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  • Artikel: DFG Deutsche Nationallizenzen  (205)
  • 1985-1989  (205)
  • 1986  (205)
  • Physical Chemistry  (114)
  • Biochemistry  (91)
Datenquelle
  • Artikel: DFG Deutsche Nationallizenzen  (205)
Materialart
Erscheinungszeitraum
  • 1985-1989  (205)
Jahr
Schlagwörter
  • 1
    Digitale Medien
    Digitale Medien
    Myoadenylate deaminase deficiency (1986)
    Springer
    Journal of molecular medicine 64 (1986), S. 342-347 
    Details
    ISSN: 1432-1440
    Schlagwort(e): Myoadenylate deaminase deficiency ; Histochemistry ; Biochemistry ; Metabolic myopathy
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary This report concerns two unrelated males; one had sarcoidosis, sarcoid myopathy and muscle weakness, and the other had exercise-induced weakness and myalgia. Both patients had a lack of ammonia rise in their serum after an ischemic work test, minimal histochemical activity of myoadenylate deaminase in repeated muscle biopsies, and less than 5% of normal biochemical activity of myoadenylate deaminase in their skeletal muscles. These three criteria establish primary myoadenylate deaminase deficiency as a separate primary metabolic muscle disease which merits differential diagnostic consideration when patients complain of muscle weakness and cramps.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF01711958
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  • 2
    Digitale Medien
    Digitale Medien
    Intrinsic actions of the benzodiazepine receptor antagonist Ro 15-1788 (1986)
    Springer
    Psychopharmacology 88 (1986), S. 1-11 
    Details
    ISSN: 1432-2072
    Schlagwort(e): Ro 15-1788 ; Benzodiazepine antagonist ; Behaviour ; Electrophysiology ; Biochemistry ; Neurology
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract The imidazodiazepine Ro 15-1788 is a benzodiazepine receptor antagonist that was initially reported to be lacking in intrinsic activity in a variety of test situations in which benzodiazepine-like effects can be identified. However, many recent studies have shown that this compound does indeed have intrinsic activity in a variety of behavioural, neurological, electrophysiological and biochemical preparations in both animals and man. The purpose of the present review is firstly to describe these intrinsic actions, and secondly to consider to what extent these intrinsic actions of Ro 15-1788 have implications for current concepts of the functioning of the benzodiazepine receptor.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00310505
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  • 3
    Digitale Medien
    Digitale Medien
    Assessment of myocardial metabolism by PET —a sophisticated dream or clinical reality? (1986)
    Springer
    European journal of nuclear medicine 12 (1986), S. S70 
    Details
    ISSN: 1619-7089
    Schlagwort(e): Positron emission tomography ; Biochemistry
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF00258111
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  • 4
    Digitale Medien
    Digitale Medien
    The beta-adrenoceptor-adenylate cyclase complex (1986)
    Springer
    Pharmacy world & science 8 (1986), S. 209-222 
    Details
    ISSN: 1573-739X
    Schlagwort(e): Biochemistry ; Pharmacology ; Receptors, adrenergic, beta ; Review
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Developments in the receptor concept have greatly influenced our current knowledge of the beta-adrenoceptor. The triad of pharmacology, organic chemistry and studies in structure-activity relationships is discussed along historical lines, as it has been and still is an impetus for progress in the biochemistry of ligand-receptor interactions. With respect to the beta-adrenoceptor complex these advances which have led to a model in which three protein structures are functionally interacting within the frame of the cell wall: the beta-adrenoceptor, the regulatory guanine nucleotide binding protein, and the enzyme adenylate cyclase, are reviewed.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1007/BF01957781
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  • 5
    Digitale Medien
    Digitale Medien
    Interaction energy studies of pyrrolopyrimidine nucleoside antibiotics-toyocamycin (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 7 (1986), S. 13-19 
    Details
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: The biological activity of toyocamycin has been examined on the basis of the model developed by Sanyal et al. for the incorporation of nucleoside analogs during transcription. Using the simplified formula of Claverie for intermolecular interactions, computations have been carried out on the pairing energy of toyocamycin base with the complimentary bases as well as on the interaction energy with nucleic acid base pairs. The results are compared with the results of similar computations with nucleic acids. On the basis of the model an attempt has been made to explain the mechanism of the biological action of toyocamycin.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/jcc.540070103
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  • 6
    Digitale Medien
    Digitale Medien
    Preliminary announcement: 6th International Congress on Quantum Chemistry (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 7 (1986), S. 254-254 
    Details
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/jcc.540070218
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  • 7
    Digitale Medien
    Digitale Medien
    Molecular associations: Values of the expansion parameters for new classes of atoms (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 7 (1986), S. 55-57 
    Details
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: Expansion parameters, for use in a 1/R expansion developed at this laboratory for the study of molecular interactions, have been determined for new classes of atoms. Test calculations with these new parameters have yielded very satisfactory results for the glycine zwitterion, in dimer form and solvated, confirming the goodness of the parameters and the appropriateness of the formulation.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/jcc.540070107
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  • 8
    Digitale Medien
    Digitale Medien
    Symmetry properties of chemical graphs. IX. The valence tautomerism in the P73- skeletonThis contribution is dedicated to Professor F. A. Cotton for his prolonged support and appreciation of chemical graph theory. (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 7 (1986), S. 35-54 
    Details
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: We investigate the intramolecular rearrangement of the P73- ion in which P—P bonds are continuously broken and reestablished resulting in a dynamic structure with all seven phosphorus atoms being chemically equivalent. This leads to 7/3 = 1680 valence tautomers. The P73- ion is a typical fluctuating molecule, distantly related to C10H10 bullvalene. In order to determine the symmetry of the process we first consider the problem of the construction of the rearrangement graph. Initial steps toward this goal are illustrated, and additional characterizations of the graph are derived after its construction by computer. A number of properties of this rather complicated graph having 1680 vertices and 2520 edges are discussed: in particular the occurrence of various cycles, the maximal distance between vertices, the count of neighbors at different distance, and finally its symmetry.
