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  • Articles  (22)
  • Inorganic Chemistry  (13)
  • Physical Chemistry  (9)
  • Gas chromatography
  • Wiley-Blackwell  (22)
  • 1975-1979  (22)
  • 1976  (22)
  • 1
    Electronic Resource
    Electronic Resource
    Preparation of nonreactive surfaces for reaction-rate studies (1976)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 8 (1976), S. 23-24 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550080104
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  • 2
    Electronic Resource
    Electronic Resource
    Studies on MM″(NCS)4 [M=Ni(II), Fe(II), Zn(II), and M″=Hg(II) Zn(II)] complexes (1976)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 423 (1976), S. 173-179 
    Details
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Untersuchungen an MM″ (NCS)4-Komplexen (M = NiII, FeII, ZnII; M″ = HgII, ZnII)Komplexe des Typs MM′(NCS)4 · xL M = NiII, FeII, ZnII; M″ = HgII, ZnII; x = 2, 4, 6; L = Nicotinamid (nia), Isonicotinsaiurehydroxid (inh) 2-Aminopyrimidin (2apm)] wurden dargestellt und charakterisiert durch Elementaranalyse, molare Leitfähigkeit, magnetisches Moment, IR- und Elektronenspektren.
    Notes: Coordination complexes of the type MM″(NCS)4 · xL M = Ni(II), Fe(II), Zn(II), M″ = Hg(II), Zn(II), x = 2, 4, 6 and L = nicotinamide (nia), 3-cyanopyridine (3-cpy), 4-cyanopyridine (4cpy), 4-aminopyridine (4apy), isonicotinic acid hydrazide (inh), 2-aminopyrimidine (2apm)l have been prepared and characterized by elemental analysis, molar conductance, magnetic moment, infrared and electronic spectral studies. Molar conductance data of NiZn(NCS), complexes are equivalent to 1:1 electrolyte. The infrared spectral studies indicate that only bridged thiocyanate groups are present in the complexes of the type NiHg(SCN)4 · 4L [L=3 and 4cpy, inh] and FeHg(SCN)4 · 2L [L = nia, 2apm], whereas both bridged and terminal thiocyanates are present in the complexes of the type NiHg(SCN)4 · 4L [L = nia, 3apy and ZnHg(SCN)4 · 2(inh). BOHR magneton values and electronic spectral data indicate an octahedral environment around nickel and iron in their complexes. Symmetry and group theory have also been used to establish the structure of the complexes.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19764230211
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  • 3
    Electronic Resource
    Electronic Resource
    Elektrochemische Synthesen, IV: Die Elektrosynthese von 1,3,5-Triazinen aus Aldehyden (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1346-1352 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Electrochemical Syntheses, IV: The Electrosynthesis of 1,3,5-Triazines from AldehydesThe electrochemical oxidation of acetaldehyde in methanol/ammonia yields 2,4,6-trimethyl-1,3,5-triazin (3) in at least 20% yield, whereas benzaldehyde gives only a 1% yield of the triphenyl derivative 4. No s-triazine (5) is obtained from formalin. In addition to the triazines 1-3 the mixed triazines 6-8 are obtained by electrolyzing an acetaldehyde/isobutyraldehyde mixture. The reason for the difference in the yields of the triazines from aldehydes is to be sought in the equilibrium concentration fo the precursing amino-methoxy adduct RCH(NH2)OCH3.
    Notes: Die elektrochemische Oxidation von Acetaldehyd in Methanol/Ammoniak liefert 2,4,6-Trimethyl-1,3,5-triazin (3) in 20% Ausbeute, die von Benzaldehyd jedoch nur 1% des Triphenylderivates 4; aus Formalin konnte kein s-Triazin (5) erhalten werden. Mit einem Acetaldehyd/Isobutyraldehyd-Gemisch konnten neben 1,2 und 3 auch die gemischten Triazine 6-8 erhalten werden. Als Ursache für den unterschiedlichen Erfolg dieser Triazinsynthese wird die Gleichgewichtskonzentration des Aminomethoxy-Aldehydadduktes RCH(NH2)OCH3 angesehen.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090415
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  • 4
    Electronic Resource
    Electronic Resource
    Das Verhalten von Mono- und Diorganylphosphinsulfiden gegenüber Metallcarbonylsystemen, IX. Das Verhalten von Mono- und Diorganylphosphinsulfiden gegenüber Metallcarbonylsystemen, IX. Über Reaktionen an der SH-Gruppe von Pentacarbonyl-(mercaptodimethylphospin)chrom(O) (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 3323-3330 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Behavior of Mono- and Diorganylphosphine Sulfides towards Metal Carbonyl Systems, IXReactions with the SH Group of Pentacarbonyl(mercaptodimethylphosphine)chromium(O)The acidic SH group in the complex (OC)5CrP(CH3)2SH (1) can be methylated with CH2N2 to give 2. The anion in 3a, b is obtained by reaction of N(C2H5)3 or sodium with 1. The binuclear via phosphorus and sulfur linked dichromate anion in 5 Results from 3a and (OC)5CrTHF. The i. r., 1H, and 31P n. m. r. spectra of the new prepared compounds 2, 3a, b, and 5 as well as a correlation between the 31P n. m. r. spectra and v(P-S) are discussed.
