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  • Chemistry  (3)
  • 33.50Dq  (2)
  • Pentafluorosulfanyl-substituted perfluorinated carbanions  (1)
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  • 1
    ISSN: 1432-0649
    Keywords: 82.40Py ; 33.50Dq
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Nitrogen atoms have been detected in stoichiometric flat premixed H2/O2/N2 flames at 33 and 96 mbar doped with small amounts of NH3, HCN, and (CN)2 using two-photon laser excitation at 211 nm and fluorescence detection around 870 nm. The shape of the fluorescence intensity profiles versus height above the burner surface is markedly different for the different additives. Using measured quenching rate coefficients and calibrating with the aid of known N-atom concentrations in a discharge flow reactor, peak N-atom concentrations in these flames are estimated to be on the order of 1012−5×1013 cm−3; the detection limit is about 1×1011 cm−3.
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  • 2
    ISSN: 1432-0649
    Keywords: 82.40Py ; 33.50Dq
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Temperature profiles in several premixed low pressure H2/O2/N2 flames and in an atmospheric pressure CH4/air flame were determined by laser-induced fluorescence (LIF) and by CARS experiments. In the LIF study, temperatures were derived from OH excitation spectra, CARS temperatures were deduced from N2 Q-branch spectra. The present study is the first quantitative comparison of these two methods for temperature determination in flames burning at pressures up to 1 bar. The resulting temperatures showed good agreement.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 557 (1988), S. 182-190 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal Structure of the SF5--AnionThe carbanion SF5—C(CF3)2- decomposes slowly forming SF5-, and (CF3)2C=C(CF3)2. The pentafluorosulfates(IV) grow in large crystals which are stable for prolonged times in presence of a SF4 vapour pressure. Crystal structure analysis of Rb+SF5- (Pbnm, a = 776.1(14), b = 990.3(5), c = 614.1(3) pm, Z = 4) revealed the SF5- anion in the expected square pyramidal structure. The axial bond is 15.9 pm shorter than the average equatorial bonds. The sulfur atom is located below the equatorial fluorine atoms. Pure Cs+SF5--crystals seem to be notoriously twinned. Accidentally we isolated a double salt (Cs+)6(SF5-)4 (HF2-)2 (P4b2, a = 1031.7(15), c = 627.6(9) pm, Z = 1). Herein the anion SF5- has the same structure as in Rb+SF5-.
    Notes: Das Carbanion SF5—C(CF3)2- zersetzt sich langsam zu SF5- und (CF3)2C=C(CF3)2. Die Pentafluorosulfate(IV) wachsen dabei in großen Kristallen, die in Gegenwart eines SF4-Gasdruckes längere Zeit haltbar sind. Die Kristallstrukturanalyse des Rb+SF5- (Pbnm, a = 776,1(14), b = 990,3(5), c = 614,1(3) pm, Z = 4) zeigt das SF5--Anion in seiner erwarteten quadratisch-pyramidalen Struktur. Die axiale Bindung ist beträchtliche 15,9 pm kürzer als die durchschnittliche äquatoriale S—F-Bindung. Auch befindet sich der Schwefel deutlich unterhalb der Ebene, die durch die vier äquatorialen Fluoratome gebildet wird.Vom reinen Cs+SF5- konnten bisher nur Zwillingskristalle erhalten werden. Durch Zufall gelang die Isolierung eines Doppelsalzes (Cs+)6(SF5-)4 (HF2-)2. Die Kristallstrukturanalyse (P4b2, a = 1031,7(15), c = 627,6(9) pm, Z = 1), zeigt das Vorhandensein der gleichen SF5-Struktureinheiten wie im Rb+SF5-.
    Additional Material: 4 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 602 (1991), S. 89-96 
    ISSN: 0044-2313
    Keywords: Pentafluorosulfanyl-substituted perfluorinated carbanions ; electrochemical and ESR investigation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Electrochemical Investigations of SF5-Substituted CarbanionsThe perfluorinated carbanions SF5—C(CF3)2- and [(SF5)2C—CF3]- are sufficently stable in acetonitrile to be investigated by electrochemical methods. The oxidation of [(SF5)2C—CF3]- at +1.24 V (vs. SCE) results in the formation of the radical [(SF5)2C—CF3], which can be detected by ESR methods. The oxidation of [SF5—C(CF3)2]- at +1.55 V leads only to the radical (CF3)2C = C(CF3)2-, a secondary product. The carbanions [SF5—C(CF3)2]- and [(SF5)2C—CF3]-, the unsaturated compounds (SF5)2C = CF2, SF5—C(CF3) = CF2 and SF5—C(CH3) = CF2 as well as (SF5)2CH2 are irreversibly reduced at a potential range from -0.6 V to -0.8 V.
    Notes: Die perfluorierten Carbanionen [SF5—C(CF3)2]- und [(SF5)2C—CF3]- sind in Acetonitril hinreichend stabil, um elektrochemisch untersucht werden zu können. Die Oxidation von [(SF5)2C—CF3]- führt bei +1,24 V (vs. SCE) zu dem in ESR-Experiment beobachtbaren Radikal [(SF5)2C—CF3]. Für [SF5—C(CF3)2]-führt die Oxidation bei +1,55 V nur zu dem radikalischen Folgeprodukt (CF3)2C = C(CF3)2-. Die Carbanionen [SF5—C(CF3)2]- und [(SF5)2C—CF3]-, die ungesättigten Verbindungen (SF5)2C = CF2, SF5—C(CF3) = CF2 und SF5—C(CH3 = CF2) wie auch (SF5)2CH2 werden im Potentialbereich von -0,6 V bis -0,8 V irreversibel reduziert.
    Additional Material: 3 Ill.
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  • 5
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reactions of ground state oxygen atoms with trans-2-butene, cis-2-butene, 2-methylpropene, 2-methyl-2-butene, and 2,3-dimethyl-2-butene was investigated in the temperature range 200 to 370K. In this range, the rate constants are (in units 10-11 cm3 s-1): (1.1 ± 0.1) exp[+(180 ± 24)K/T]; (0.98 ± 0.09) exp[+(149 ± 23)K/T]; (1.14 ± 0.13) exp[+(128 ± 33)K/T]; (2.34 ± 0.16) exp[+(250 ± 16)K/T]; and (3.31 ± 0.50) exp[+(257 ± 36)K/T], respectively. The atoms were generated by the H2 laser photolysis of NO and detected by the time resolved chemiluminescence in the presence of NO. The concentrations of the O(3P) atoms were kept so low that secondary reactions with products are unimportant. © 1995 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
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