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/jcc.540070106
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  • 9
    Digitale Medien
    Digitale Medien
    Symposium on Computational and Mathematical Chemistry. Satellite Symposium of the Canadian Institute of Chemistry Conference Saskatoon, Canada, June 1-4, 1986 (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 7 (1986), S. 89-89 
    Details
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/jcc.540070110
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  • 10
    Digitale Medien
    Digitale Medien
    Mindo/3 and mndo calculations of closed- and open-shell cations containing C, H, N, and O (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 7 (1986), S. 93-104 
    Details
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: Heats of formation of 119 closed- and open-shell carbocations calculated by the semiempirical quantum chemical methods MINDO/3 and MNDO are reported and compared with experimental data. With proper consideration of failures in specific areas, both methods can be used for the thermodynamics of carbocations containing C, H, N, and O. MINDO/3 predicts unrealistic values for nitrogen containing cations with nitrogen multiple bonds and is not suited for closed-shell cations containing oxygen. Saturated acyclic hydrocarbon radical cations often are computed with abnormally long CC bonds by MNDO. Otherwise, the standard deviation of the two methods is not very different, being in the range of ±13 kcal/mol. MINDO/3 tends to overestimate the cation stabilities, whereas MNDO calculates cations usually too high in energy. Some of the errors which were found in the calculations of the ions are related to the computed values for the parent neutral structures, but others are not.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/jcc.540070202
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  • 11
    Digitale Medien
    Digitale Medien
    A force-field study of the conformational characteristics of the iduronate ring (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 7 (1986), S. 105-112 
    Details
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: Methods of molecular mechanics were applied to investigate the conformation of the (methyl 2-O-sulfate-4-methyl-α-L-idopyranose) uronic acid (DMIS), in order to correlate the peculiar vicinal proton coupling constants observed in polysaccharides containing the iduronate ring to the conformational characteristics of this sugar ring. We found three conformers with comparable energies, namely the two chair forms 1C4 and 4C1 and the skew-boat form 2S0(L); the latter is separated from each chair form by a barrier of about 9 kcal/mol. Along the pseudorotational path three additional minima (3S1, 1S3, and 1S5) were found, yet at least 4 kcal/mol higher than 2S0. The results obtained for the relative energies of the three conformers and the conformation of the side groups were affected by the inclusion of the electrostatic term and, in particular, by the charge assigned to the ionic groups of DMIS. However, the conformational properties of the idopyranosidic ring in DMIS (and in related compounds) should still be interpreted in terms of equilibrium among these three conformers only.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/jcc.540070203
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  • 12
    Digitale Medien
    Digitale Medien
    An improved set of mndo parameters for sulfur (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 7 (1986), S. 140-143 
    Details
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: The MNDO parameters for sulfur have been reoptimized. Calculations for a number of sulfur compounds indicate a very significant improvement. Inclusion of d AOs failed to correct the errors for compounds of sulfur in its higher valence states. Since d AOs are not included, the calculations are still confined to compounds of divalent sulfur.