    Notes: Die acide SH-Gruppe im Komplex (OC)5CrP(CH3)2SH (1) läßt sich mit CH2N2 zu 2 methylieren. Das Anion in 3a, b erhält man durch Einwirkung von N(C2H5)3 oder Natrium auf 1. Aus 3a und (OC)5CrTHF entsteht das zweikernige, über Phosphor und Schwefel verbrückte Dichromat-Anion in 5. Die IR-, 1H- und 31P-NMR-Spektren der neu dargestellten Verbindungen 2, 3a, b and 5 sowie ein Zusammenhang zwischen den 31P-NMR-Spektren und v(P-S) werden diskutiert.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761091007
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  • 5
    Electronic Resource
    Electronic Resource
    An absolute measurement of the rate constant for t-butyl radical combination (1976)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 8 (1976), S. 45-58 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constant for tert-butyl radical recombination has been measured near 700°K by the very-low-pressure pyrolysis (VLPP) technique and was found to be 108.8±0.3 M-1·sec-1 with neglibible temperature dependence. The thermochemical parameters for tert—butyl radicals were varied within reasonable limits to bring into agreement the data for the decomposition of 2,2,3,3-tetramethyl butane and the recombination of tert-butyl radicals. The revised thermochemistry also makes the gas-phase results and liquid-phase results compatible.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550080107
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  • 6
    Electronic Resource
    Electronic Resource
    Kinetics of the Diels-Alder addition of acrolein to cyclohexa-1,3-diene and its reverse reaction in the gas phase (1976)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 8 (1976), S. 641-649 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Diels-Alder addition of acrolein to cyclohexa-1,3-diene has been studied between 486 and 571°K at pressures ranging from 55 to 240 torr. The products are endo- and exo-5-formylbicyclo[2.2.2]oct-2-ene (endo- and exo-FBO), and their formations are second order. The rate constants (in l./mole · sec) are given by \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} {\rm}k_{{\rm endo}} = -(19,470 \pm 50)/4.576T + (5.65 \pm 0.02)$$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} {\rm}k_{{\rm exo}} = - (20,630 \pm 50)/4.576T + (5.51 \pm 0.02)$$\end{document}The retro-Diels-Alder pyrolysis of endo-FBO has also been studied. In the ranges of 565-638°K and 6-38 torr, the reaction is first order, and its rate constant (in sec-1) is given by \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} {\rm}k_{{\rm p}} = - (46,390 \pm 110)/4.576T + (12.98 \pm 0.04)$$\end{document}The reaction mechanism is discussed. The heat of formation and the entropy of endo-FBO are estimated.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550080502
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  • 7
    Electronic Resource
    Electronic Resource
    Charge transfer reactions in alkane and cycloalkane systems. Estimated ionization potentials (1976)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 8 (1976), S. 725-739 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants of change transfer reactions kCT, involving C3—C9 alkanes and cycloalkanes, have been determined in an ion cyclotron resonance mass spectrometer. The rate constants are significantly lower than the corresponding rate constants for collision when the reaction is less than about 0.5 eV exothermic for linear alkane ions, or less than about 0.2 eV exothermic for cycloalkane ions. In this region of low reaction efficiency, the efficiency of reaction with linear or branched alkanes seems to depend primarily on reaction exothermicity. (The efficiencies of reaction of a given ion with cyclic alkanes also depend on ΔHrn, but are higher than for reactions with other compounds). Although the lowered reaction efficiencies probably result, at least in part, from unfavorable Franck-Condon factors in the energy range near the ionization onset, quantitative correlations between reaction efficiency and estimated relative Franck-Condon factors were not observed. When the enthalpy of reaction is small (less than about -0.15 eV), it is seen that the reverse charge transfer can also occur, and equilibrium is established under the conditions of these experiments. From the observed equilibrium constants, values for the standard free energy change are derived, and assuming that ΔS is small for electron transfer equilibria, values of ΔHrn are estimated. In the case of the equilibria involving cyclohexane ion, these values of ΔHrn lead to estimates of the ionization potentials of methylcyclopentane, 3-methylpentane, n-octane, 2,2-dimethylbutane, and 2,3-dimethylbutane, which are lower than the ionization potentials of cyclohexane, that is, 〈9.88 eV, although all these compounds had previously been reported to have ionization potentials above 10.03 eV. That the ionization potentials are indeed lower than 10.03 eV is confirmed by determining the quantum yields of ionization with 10.03-eV photons.It is pointed out that the conclusions reached here apparently also apply to the charge transfer reactions of alkane ions in the liquid phase.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550080508
