen Temperaturen in reinen Salzen ebenso wie bei großer Verdünnung von einigen Prozenten in Ton.

---

Résumé Les interactions des constituants minéraux des échantillons d'argile et d'argilite pendant l'analyse thermique ont été examinées. Suivant les conditions expérimentales, l'interaction de la pyrite et des carbonates peut provoquer un tracé des courbes ATD et ATG qui s'écarte de l'allure type. La présence simultanée de sylvine et d'halite produit un abaissement de leur point de fusion et ce phénomène apparaít aussi bien avec les sels purs qu'avec ceux fortement dilués, à raison de quelques pour cent, dans les argiles.

---

, , ., () (). . , .

     

Comparison of the sulfurization of CoMoK/Al2O3 catalyst with H2S and CS2

Only H₂S consumption and H₂O formation was found in the sulfurization of CoMoK/Al₂O₃ water gas shift catalyst with H₂S/H₂, but CO₂ was formed first, then CH₄, H₂O and H₂S appeared in the later part of TPS with CS₂/H₂. Carbon deposition on the catalyst during the sulfurization with CS₂/H₂ caused a lower activity than the catalyst sulfurized with H₂S but could be removed in the run of WGS reaction.

---

, CoMoK/Al₂O₃, H₂S/H₂ H₂S H₂O, CS₂/H₂ CO₂ CH₄, H₂O H₂S. CS₂/H₂ H₂S, , .

     

Influence of organic reagents on nickel alumina supported catalysts. II. hydrogenolysis of n-butane

The influence of organic reagents on the rate, selectivity and activation energy of n-butane hydrogenolysis has been studied. Increasing of the functional groups and coordination place in used organic reagents the caused higher mean values of reaction rates, activation energy and selectivity towards methane.

---

, -. , .

     

Influence of the various forms of molybdena on the adsorptive and catalytic (dehydrogenation and hydrogenolysis) properties of molybdena-alumina catalysts

The contents of three forms of molybdenum oxide compounds in molybdena-alumina catalysts have been determined by their solubility in water and ammonia. The form which is readily soluble in water and reducible to Mo(IV) at 400°C and P_H2=10⁵ Pa is active in cyclohexane dehydration, and the forms soluble in water and ammonia are active in thiophene hydrogenolysis.

---

. , 400°C P_{H 2}=I Mo(IV); — .

     

Residual entropy of glasses and their relation with the crystallization behaviour

For the alloy of eutectic composition in the quasibinary GeSe₂-Sb₂Se₃ system the heat capacities of the glass, undercooled and stable liquid and crystalline phases have been measured using differential scanning calorimetry. Enthalpy, entropy and Gibbs free energy differences of vitreous and crystalline forms have been deduced for this alloy. The kinetic parameters of crystallization for glasses of nearby composition have been obtained by continuous heating experiments. The effective activation energy obtained has a value that accounts for the activation energy for nucleation calculated using simple nucleation theory formulae.

---

Zusammenfassung Die Wärmekapazitäten von Glas, unterkühlter und stabiler Flüssigkeit und kristallinen Phasen von Mischungen der eutektischen Zusammensetzung des quasibinären Systems GeSe₂-Sb₂Se₃ werden mittels DSC gemessen. Aus den Ergebnissen werden Enthalpie, Entropie und freie Enthalpie der glasartigen und kristallinen Formen dieser Mischung abgeleitet. Die kinetischen Parameter der Kristallisation von Gläsern benachbarter Zusammensetzungen wurden durch temperaturprogrammierte Untersuchungen ermittelt. Die erhaltenen effektiven Aktivierungsenergien entsprechen dem für die Keimbildung nach einfachen theoretischen Formeln berechneten Wert.

---

, , GeSe₂-Sb₂Se₃. , . . , .

---

---

This research was supported by the Comisión Asesora de Investigatión Cientifica y Técnica (CAICYT) project no. 759-84 which is gratefully acknowledged.