    Zusätzliches Material: 4 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/jcc.540070206
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  • 13
    Digitale Medien
    Digitale Medien
    The effect of including polarization functions on the geometrical parameters calculated for pyridine (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 7 (1986), S. 153-157 
    Details
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: Geometrical parameters for pyridine have been calculated using the 6-31G, 6-31G*(5D), 6-31G**(6D), and 6-31G(2 × 6D) basis sets. Comparisons are made with a microwave substitution structure and with results of other ab initio calculations reported in the literature. Particular attention is paid to the influence of polarization functions on the magnitude of the ring angle, 〈C6N1C2, which is analogous to the ipso angle in monosubstituted benzene derivatives.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/jcc.540070208
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  • 14
    Digitale Medien
    Digitale Medien
    Spatially constrained minimization of macromoleculesSupported in part by grants from the national science foundation and the national institutes of health. (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 7 (1986), S. 165-175 
    Details
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: A structural minimization procedure which converges rapidly and restricts the atomic shifts is outlined. It is implemented by adding a harmonic penalty term for the displacements of atomic positions and resetting the reference coordinates with respect to which the constraints are computed during the minimization. The resetting serves to reduce the constraint energy of the minimized structure to negligible levels.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/jcc.540070210
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  • 15
    Digitale Medien
    Digitale Medien
    Conformational study of the trinucleotide CpGpCp-pentapeptide Gly5 complex: The important role of bridging water in the complex formation (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 7 (1986), S. 189-200 
    Details
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: Conformational changes in the RNA-protein interaction were studied by calculating the intramolecular interaction energy of a model complex with the use of potential functions. The model complex has hydrogen-bonded water molecules bridging polypeptide NH groups to 2'-hydroxyl groups and sugar ring oxygen atoms. Since the sugar ring is constrained by the bridging water, preliminary calculations with the model compounds, the sugar ring, mononucleoside diphosphates, pCp and pGp, were carried out, and the flexibility and energetics of the sugar ring were compared with the previous results of DNA. The shift of the phase angle of the sugar ring occurred in the complex formation because of the hydrogen bond through the bridging water and the flexibility of the sugar ring. The free energy difference at 298 K is about -74.0 kcal/mol which was obtained from the intramolecular interaction energy difference of -67.5 kcal/mol by adding the conformational entropy change of 21.9 e.u., which in turn was calculated from the evaluation of the determinant of the matrix containing variances and covariances of the internal coordinates.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/jcc.540070212
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  • 16
    Digitale Medien
    Digitale Medien
    Matrix elements for anharmonic potentials: Application to I2 morse oscillator (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 7 (1986), S. 208-212 
    Details
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: Many authors have contributed expressions for obtaining analytical matrix elements for Morse oscillators. In this work, we discuss the advantages of using these expressions. At the same time, we propose a full numerical method to calculate these matrix elements and we compare, for the I2 system, the different results given by Gallas, Vasan, and Cross, and the variational method.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/jcc.540070214
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  • 17
    Digitale Medien
    Digitale Medien
    Masthead (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 7 (1986) 
    Details
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/jcc.540070401
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  • 18
    Digitale Medien
    Digitale Medien
    MINDO/3 Study of the Rearrangement of 1-Methylcyclohexyl Cation to 1,2-Dimethylcyclopentyl Cation (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 7 (1986), S. 417-427 
    Details
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: The rearrangement of the 1-methylcyclohexyl cation to the 1,2-dimethylcyclopentyl cation has been studied by MINDO/3 calculations, as an application of the branching mechanism model for cycloalkanes. Possible intermediates and transition states have been characterized by diagonalization of their Hessian matrixes. Two nonequivalent pathways, α and β scissions, are relatively close in energy. The calculated transition states are almost equivalent in energy to those found for cyclohexyl cation. Hence, the energy barriers are higher for the rearrangement of the 1-methyl than for cyclohexyl cation, because the former is less stable than the latter.
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/jcc.540070405
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  • 19
    Digitale Medien
    Digitale Medien
    Transport Properties of Macromolecules by Brownian Dynamics Simulation: Vectorization of Brownian Dynamics on the Cyber-205 (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 7 (1986), S. 457-463 
    Details
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: Time consuming portions in the computation of transport properties of rigid and flexible molecules are the evaluation of subunit hydrodynamic interaction tensors Q and σ, and the procedure for satisfying subunit-subunit distance constraints. Vector algorithms to speed up these parts of the computation are given. Using these algorithms, a vector version of the Ermak-McCammon Brownian dynamics code has been developed on a Cyber-205. To demonstrate the order of speedups that can be achieved, the code was tested on a rigid “trimer” system comprising 24 spherical subunits with a fixed geometry. A speedup of about 14 times for the whole program, and of 45, 6, and 18 times for the computation of Q, σ, and for the procedure to enforce the constraints, respectively, were obtained.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/jcc.540070408
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  • 20
    Digitale Medien
