The composition of volatile and particulate hydrocarbons in urban air

Summary The hydrocarbon composition of the particle and gas phases in the urban atmosphere has been studied by filtration and parallel adsorption on active charcoal and polyurethane foam (PUF). Gas chromatography (GC) and GC coupled to mass spectrometry (GC-MS) have been used for the analysis of the organic matter extracts obtained with each system. In the case of the particle and PUF samples these extracts were fractionated into aliphatic and aromatic compounds. This approach has allowed to identify up to 247 hydrocarbon molecules showing that C0–C5 alkylbenzenes are the major compounds in the charcoal extracts whereas C14–C23 n-alkanes, C0–C4 alkylnaphthalenes, C0–C4 alkylbiphenyls and C3–C5 alkylbenzenes are those predominantly found in the PUF materials. The particles essentially contain C17–C38 n-alkanes and parent polycyclic aromatic hydrocarbons (PAH). These qualitative differences are paralleled by a progressive concentration decrease from the more to the less volatile hydrocarbons. Thus, the total charcoal extracts average 80 g/m³, the PUF compounds represent 4 /m³ and the particle hydrocarbons 0.7 g/m³. These latter airborne materials are essentially composed of petrogenic residues 0.6 g/m³ (aliphatic fraction) whereas the pyrolytic PAH only involve 0.08 g/m³.     

The autocatalytic character of the reaction methanol to hydrocarbons over amorphous silica-alumina catalysts

Conversion of methanol to hydrocarbons was studied on an amorphous silica-alumina over the 330–420°C temperature range and contact times up to 8 h. The reaction was confirmed as autocatalytic from the results of varying both contact time and temperature.

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330–420°C 8 . , , , .

     

Oxidative coupling of carbazole derivatives to dicarbazyls in the presence of Pd(OAc)2

The interaction of 9-R-carbazoles (R=H, Me, Et) with Pd(OAc)₂ in AcOH solution was used to obtain the corresponding derivatives of 3, 3-dicarbazyls, the yield of the coupling products being 30–58% based on Pd(OAc)₂. Under similar conditions poly(9-vinylcarbazole) gives 8.6% of intermolecular coupling products.

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9-R- (R=H, Me, Et) c Pd(OAc)₂ AcOH - 3,3- 30–58% Pd(OAc)₂. -9-- 8,6% - .

     

Influence of the preparation method on the pore spectrum of Pt?Cr/Al2O3 and Pt?Sn/Al2O3 catalysts

It is shown that, in contrast to classical impregnation methods, in bimetallic catalyst production the texture of the carrier is stabilized by introducing the promoting ion on the surface of Pt/Al₂O₃ with vapors of CrO₂Cl₂ or SnCl₄. This is shown by a relatively slower decrease of the specific area and the volume of the pores upon calcination.

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, Pt/Al₂O₃- CrO₂Cl₂ SnCl₄ . .

     

Kinetic equations with a complex balanced stationary point

A class of ordinary differential equations including nonideal nonisothermal kinetics is introduced. The behavior of their solutions for the system with a positive complex-balanced stationary point is studied. Sufficient conditions for this point to exist are described.

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, . . .

     

Infrared spectroscopic study of the adsoprtion of methacrylates on aerosil

The type and ratio of the attached groups was measured by FT-IR spectroscopy for the adsorption of three methacrylates. The adsorption enthalpies can be determined from a correlation with infrared frequency shifts.

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--. -.

     

Effect ofβ-cyclodextrin complexation on the photohaemolitic activity induced by Ketoprofen and Naproxen sensitization

Red blood cell lysis photosensitized by two non-steroidal anti-inflammatory drugs Naproxen (NAP) and Ketoprofen (KPF) was investigated in the presence of -cyclodextrin (-Cyd). The photohaemolysis was inhibited by the addition of -Cyd both for NAP and, to a lesser extent, for KPF. The protective action was found only in a restricted range of concentration of -Cyd. Higher amounts of -Cyd interfered with the resistance of the cell to the osmotic shock induced by the photosensitization process. The complexing action of -Cyd was ascertained through UV-vis absorption spectroscopy, induced circular dichroism and emission spectroscopy.The isolated complexes Naproxen--Cyd (NAP--Cyd) and Ketoprofen--Cyd (KPF--Cyd) were found to protect from the photosensitized membrane damage induced by the two drugs, even if it occurred only in a limited range of concentration. This suggests a valid tool in alleviating thein vitro phototoxic consequences caused by these compounds, even if care has to be taken in therapeutic administration due to the presence of the uncomplexed -Cyd.     

Investigation about methods of quantitative evaluation of DTA curves

The investigation gives a comparison of the best-known kinetic evaluation methods for DTA curves. With regard to accuracy and error-compensation, the methods of Borchardt and Daniels, Coats and Redfern and atava and kvara in particular are to be recommended if simple irreversible reactions are to be evaluated on the basis of homogeneous kinetics. The complete exponential integral method is described which totally eliminates the approximative character of the practical procedure of Coats and Redfern. Hence, it becomes theoretically exact again.

