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  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Environmental science & technology 19 (1985), S. 849-854 
    ISSN: 1520-5851
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Energy, Environment Protection, Nuclear Power Engineering
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Journal of atmospheric chemistry 31 (1998), S. 349-350 
    ISSN: 1573-0662
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract When this paper was first published Figure 5 was incorrect. The publisher regrets this oversight. The complete page with correct figure and original pagination is printed overleaf.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Journal of atmospheric chemistry 34 (1999), S. 339-364 
    ISSN: 1573-0662
    Keywords: aromatic hydrocarbons ; primary reaction products ; OH reactions ; ring-cleavage/ring-retaining compounds
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract A study was conducted to examine the OH-initiated degradation products of the four title compounds in the presence of sub-part-per-million levels of NOx. The oxidation was conducted in a dynamic reactor to minimize the conversion of the aromatic compounds. The experiments were designed to represent reaction pathways that occur in the atmosphere at ambient NO2 concentrations. A wide range of ring-retaining and ring-cleavage products having widely varying yields were measured during the study. For m-xylene, the major primary products observed (with molar yields) were methyl glyoxal (0.40), 4-oxo-2-pentenal (0.12), glyoxal (0.079), and m-tolualdehyde (0.049). For p-xylene, the major primary products were p-tolualdehyde (0.103), 2,5-dimethylphenol (0.13), cis-3-hexene-2,5-dione (0.176), trans-3-hexene-2,5-dione (0.045), 2-methyl-butenedial (0.071), glyoxal (0.394), and methylglyoxal (0.217). Several other reaction products were measured at yields less than 3%. The primary products for OH + 1,2,4-trimethylbenzene were found as follows: methylglyoxal (0.44), glyoxal (0.066), cis-3-hexene-2,5-dione (0.13), trans-3-hexene-2,5-dione (0.031), biacetyl (0.114), 3-methyl-3-hexene-2,5-dione (0.079), and 2-methyl-butenedial (0.045). Six other (ring retaining) products were measured at yields less than 3%. The primary products for OH + 1,3,5-trimethylbenzene were methylglyoxal (0.90), 3-methyl-5-methylidene-5(2H)-furanone (0.1), 3,5-dimethyl-3(2H)-2-furanone (0.1), 3,5-dimethyl-5(2H)-2-furanone biacetyl (0.08), and 2-methyl-4-oxo-2- pentenal (0.05). Three other products were detected at molar yields less than 5%. In some cases, the yields for the ring fragmentation products could only be based on calibrations from surrogate compounds. Yields for several of the unsaturated dicarbonyl compounds have not been reported previously while yields for methylglyoxal, glyoxal, and biacetyl are largely consistent with previous reports. Some of the primary furanone products are the identical to those reported as secondary products in aromatic systems.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Journal of atmospheric chemistry 30 (1998), S. 209-228 
    ISSN: 1573-0662
    Keywords: toluene ; photooxidation mechanism ; aromatic hydrocarbon ; OH reactions ; ring-cleavageproducts ; ring-retaining products
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract A study has been conducted to examine the OH-initiated degradation products of toluene in the presence of sub part-per-million levels of NOX. The experiments were conducted in a dynamic reactor to minimize the conversion of the aromatic compounds while allowing a sufficient mass of products to be collected for analysis. The major primary products detected in the toluene system (with molar yields) include glyoxal (0.238), methylglyoxal (0.167), o-cresol (0.120), benzaldehyde (0.06), 4-oxo-2-pentenal (0.03), and p-cresol (0.03). Six other reaction products, most being ring cleavage products, were measured at yields below 3%. Corrections for secondary OH reactions with the products were made where necessary. The formation of the cresol isomers was found to be invariant to the NO2 concentrations which indicates that under atmospheric conditions the initial hydroxycyclohexadienyl radical reaction with NO2 is a minor process and that most of the reaction occurs with O2. The product yields found in this study are expected to be representative of those that occur in the urban atmosphere at ambient NO2 concentrations.