    Digitale Medien
    On the Use of Constraints in Molecular Mechanics. Rigid Group Refinement (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 7 (1986), S. 476-481 
    Details
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: It is shown how the refinement of groups of atoms as rigid entities can be implemented in a molecular mechanics program. The method is worked out for the Newton-Raphson scheme and eventually combined with other constraints, including the Eckart conditions. An example is also given.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/jcc.540070410
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  • 21
    Digitale Medien
    Digitale Medien
    Optimization of the Generalized Valence Bond Method for Vector ProcessorsWork performed under the auspices of the Office of Basic Energy Sciences, Division of Chemical Sciences, U. S. Department of Energy, under Contract W-31-109-Eng-38. (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 7 (1986), S. 500-512 
    Details
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: The Generalized Valence Bond [GVB(pp)] multiconfiguration self-consistent field wave function optimization program has undergone substantial revision in migration from serial scalar computers (like IBM and VAX) to the FPS-164, a minisupercomputer. Many of the code optimization strategies applied to the GVB program are portable and applicable to a wide range of scientific application codes. In benchmark calculations, the optimized FPS-164 program, GVB164, is 6.5 times faster than the initial FPS-164 implementation, both programs storing the two-electron integral list on disk. GVB164 runs 30 times faster in wall time (limited by the FPS-164 disk access speed) than a reference version of GVB2P5 on the VAX 11/780. The performance of GVB164 nearly doubles again when all of the two-electron integrals can be stored in main memory.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/jcc.540070413
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  • 22
    Digitale Medien
    Digitale Medien
    Masthead (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986) 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180101
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  • 23
    Digitale Medien
    Digitale Medien
    Hydrogen abstraction by hydrocarbon radicals. I. Interactions between 1-phenyl ethyl radicals and 1-phenyl ethanol as well as benzyl alcohol (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 31-40 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Hydrogen abstraction by 1-phenylethyl radicals (ṘH) from phenylmethyl-carbinol (HROH) and benzyl alcohol (H2R′OH) has been studied in the liquid phase at 120°C. 1-Phenylethyl radicals have been generated by thermal decomposition of azo-bis-1-phenyl ethane and the formation of ethylbenzene (RH2), acetophenone (RO), and 2,3-di-phenyl butane (R2H2) has been monitored during the reaction.In order to optimize the experimental conditions, a mechanism has been assumed for the various pathways of the disappearance of ṘH and by using estimated rate parameters a presimulation was performed.The relative rate constants obtained are: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {\frac{{k_{\rm H} }}{{\sqrt {{\rm 2}k_t } }} = 1.4{\rm } \times {\rm }10^{ - 4} {\rm L}^{1/2} {\rm mol}^{ - 1/2} {\rm s}^{ - 1/2} } & {{\rm for}} & {{\rm HROH}} \\ \end{array} $$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {\frac{{k_{\rm H} }}{{\sqrt {{\rm 2}k_t } }} = 1.0{\rm } \times {\rm }10^{ - 4} {\rm L}^{1/2} {\rm mol}^{ - 1/2} {\rm s}^{ - 1/2} } & {{\rm for}} & {{\rm H}_{\rm 2} {\rm R'OH}} \\ \end{array} $$\end{document} where kH refers to the hydrogen abstraction while kt is the combination rate coefficient of the radicals ṘH.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180104
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  • 24
    Digitale Medien
    Digitale Medien
    A reevaluation of low temperature experimental rate data for the reactions of O atoms with methane, ethane, and neopentane (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 59-82 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The experimental data for the reactions of oxygen atoms with methane, ethane, and neopentane at temperatures below ca. 600 K have been reexamined. In the case of CH4 and C2H6 reactions, detailed computer models have been assembled to test the assumptions regarding stoichiometries that were made in the original studies in order to derive elementary rate coefficients from the experimentally observed reaction rates. It was found in both cases that the measurements are especially sensitive to secondary reactions not taken into account and impurities in the reagent alkane. Because the original reports did not include sufficient experimental details, it is not now possible to correct their results quantitatively. However, it appears, qualitatively, that the values for the O + CH4 and O + C2H6 rate coefficients were overestimated by factors of approximately 2 to 3 in the 250-400 K temperature range, with the error increasing as T decreases. Although the experimental results for the O + neopentane reaction are not as sensitive to the same kinds of complications, a comparison of the low-temperature measurements with those for the O + ethane reaction suggests that the previously recommended rate coefficients, based on the data of Herron and Huie, are probably also too high by a factor of 2 to 3.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180107
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  • 25
    Digitale Medien
    Digitale Medien
    Determination of absolute rate data for the reactions of atomic sodium, Na(32S1/2), with CH3F, CH3Cl, CH3Br, HCl, and HBr as a function of temperature by time-resolved atomic resonance spectroscopy (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 83-98 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We present a kinetic study of the reactions of ground-state sodium atoms with the molecules CH3F, CH3Cl, CH3Br, HCl, and HBr at elevated temperatures (537-966 K). Na(32S1/2) was generated by the pulsed irradiation of various sodium halide vapors and monitored by time-resolved atomic resonance absorption of the unresolved D-lines at λ = 589 nm [Na(32PJ) ← Na(32S1/2)] in the “single-shot mode.” The photoelectric signals were amplified without distortion, captured, and digitized in a transient recorder interfaced to a microcomputer for data analysis. Absolute second-order rate constants were measured at various temperatures in each case, yielding the following Arrhenius parameters (kRX = A exp(-E/RT), errors 1σ): which constitute, to the best of our knowledge, the first direct measurements of these quantities. The reaction between Na and HBr demonstrated anomalous behaviour which is discussed in terms of potential surfaces that have been calculated previously for this type of collisional process. The data are compared with analogous results for Na + CF4, CF3Cl, and CF3Br and with single-temperature measurements on diffusion flames.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180108