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  • 8
    Electronic Resource
    Electronic Resource
    Excited-state kinetics in the photolysis of azoethane and hexafluoroazomethane at 366 nm, up to one atmosphere pressure, and from room temperature to 150°CAlthough the Stern-Volmer equation originally relates to the electronic quenching of an excited electronic state, it is convenient to use the terminology for vibrational relaxation; more than one (distinguishing equilibrated states) electronic state is involved in any case (1976)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 8 (1976), S. 959-969 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photochemistry of azoethane and hexafluoroazomethane at 366 nm has been reinvestigated up to 1 atm pressure, and over a range of temperature from 27 to 150°C. The Stern-Volmer type quenching plots primarily demonstrate the decomposition of a single electronic and vibrationally excited state for azoethane, but competitive photodissociation from two different electronic and vibrationally excited states, which was previously postulated for hexafluoroazomethane and azoisopropane, is confirmed for hexafluoroazomethane. It is concluded, however, that two different electronic and vibrationally excited photodissociating states are present in azoethane photolysis, but that one of them is difficult to detect, at least by the present approachPhotosensitization with biacetyl at 436 nm also causes the dissociation of azoethane, and this is probably from the vibrationally equilibrated first triplet state. The energy barrier for this process was found to be 5.0 kcal/mol.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550080613
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  • 9
    Electronic Resource
    Electronic Resource
    An investigation of nonequilibrium kinetic isotope effects in chemically activated vinyl radicals (1976)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 8 (1976), S. 825-857 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New experimental data have been obtained for H + C2H2, D + C2H2, H + C2D2, and D + C2D2 at room temperature. Two previously described apparatus were used in order to measure the pressure dependence of the reactions. The absolute rate constants are compared to results from other laboratories. The present results and those of Payne and Stief are used to obtain the high-pressure limiting rate constant at room temperature. When the activation energy from the work of Payne and Stief is considered, it is shown that the A factor for H + C2H2 is too low by a factor of ∼20. If a transmission coefficient is introduced which is constant for all isotopic variations, the pressure dependence can be explained in terms of the randomly energized radicals. RRKM theory is then invoked to explain the observed statistical nonequilibrium kinetic isotope effects.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550080605
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  • 10
    Electronic Resource
    Electronic Resource
    The kinetics of the anation reaction of aquopentaamminecobalt(III) by malonate in acidic aqueous solution (1976)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 8 (1976), S. 411-423 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Co(NH3)5OH23+ ion reacts with malonate to form Co(NH3)5O2CCH2CO2H2+ or Co(NH3)5O2CCH2CO2+, depending on the pH of the reaction solution. The kinetics of this anation reaction have been studied as a function of [H+] for the acidity range 1.5 ≤ pH ≤ 6.0 in the temperature range of 60 to 80°C, the [total malonate] ≤ 0.5 M, and the ionic strength 1.0M. The anation by malonic acid follows second-order kinetics, the rate constant being 8.0 × 10-5 M-1·sec-1 at 70°C, and the anations by bimalonate (Q1, k1) and malonate ion (Q2, k2) are consistent with an Id mechanism. Typical values at 70°C for the ion pair formation constants are Q1 = 1.3, Q2 = 5.4M-1; and for the interchange rate constants k1 = 5.3 × 10-4; k2 = 7.3 × 10-4 sec-1. The activation parameters for the various rate constants are reported and the results discussed with reference to previously reported data for similar systems.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550080308
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