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Zusammenfassung Die Untersuchung beschäftigt sich mit dem Vergleich der bekanntesten kinetischen Auswerteverfahren für DTA-Kurven. Unter Beachtung der Genauigkeit und des Fehlerausgleiches wird festgestellt, daß die Methoden von Borchardt und Daniels, Coats und Redfern sowie atava und kvara besonders empfehlenswert sind, wenn man einfache irreversible Reaktionen auf der Grundlage der Homogenkinetik auswerten will. — Im zweiten Teil wird die Methode des vollständigen Exponentialintegrals beschrieben, die den Näherungscharakter in dem praktikablen Verfahren von Coats und Redfern aufhebt. Dadurch wird es wieder theoretisch exakt.

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Résumé L'étude porte sur la comparison des méthodes les plus connues d'exploitation cinétique des courbes ATD. Du point de vue de l'exactitude et de la compensation des erreurs, on établit que les méthodes de Borchardt et Daniels, de Coats et Redfern ainsi que de atava et kvara peuvent être recommandées pour l'étude des réactions irréversibles simples en cinétique homogène. Dans la seconde partie, on décrit la méthode d'intégration exponentielle complète qui supprime totalement le caractère approximatif de la méthode de Coats et Redfern.

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Cd(NH₃)₂Hg(CN)₄·2₆₆. , . . .

     

Oxygen chemisorption and activity studies on unpromoted and promoted TiO2 supported tungsten sulfide catalysts

Low temperature oxygen chemisorption (LTOC) has been applied to characterize unpromoted and promoted tungsten sulfied catalysts supported on TiO₂. LTOC, hydrodesulfurization and hydrogenation are found to correlate with the W loading.

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() - TiO₂ . , - W .

     

n-Pentane isomerization in a continuous-flow reactor on Pt/Al2O3 catalysts modified by adsorbed bismuth and palladium

Isomerization of n-pentane has been studied in a continuous-flow reactor at atmospheric pressure on Pt/Al₂O₃ catalysts modified by adsorbed bismuth and palladium. Lower activity and higher selectivity have been obtained on a catalyst modified by bismuth. Both activity and selectivity have decreased on a catalyst modified by palladium. After oxygen treatment the Pd–Pt/Al₂O₃ catalyst showed the most pronounced change in catalytic properties and its stability was lower than that of the unmodified Pt/Al₂O₃ catalyst.

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- , Pt/Al₂O₃, . , . , , . Pd–Pt/Al₂O₃ , Pt/Al₂O₃.

     

The effect of sample geometry on the melting point of polyethylene

We have examined the influence which sample geometry has on the melting point of isothermally melt crystallized polyethylene. The peak positions of curves obtained using a Perkin-Elmer DSC were used as the apparent melting points (Tm). With a constant sample weight (ca. 0.05 mg), we observed an increase of 1.7 K for Tm when the sample thickness was increased from 1 to 8 m. Experiments which demonstrate the heat transfer problems related to the melting of polymer samples are also presented. This work indicates that, if one is attempting to reduce the heating rate dependence of polymer samples, reduction of sample weight alone is not suffiicient. Rather one should aim at increasing the sample pan contact area and reducing the sample thickness simultaneously.

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Zusammenfassung Der Einfluß der Probengeometrie auf den Schmelzpunkt isotherm geschmolzenen kristallinen Polyäthylens wurde untersucht. Die Peakpositionen in den mit einem Perkin-Eimer DSC erhaltenen Diagrammen wurden als scheinbare Schmelzpunkte (Tm) benutzt. Bei konstantem Probengewicht (etwa 0.05 mg) wurde für Im ein Anstieg um 1.7 K beobachtet, wenn die Schichtdicke der Probe von 1 auf 8 m erhöht wurde. An Experimenten werden auch die mit dem Schmelzvorgang bei Polymerproben zusammenhängenden Wärmeübergangsprobleme aufgezeigt. Diese Arbeit macht deutlich, daß eine Verminderung des Probengewichts allein zur Verminderung der Aufheizgeschwindigkeitsabhängigkeit der Polymerproben nicht ausreichend ist. Es soll vielmehr eine gleichzeitige Vergrößerung der Probenträgerkontaktfläche und Verringerung der Probenschichtdicke angestrebt werden.

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. , ( -), . ( 0.05 ), 1 8 , . 1.7 , , . , , . .

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The authors gratefully acknowledge the support of the National Science Foundation (Polymers Division) Grant No. DMR 78-25233.     

Formic acid decomposition on polycrystalline tungsten

The rates of HCOOH decomposition on polycrystalline tungsten are examined over a wide range of catalyst temperatures (600

HCOOH (600     

Selectivity of platinum-copper alloys in reactions of butanol

A short study on the title reaction confirms that at low hydrogen pressures no ether formation occurs, while when a higher hydrogen pressure suppresses the fast dehydrogenation, ethers are formed. A comparison of Pt and Pt alloys shows that ether formation is faster on large ensembles of Pt atoms, requirements of decarbonylation are less in this respect. Results of earlier studies on Ni/Cu alloys have thus been confirmed.