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  • 26
    Digitale Medien
    Digitale Medien
    Rate constants for the decarboxylation of the t-butoxicarbonyl radical and concurring radical terminations directly obtained by kinetic ESR (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 145-158 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Rate constants of various simultaneous reactions of t-butoxicarbonyl and t-butyl radicals generated by photolysis of t-butylpivalate in n-heptane are directly determined by kinetic electron spin resonance. The temperature dependence of the decarboxylation reaction t-BuOĊO → t-Bu. + CO2 obeys log )K/S-1( = 13.8-49.0/θ where θ = 2.303 RT/kJ . mol-1. The self- and cross-termination of the radicals are diffusion limited.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180202
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  • 27
    Digitale Medien
    Digitale Medien
    Masthead (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986) 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180301
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  • 28
    Digitale Medien
    Digitale Medien
    Linearization of second-order reaction data (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 281-286 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Reaction data described by the second-order growth function A(t) = A∞(αt) (1 + αt)-1, where A∞ is the ultimate value of the product concentration A(t), can be linearized by plotting a suitable function F(t) against the time (t). The slope of the straight line obtained is (2α), where α is the product of the rate constant (k2) and the initial concentration of either reactant, with the result that k2 can be determined without knowledge of Aϰ. Optimal determination of the parameter α requires that data taking be limited to the interval 0 ≤ t ≤ T, where (αT) is approximately 4.0. Numerical data derived from an experiment on the exchange of lead by zinc ions in the enzyme carbonic anhydrase are analyzed to illustrate the method. The effects of small errors in the initial concentrations and of small deviations from second-order kinetics are briefly discussed.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180302
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  • 29
    Digitale Medien
    Digitale Medien
    Effects of nonionic, cationic, and anionic micelles on the kinetics of the complexation reaction of nickel (II) with pyridine-2-azo-p-dimethylaniline (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 609-621 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The stopped-flow technique has been used to study the effect of cationic (CTAN), nonionic (Triton X-100), andanionic (SDS) micelles on the rate of the reaction between nickel(II) ion and the ligand pyridine-2-azo-p-dimethylaniline (PADA) at 20.0°C and ionic strength 0.03 mol dm-3. The complex formation reaction is markedly inhibited by both CTAN and Triton X-100 micelles. The kinetic dataare found to conform to a reaction mechanism which implies only partitioning of the ligand between water and the micellar phase, the estimated bindingconstant of PADA being significantly larger in the presence of CTAN aggregates. Anionic micelles strongly speed the complexation reaction, Which occurs in the micellar phase with the same rate and the same mechanism as in water. The extent of binding of PADA to anionic micelles is similar to that found for the cationic micellar aggregates.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180602
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  • 30
    Digitale Medien
    Digitale Medien
    Erratum (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 719-720 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180609
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  • 31
    Digitale Medien
    Digitale Medien
    Kinetics and mechanism of the oxidation of primary alcohols by sodium N-chloroethylcarbamate (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 689-699 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The oxidation of primary alcohols by sodium N-chloroethylcarbamate in acid solution, results in the formation of corresponding aldehydes. The reaction is first order with respect to the oxidant and alcohol. The rate increases with an increase in acidity. The oxidation of α,α-dideuterioethanol exhibited a primary kinetic isotope, kH/kD = 2.11 at 298 K. The value of solvent isotope effect k(H2O)/k(D2O) = 2.23 at 298 K. Addition of ethyl carbamate does not affect the rate. (EtOC(OH)NHCl)+ has been postulated as the reactive species. Plots of (log k2 + Ho) against (Ho + log[H+]) are linear with the slope, φ, having values from 1.78-1.87. This suggested a proton abstraction by water in the rate-determining step. The rates of oxidation of alcohols bearing both electron-withdrawing and electron-donating groups are more than that of methanol. A concerted mechanism involving transfer of a hydride ion from the C—H bond of the alcohol tothe oxidant and removal of a proton from the O—H group by a water molecule has been proposed.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180607
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  • 32
    Digitale Medien
    Digitale Medien
    Theory of fast multiple bond-switching reactions: NO + NH2 (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 721-737 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A theoretical treatment is given for fast, multiple bond-switching reactions, such as NO + NH2 → N2 + H2O. These reactions are characterized by all or most of the bonds being broken. The collision complex involved (whether long or short lived) is shown to be extremely anharmonic. Consideration of the master equation describing the competing processes of complex formation, internal rearrangement and collisional deactivation yields easily applied sufficient conditions for the recombination rate coefficient being independent of pressure.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180702
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  • 33
    Digitale Medien
    Digitale Medien