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 27 (1995), S. 453-472 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tertiary-amyl methyl ether (TAME) is proposed for use as an additive to increase the oxygen content of gasoline as stipulated in the 1990 Clean Air Amendments. The present experiments have been performed to examine the kinetics and mechanisms of the atmospheric removal of TAME. The kinetics of the reaction of OH with TAME was examined by using a relative rate technique in which photolysis of methyl nitrite or nitrous acid was used as the source of OH. The OH rate constant for TAME and two major products (t-amyl formate and methyl acetate) were measured and yields for ten products were determined as primary products from the reaction.Values determined for the rate constants for the reaction with OH were 5.48 × 10-12 (TAME), 1.75 × 10-12 (t-amyl formate), and 3.85 × 10-13 cm3 molec-1 s-1 (methyl acetate) at 298 ± 2 K. The primary products (with corrected yields where required) from the OH + TAME that have been observed include (1) t-amyl formate (0.366), methyl acetate (0.349), acetaldehyde (0.43, corrected), acetone (0.036), formaldehyde (0.549), t-amyl alcohol (0.026), 3-methyoxy-3-methyl-butanal (0.044, corrected), t-amyloxy methyl nitrate (0.029), 3-methyoxy-3-methyl-2-butyl nitrate (0.010), and 2-methoxy-2-methyl butyl nitrate (0.004). Mechanisms leading to these products involve OH abstraction from each of the four different hydrogen atoms of TAME. © 1995 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 23 (1991), S. 907-924 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methyl tertiary butyl ether (MTBE) has been proposed and is being used as an additive to increase the octane of gasoline without the use of tetraethyl lead and alkylbenzenes. The present experiments have been performed to examine the kinetics and mechanisms of the atmospheric removal of MTBE. The kinetics of the reaction of OH with MTBE was examined by using a relative rate technique in which photolysis of methyl nitrite was used as the source of OH. With n-butane as the reference compound a value of (2.99 ± 0.12) × 10-12 cm3 molecule-1 s-1 at a temperature of 298 K was obtained for the rate constant. The products (and product yields) for the OH reaction with MTBE in the presence of NOx were also determined and found to be t-butyl formate (0.68 ± 0.05), methyl acetate (0.14 ± 0.02), acetone (0.026 ± 0.003), t-butanol (0.062 ± 0.009), and formaldehyde (0.48 ± 0.05) in mols/mol MTBE converted. The OH rate constant for the major product formed, t-butyl formate was also measured and found to be (7.37 ± 0.05) × 10-13 cm3 molecule-1 s-1. Mechanisms to rationalize the formation of the products are presented.
    Additional Material: 5 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1355-1371 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study was conducted to measure the hydroxyl radical rate constants using a relative rate procedure in which the photolysis of methyl nitrite was the source of OH. During the course of this study, the OH rate constant was measured for a number of chlorinated solvents for which measurements have not previously been reported or for which there are few reliable measurements.Room temperature OH rate constants are presented for six chlorinated hydrocarbons (allyl chloride, benzyl chloride, chlorobenzene, epichlorohydrin, trichloroethylene, and vinylidene chloride) and four oxygenated hydrocarbons (acrolein, methacrolein, methyl ethyl ketone, and propylene oxide). Also included are OH rate constants for alkanes (ethane, propane, isobutane, and cyclohexane), alkenes (trans-2-butene and isoprene), and aromatic hydrocarbons (benzene, toluene, o-, m-, and p-xylene). Rate constants for compounds not previously reported include vinylidene chloride (1.49 ± 0.21 × 10-11 cm3 molecule-1 s-1) and benzyl chloride (2.96 ± 0.15 × 10-12 cm3 molecule-1 s-1). The analysis for chlorinated hydrocarbons included a correction for possible chlorine atom reactions.
    Additional Material: 4 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 24 (1992), S. 199-215 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ethyl tertiary butyl ether (ETBE) is being proposed as an additive for use in reformulated gasolines. In this study, experiments were performed to examine the kinetics and mechanism of the atmospheric removal of ETBE. The kinetics of the reaction of ETBE with OH radicals were examined by using a relative rate technique with the photolysis of methyl nitrite to generate OH radicals. With n-hexane as the reference compound, a value of (9.73 ± 0.33) × 10-12 cm3 molecule-1 s-1 was obtained for the rate constant. The OH rate constant for t-butyl acetate, a product of the oxidation of ETBE, was (4.4 ± 0.4) × 10-13 cm3 molecule-1 s-1 at 298 K.The primary products and molar yields for the OH reaction with ETBE in the presence of NOx were t-butyl formate (0.64 ± 0.03), t-butyl acetate (0.13 ± 0.01), ethyl acetate (0.043 ± 0.003), acetaldehyde (0.16 ± 0.01), acetone (0.019 ± 0.002), and formaldehyde (0.53 ± 0.04). Under the described reaction conditions, the formation of t-butyl nitrite was also observed. From these molar yields, approximately 98% of the reacted ETBE could be accounted for by paths leading to these products. Chemical mechanisms to explain the formation of these products are presented.
    Additional Material: 4 Ill.
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  • 9
    Publication Date: 1979-05-15
    Print ISSN: 0021-9606
    Electronic ISSN: 1089-7690
    Topics: Chemistry and Pharmacology , Physics
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  • 10
    Publication Date: 1981-04-15
    Print ISSN: 0021-9606
    Electronic ISSN: 1089-7690
    Topics: Chemistry and Pharmacology , Physics
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