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  • 1
    Electronic Resource
    Electronic Resource
    Generation of ground electronic state haloalkyl radicals in the gas phase (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 639-649 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Gaseous haloalkyl radicals were prepared by the photolysis of iodohaloalkanes in Pyrex vessels containing mercury (I) halides. Cleavage of the carbon-iodine bond gave mercury (II) halide and a radical which was subsequently shown to react on the ground state electronic energy surface. The usefulness of this method for chemical activation rate constant studies is illustrated by measurement of unimolecular rate constants for decomposition of CH2ClCH2Cl and CF3CH3. Possible mechanisms for photodecomposition of iodoalkanes in the presence of mercury (I) halides are discussed.
    Additional Material: 4 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of the atmospheric oxidation of Ethyl tertiary butyl ether (1992)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 24 (1992), S. 199-215 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550240208
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  • 3
    Electronic Resource
    Electronic Resource
    Room temperature rate constants for the reaction of OH with selected chlorinated and oxygenated hydrocarbons (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1355-1371 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550181207
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  • 4
    Electronic Resource
    Electronic Resource
    The photooxidation of methyl tertiary butyl ether (1991)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 23 (1991), S. 907-924 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550231006
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  • 5
    Electronic Resource
    Electronic Resource
    The dark reactions F2 + CF3I, C2F5I, and n-C3F7I (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 43-55 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions between F2 and the lowest members of the homologous series of perfluoroalkyl iodides (CF3I, C2F5I, and n-C3F7I) have been studied. For these compounds, an exponential decrease in the alkyl iodide concentration over time following an induction period is observed for certain experimental conditions. Other conditions lead to chaotic-like kinetic behavior where the rate of alkyl iodide consumption continually changes. Kinetic rate data with CF3I show that the disappearance rate depends upon both the type of surface and surface preparation. For all three compounds, Arrhenius plots reveal activation energies on the order of 10 kcal/mol, consistent with effective initiation steps of F2 + RI → RIF + F, where R represents the CF3, C2F5, or n-C3F7 radical respectively. The end products of the F2 + RI reactions are RF, R2, and IF5, suggesting that the R radicals play an important kinetic role. Introducing O2 into the F2 + RI reaction systems results in successive oxidation of R by O2, leading to the formation of CF2O as an additional end product. IF(B → X) emission is observed from the RI-rich F2 + RI reactions, confirming the existence of IF as an intermediate. © 1996 John Wiley & Sons, Inc.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.6
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  • 6
    Electronic Resource
    Electronic Resource
    Stereochemical studies. XXXIVPart XXXIII, I. G. Mursakulov, V. A. Svyatkin, V. V. Samoshin, N. S. Zefirov, Zh. Org. Khim. 22, 773-776 (1986).. Quantitative description of ring puckering via torsional angles. The case of six-membered rings (1990)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 147-158 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The quantitative description of ring puckering suggested by the authors is compared with that of Cremer and Pople. The applicability of both methods is discussed for the case of six-membered rings with the use of model calculations simulating various ring distortions and with the analysis and comparison of puckering parameters computed on the basis of x-ray data for 40 six-membered rings in different cyclic structures. The 2N times reduction of the field of variation of puckering parameters for the N-membered ring is suggested and the algorithm for the renumbering of the ring atoms for this purpose is described for six-membered rings.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610030304
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  • 7
    Electronic Resource
    Electronic Resource
    Ionization kinetics of rhodamine b leucocyanide in the presence of poly(vinylbenzyltrimethylammonium chloride) (1992)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 5 (1992), S. 595-599 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The participation of the carboxylate group in the ionization of Rhodamine B leucocyanide was studied in an aqueous solution of poly(vinylbenzyltrimethylammonium chloride) (PVBTA) or cetyltrimethylammonium bromide (CTAB) at constant temperature and pH 8. The experimental rate constant (kexp) decreases with increasing PVBTA concentration. The results are interpreted in terms of the binding of the ionized form of Rhodamine B leucocyanide (RBCN-) to a single class of completely independent binding sites on the PVBTA. From this model, a value of 1.09 × 106 l mol-1 was obtained for the binding constant. The effect of CTAB is different from that obtained with PVBTA. After a region in which there are large changes in kexp with the CTAB concentration, this constant reaches a zone where its value is independent of the surfactant concentration. The decrease in kexp in the first zone was explained in terms of an ionic association between RBCN- and the cationic heads. In the second zone, it was assumed that a micellar effect operates on the ionization kinetics. In a similar form, the esterification of the carboxylate group leads to a slower ionization rate.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610050907
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  • 8
    Electronic Resource
    Electronic Resource
    Stereochemistry of aminolysis of N-pentafluorophenylcarbonimidoyl dichloride. Crystal and molecular structures of N2-pentafluorophenyl-N1,N1-dibenzylchloroformamidine (1993)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993), S. 319-325 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It has been established that the product of the reaction of N-pentafluorophenylcarbonimidoyl dichloride (1) with dibenzylamine, viz. N2-pentafluorophenyl-N1,N1-dibenzylchloroformamidine (4a) is a Z-isomer, whereas according to the concept of stereoelectronic control one might have expected a product with E-configuration. The heat of formation and the geometry of Z- and E isomer of N2-pentafluorophenyl-N1,N1-diethylchloroformamidine (4b) (the latter is a product of the reaction of 1 with diethylamine) were calculated with the semi-empirical MNDO method. The calculated geometry of (Z)-4b was found to be in a good agreement with the experimentally determined structure of 4a. The formation of (Z)-4b is more preferable energetically than that of (E)-4b; the calculated difference in the heats of formation is 2·8 kcal mol-1. Thermodynamic control of the reaction stereochemistry is proposed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610060602
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  • 9
    Electronic Resource
    Electronic Resource
    Interaction of 3,4-diphenyl-1,2,5-thiadiazole 1,1-dioxide with proton donor solvents (1993)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993), S. 341-346 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The UV spectra of 3,4-diphenyl-1,2,5-thiadiazole 1,1-dioxide (I) and that of its thiadiazoline and thiadiazolidine derivatives were measured in several aprotic and protic solvents. Strong specific interactions of I with protic solvents are observed and the formation of stable carbinolamine type derivatives of I with methanol or ethanol is proposed. Spectroscopic data (UV, 1H and 13C NMR) and electrochemical evidence for their formation are given and a new thiadiazoline derivative of I (3-ethoxy-2-methyl-3,4-diphenyl-1,2,5-thiadiazoline 1,1-dioxide) was synthesized. The equilibrium constant for the reaction of I with ethanol is reported.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610060605
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  • 10
    Electronic Resource
    Electronic Resource
    The homogeneous gas phase H2—D2 metathesis at room temperature: Reaction induced by specific vibrational excitation (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 93-106 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have demonstrated that reactions for which substantial activation energies are needed can be induced to occur at room temperature via specific vibrational excitation. Indeed, the indications are that the atom-switching reactions for which Ea 〉 25 kcal take place with high probability only when the activation energy is localized in the vibrational mode. In this preliminary report on the utilization of the stimulated Raman effect to generate substantial populations in the critical vibrational states required for the homogeneous atom exchange between H2 and D2, we first summarized the historical development of the concept. The experimental arrangement is then described and the analytical results tabulated; the observed dependence on relative concentrations is semiquantitatively rationalized on the basis of a model proposed in 1964. Independent shock tube and molecular beam investigations were similarly accounted for. Attention is called to the discrepancy between the generally concordant experimental results and the ab initio quantum mechanical calculations of the potential energy surface for 4H atoms.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050109
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