    Kinetic analysis of the disproportionation of aqueous glyoxal (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 757-773 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Rates of disproportionation of 0.015-0.4 mM aqueous glyoxal toglycolic acid were measured at 0.24-75 mM NaOH and constant ionic strength, leading to the empirical rate expression r = (a1[OH-] + a2[OH-]2) [GT]/(1 + a3[OH-]), where [GT] is the total glyoxal concentration. These results were confirmed in bicarbonate/carbonate buffer and at 2-20 mM [GT]. The rate form is in contradiction to earlier work on glyoxal, which suggested a second-order dependence on [OH-], but agrees with the rate equation for phenylglyoxal disproportionation. The kinetic data can be explained by a mechanism postulating the presence of monohydrated and dihydrated forms of glyoxal in equilibrium, with the rate-limiting steps being intramolecular hydride ion transfers to the unhydrated carbonyl carbon of the mono- and divalent anions of glyoxal monohydrate.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180704
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  • 34
    Digitale Medien
    Digitale Medien
    Stopped-flow investigations of the reaction kinetics of carbon dioxide with some primary and secondary alkanolamines in aqueous solutions (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 445-457 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The reaction kinetics of carbon dioxide with four alkanolamines of industrial importance (MEA, DGA, DEA, and DIPA) have been investigated with the aid of the stopped-flow technique, allowing the determination of rate constants for carbamates formation. The constants obtained for MEA at 20°C and 25°C are in good agreement with recent literature data. The kinetic behavior of DGA was found to be almost identical to that of MEA.The rate constants obtained for DIPA at 25°C (54 M-1 s-1) is half as large as that for DEA (110 M-1 s-1). The former one is satisfactorily compared with the recent values proposed by Blauwhoff et al. Activation energies have also been obtained for DEA (23.2 kJ mol-1) and for DIPA (58.7 kJ mol-1) and their mechanistic implications are discussed in relation with the relevanceof a rate-determining proton transfer step in the process of carbamate formation.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180404
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  • 35
    Digitale Medien
    Digitale Medien
    Kinetics and mechanism of the pyrolysis of 1-Chloro-1, 1-difluoroethane in the presence of chlorine (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 497-504 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The first stage thermal reactions of CF2CICH3 in the presence of chlorine have been studied between 554 and 614 K. These are and \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CF}_{\rm 2} {\rm CICH}_{\rm 3} {\rm + CI}_{\rm 2} \to {\rm CF}_{\rm 2} {\rm CICH}_{\rm 2} {\rm CI + HCI} $$\end{document} Rate equations derived from a radical mechanism are shown to fit the experimental results. Values of Arrhenius parameters for the decomposition of the CF2ClCH2. radical and its reactions with Cl2 and Cl are given.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180408
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  • 36
    Digitale Medien
    Digitale Medien
    Radical steps in diethyl ether decomposition (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 829-836 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The thermal decomposition of diethyl ether was studied in the temperature range 697.2-760.5 K. The rate constant of reaction (1), and the ratio of the rate constant of reaction (2) to that of (12): were calculated from the amounts of products: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_1 ({\rm s}^{{\rm - 1}}) = (17.2 \pm 0.6) - (82.4 \pm 2.0{\rm kcal mol}^{{\rm - 1}})/2.3RT $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_2 /k_{12^{1/2} } ({\rm dm}^{{\rm 3/2}} {\rm mol}^{{\rm - 1/2}}) = (4.1 \pm 0.4) - (11.9 \pm 1.3{\rm kcal mol}^{{\rm - 1}})/2.3RT $$\end{document}
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180803
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  • 37
    Digitale Medien
    Digitale Medien
    The chromatographic retention of H and D atoms on quartz (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 861-869 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The chromatographic retention of H and D atoms has been observed in a quartz tube using argon as a carrier gas for D and six different gases for H. The results give equilibrium constants for the reversible adsorption of H and D on quartz as well as the rates of desorption. Self-consistent conclusions can be drawn from the data. The adsorption energy appears to be ca. 50 kJ mol-1 indicating weak chemisorption. The observations are consistent with vibration frequencies on the surface of around 700-900 cm-1 for D. and around 1000-1300 cm-1 for H. It appears that only a fraction of the surface atoms (ca. 10-2) act as adsorption sites.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180806
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  • 38
    Digitale Medien
    Digitale Medien
    Measurements of the bimolecular rate constants for S + O2 → SO + O and CS2 + O2 → CS + SO2 at high temperatures (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 871-884 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The bimolecular reactions in the title were measured behind shock waves by monitoring the O-atom production in COS—O2—Ar and CS2—O2—Ar mixtures over the temperature range between 1400 and 2200 K. A value of the rate constant for S + O2 → SO + O was evaluated to be (3.8 ± 0.7) × 1012 cm3 mol-1 s-1 between 1900 and 2200 K. This was connected with the data at lower temperatures to give an expression k2 = 1010.85 T0.52 cm3 mol-1 s-1 between 250 and 2200 K. An expression of the rate constant for CS2 + O2 → CS + SO2 was obtained to be k21 = 1012.0 exp(-32 kcal mol-1/RT) cm3 mol-1 s-1 with an error factor of 2 between 1500 and 2100 K.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180807
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  • 39
    Digitale Medien
    Digitale Medien
    Masthead (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986) 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180901
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  • 40
    Digitale Medien
    Digitale Medien
    Preface (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. vi 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180902
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  • 41
    Digitale Medien
    Digitale Medien