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, , , . Pt , , .. . , Ni/Cu.

     

On the use of a dead-time meter for pile-up corrections

Correction for pile-up losses in the amplifier is possible by the dead-time fraction indicator of the ADC in case of long-lived radionuclides. If the dead-time meter has been calibrated, an accuracy of 1.5% is feasible up to a dead-time fraction of 25%. The precision decreases from 1.5% at 10% dead-time fraction to 3% at a deadtime fraction of 30%.     

Dehydrogenation activity of H-Y and RE-Y zeolites in decomposition of tetrahydrothiophene

Dehydrosulfurization of tetrahydrothiophene in nitrogen on H-Y and RE-Y zeolites was accompanied by dehydrogenation to thiophene. Neither reaction was influenced by hydrogen and water in the feed. The selectivity was independent of catalyst coking, which suggests a common origin of both functions.

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H-Y RE-Y . , . , , .

     

Effect of electronic interaction between metal and support, II. TPD, TPR and chemisorption studies on Ru/Al2O3?MgO catalysts

TPD, TPR and chemisorption were used to characterize Ru/Al₂O₃–MgO catalysts. It is suggested that the acidity of support may influence the properties of catalysts significantly.

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, Ru/Al₂O₃–MgO. , .

     

Reactivity of benzoic acid esters towards cumylperoxy radicals

The alkoxy groups of aromatic carboxylic acid esters are attacked by cumylperoxy radicals. The rate constants for the abstraction of a hydrogen atom by cumylperoxy radicals are: for methyl benzoate k₂=(4.28±0.8)×10¹⁰ exp (–20.5±1.5/RT) and for ethyl benzoate k₂=(9.41±0.8)×10¹⁰ exp(–18.5±1.5/RT) l/mol sec. The strengths of the primary and the secondary C–H bonds of these compounds have been estimated.

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, . k₂=(4,28±0,8)·10¹⁰ exp (–20,5±1,5/RT) k₂=(9,41±0,8)·10¹⁰ exp (–18,5±1,5/RT) /·. C–H .

     

Thermoanalytical studies of combustion of cellulosics and activity of fire retardants

TG, DTG and simultaneous DTA were used to monitor the thermal decomposition processes of cellulose in nitrogen or in an oxidative atmosphere. Volatile products and solid residues formed during decomposition were analyzed to obtain additional information for elucidation of the thermal curves. An indication of possible flaming or smoldering combustion is discussed. The maximum weight-loss rate, the percentage amount of the residue at the final temperature, and the exothermic peak areas (DTA) could be considered as suitable criteria for the flammability of cellulosics and the activity of flame retardants. The formal kinetic parameters evaluated from the thermogravimetric measurements correspond to the limiting oxigen index (LOI) values. New observations were made using a combination of thermal analysis and LOI techniques. LOI — smoldering or LOI — flaming are mathematically determined from the plot of weight-loss rate versus oxygen concentration.

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Zusammenfassung TG, DTG und simultane DTA wurden zur Verfolgung der thermischen Zersetzungsprozesse von Zellulose in Stickstoff oder in einer oxidativen Atmosphäre eingesetzt. Während der Zersetzung entstandene flüchtige Produkte und feste Rückstände wurden analysiert um weitere Informationen zur Klärung der Kurven zu erhalten. Ein Hinweis auf mögliche flammende oder glühende Verbrennungen wird diskutiert. Die maximale Geschwindigkeit des Gewichtsverlusts, die prozentuale Menge des Rückstandes bei der End-temperatur und die exothermen Peakflächen (DTA) könnten als geeignete Kriterien für die Entflammbarkeit der Zellulosen und die Aktivität der feuerhemmenden Substanzen betrachtet werden. Die aus den thermogravimetrischen Messungen errechneten formalen kinetischen Parameter entsprechen den LOI (limiting oxygen index) Werten. Neue Beobachtungen wurden unter Einsatz einer Kombination der Thermoanalyse und der LOI-Techniken gemacht. LOI-Glut oder LOI-Entflammen werden mathematisch aus dem Zusammenhang zwischen der Geschwindigkeit des Gewichtsverlusts und der Sauerstoffkonzentration bestimmt.

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, . , , . . , , , (), - . , . . — — .

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We wish to express our thanks to Mrs. V. Michliková for her skilful assistance.     

Studies in dipyridyl chemistry. VII. Sulfur trioxide sulfonation of γ,γ′-dipyridyl

Reaction of ,-dipyridyl with sulfur trioxide at room temperature gives ,-dipyridyld'isulfotrioxide, which latter on heating at 200° gives ,-dipyridyl-sulfonic acid. Salts of ,-dipyridyl-3-sulfonic acid are prepared, among them the potassium, sodium, barium, and 3-cyano-,-dipyridyl salts.For Part VI see [1].