    The kinetics and the mechanism of the thermal gas-phase reaction between NO2 and 1,1-dichlorodifluoroethylene, CF2CCl2 (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 907-917 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The kinetics of the gas phase reaction between NO2 and CF2CCl2 has been investigated in the temperature range from 50 to 80°C. The reaction is homogeneous. Three products are formed: O2NCF2CCl2NO2 and equimolecular amounts of CINO and of O2NCF2C(O)Cl. The rate of consumption of the reactants is independent of the total pressure, the reaction products, and added inert gases and can be represented by a second-order reaction: \documentclass{article}\pagestyle{empty}\begin{document}$$ - \frac{{d[{\rm NO}_{\rm 2}]}}{{dt}} = - 2\frac{{d[{\rm CF}_{\rm 2} {\rm CCI}_{\rm 2}]}}{{dt}} = k[{\rm NO}_{\rm 2}][{\rm CF}_{\rm 2} {\rm CCI}_{\rm 2}] $$\end{document}However, the distribution of the products is influenced by the pressure of the present gases, which favor the formation of the dinitro-compound in a specific way. The effect of CF2CCl2 is the greatest. In the absence of added gases, the ratio of O2NCF2CCl2NO2 to that of O2NCF2C(O)Cl is proportional to (CF2CCl2 + γP products).The experimental results can be explaned by the following mechanism: P and X represent the products and the added gases: \documentclass{article}\pagestyle{empty}\begin{document}$$ - \frac{{d[{\rm NO}_{\rm 2}]}}{{dt}} = - 2\frac{{d[{\rm CF}_{\rm 2} {\rm CCI}_{\rm 2}]}}{{dt}} = k_1 [{\rm NO}_{\rm 2}][{\rm CF}_{\rm 2} {\rm CCI}_{\rm 2}] $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 = 3.16 \pm 0.5 \times 10^6 \exp ( - 10500 \pm 1000{\rm cal/}RT){\rm M}^{{\rm - 1}} {\rm s}^{{\rm - 1}} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm \gamma }_{{\rm CF}_{\rm 2} {\rm CCI}_{\rm 2} } :{\rm \gamma }_P :{\rm \gamma }_{{\rm C}_{\rm 2} {\rm F}_{\rm 5} {\rm CI}} :{\rm \gamma }_{{\rm CCL}_{\rm 3} } :{\rm \gamma }_{{\rm CF}_{\rm 4} } :{\rm \gamma }_{{\rm N}_{\rm 2} } = 1:0.22:0.15:0.14:0.054:0.015 $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm \gamma }_{{\rm NO}_{\rm 2} } 〈 0.01 $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_3 = 1.4 \pm 0.3 \times 10^8 {\rm s}^{{\rm - 1}} $$\end{document}
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180810
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  • 42
    Digitale Medien
    Digitale Medien
    Masthead (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986) 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180701
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  • 43
    Digitale Medien
    Digitale Medien
    Base-catalyzed tritium exchange between tritium-containing heavy water and deuterated chloroform-kinetics and equilibrium (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 739-755 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We develop a kinetic model for the exchange of tritium and deuteriumbetween tritium-containing heavy water and deuterated chloroform in a two-phase liquid system, catalyzed by hydroxide ion (sodium hydroxide). For the exchange reaction yielding tritiated chloroform andheavy water, the measured equilibrium constant is 0.518 at 25-45°C, independent of temperature. The rate constant (for the controlling step, deuteron abstraction from chloroform) is 0.22 L/mol s at 25°C, 0.72 at 35°C, and 2.0 at 45°C, corresponding to an activation energy of 87 kJ/mol. Comparison is made with literature data, and effects of mass transfer on the apparent rate constant are discussed.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180703
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  • 44
    Digitale Medien
    Digitale Medien
    Thermodynamic and kinetic analysis of the dimerization of aqueous glyoxal (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 775-789 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Equilibria and rates of interconversion between monomeric and dimeric glyoxal were measured in aqueous solution. The equilibrium constant [G2]/[G1]2 was 0.56 M-1 at 25°C, and was hardly affected by changes of ionic strength and pH but increased rapidly with increase of temperature. The rate of depolymerization was first-order in dimer, with the pseudo first-order rate coefficient in the pH range 1.3-7.8being of the form b1[H3O+] + b2 + b3[OH-]/(1 + b4[OH-]) + b5[OH-]. Coefficients b1 and b2 were more strongly affected by changes of temperature, though [OH-] was much the more effective catalyst. This rate form has not previously been observed for monomer-dimer inter-conversion of α-hydroxycarbonyls and α-dicarbonyls or for related reactions such as mutarotations and hydrations. Equivalent rate forms arisefrom reactions where an intermediate at steady state and low concentration is produced.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180705
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  • 45
    Digitale Medien
    Digitale Medien
    Masthead (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986) 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180801
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  • 46
    Digitale Medien
    Digitale Medien
    Reaction of the NO3 radical with CO: Determination of an upper limit for the rate constant using FTIR spectroscopy (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 819-827 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: An upper limit for the reaction rate of CO with the nitrate radical NO3 has been determined equal to 4 × 10-19 cm+3 molec-1 s-1 at 295 ± 2 K. In the experiment the isotopic species C13O16 and C13O18 mixed at 1-2 ppmv level in synthetic air have been reacted with NO3 and the reaction followed using long path infrared absorption FT spectroscopy. The result is of interest in the studies on the role played by NO3 in nighttime tropospheric chemistry.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180802
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  • 47
    Digitale Medien
    Digitale Medien
    The reaction of OH radicals with dimethyl sulfide (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 837-846 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The kinetics of the gas phase reaction of OH radicals with dimethyl sulfide (CH3SCH3) have been studied at various temperatures and total pressures using two relative rate methods and a flash photolysis technique. For the relative rate methods, rate constants were measured at 296 ± 2 K as a function of the O2 pressure at a total pressure of ca. 740 torr. Data from these three experimental techniques were not in agreement. It is concluded that the relative rate techniques are subject to secondary reactions, possibly involving CH3S radicals. A rate constant of (2.5-0.6+0.9) × 10-12 e(130 = 102)/T cm3 molecule-1 s-1 obtained using the flash photolysis-resonance fluorescence data in the absence of O2, and which is in agreement with the lower range of values previously reported in the literature, is recommended.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180804
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  • 48
    Digitale Medien
    Digitale Medien
    Kinetics and mechanism of the OH + CIO2reaction (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 847-859 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The rate constant k1 for the reaction of OH radicals with CIO2 molecules was measured in a discharge flow system over the temperature range 293 ≤ T ≤ 473 K and at low pressures, 0.5 ≤ P ≤ 1.4 torr, using electron paramagnetic resonance or laser-induced fluorescence to monitor the pseudo first-order decay of OH concentrations. At 293 K, the value obtained for k1 was (7.2 ± 0.5) × 10-12 cm3 molecule-1 s-1. Within the temperature range of this study, a negative temperature dependence was observed: k1 = (4.50 ± 0.75) × 10-13 exp[(804 ± 114)/T] cm3 molecule-1 s-1. HOCl was detected by mass spectrometry as a product of the reaction and was titrated using OH + Cl2 as a source in the calibration experiments. A simulation of the mechanism of the OH + ClO2 reaction indicated that HOCl was mainly produced in the first reaction step. Both this result and the observed T dependence of k1 suggest that this reaction proceeds via an intermediate adduct with a cyclic geometry.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180805
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  • 49
    Digitale Medien
    Digitale Medien
    Dynamical stereochemistry of the hydrogen exchange reaction: A computational study (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1023-1045 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The barrier for the hydrogen exchange reaction increases with the bend angle of H3. The implications for the dynamics of the reaction are explored on two levels. The static one uses the concept of a relaxed potential. This provides for a convenient, yet realistic representation. Itallows for the response of the molecule to the approaching atom. Among features made very evident by the relaxed potential is the possibility that hotH atoms can react by insertion. It also shows the widening of the cone of acceptance upon reagent vibrational excitation. On the dynamical level, classical trajectory computations are used to illustrate the dependence of the reactivity on the angle of attack and on the translational and vibrational excitation of the reagents. Detailed product distributions are generally not sensitive to the attack angle. An exception is the HD/H2 branching ratio in H + HD reactive collisions.
    Zusätzliches Material: 13 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180911
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  • 50
    Digitale Medien
    Digitale Medien
    Oxidation of benzyl alcohols by nitrous and nitric acids in strong sulfuric acid media (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1277-1288 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We have studied the oxidation of benzyl alcohols by nitrous and nitric acid in sulfuric acid media. The oxidation by nitrous acid is rapid and has an activation energy of 10.6 ± 0.8 kcal mol-1. A Hammett plot of logk2 vs. σ+ is linear with a ρ value of -1.4. The oxidation by nitric acid in sulfuric acid media is autocatalytic. From the kinetic and product analyses, it is concluded that a common oxidant, the nitrosonium ion is involved when either nitrous or nitric acid is used. A mechanism is proposed which involves the abstraction of hydride from the alcohols as the rate determining step. It is demonstrated that the autoxidation of the alcohols is catalyzed by nitrous acid or nitric oxide.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550181106
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  • 51
    Digitale Medien
    Digitale Medien
    Rate constant of OH + OCS reaction over the temperature range 255-483 K (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1303-1314 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The rate constant of the reaction between OH and OCS in helium over the temperature range 255-483 K has been determined using the discharge flow-resonance fluorescence technique. The OCS has been carefully purified to avoid interference from H2S and CO impurities. An FTIR with a multireflection cell was used to determine the impurity concentrations and the purified sample was found to contain less than 0.005% of H2S. At 300 K, the rate constant was determined to be (2.0 ±0.40.8) × 10-15 cm3 molecule-1 s-1. Although the rate constants showed slight positive deviation at lower temperatures, thev can be satisfactorily fitted by the Arrhenius equation, k = 1.13 × 10-13 exp(-1200/T) cm3 molecule-1 s-1. No pressure dependence was observed at all temperatures, nor was O2 enhancement observed under our experimental conditions.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550181202
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  • 52
    Digitale Medien
    Digitale Medien
    Gas phase thermal isomerization of 4-acetyl-5-methyl-isoxazole (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1333-1340 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The gas phase thermal isomerization of 4-acetyl-5-methyl-isoxazole affords 3-cyano-2,4-pentanedione as the only product in good agreement with previous proposed isomerization mechanism for isoxazoles. On the other hand, kinetic parameters and MO theoretical calculations do not agree with those previously reported. An alternative reaction mechanism which explains this fact is discussed.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550181205
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  • 53
    Digitale Medien
    Digitale Medien
    Infrared laser-induced decomposition of 2,2-dimethyloxetane (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1215-1234 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The unimolecular decomposition of 2,2 dimethyloxetance to give either isobutence and formaldehyde or ethene and acetone induced by a pulsed CO2 laser has been investigated. Absorption characteristics and fractional decomposition have been studied as a function of laser fluence, irradiation frequency, reactant pressure, and added inert bath gas. Both absorption cross section and fractional decomposition are approximately independent of pressure of 2,2-dimethyloxetane below 50 times; 10-3 torr and increase with pressure at higher pressures of 2,2-dimethyloxetane. At pressures sufficiently low that collisions are negligible during the laser pulse, added inert gases reduce the amount of decomposition. Calculations of the fractional decomposition have been carried out based on RRKM theory and assuming either a Boltzmann or a Poisson intermolecular energy distribution. Master equation calculations of both absorption and decomposition for 10R20 irradiation have also been performed. Agreement between observed and calculated results for 10R20 irradiation could be obtained only by assuming that most, but not all, of the molecules in the irradiated volume absorb the laser radiation. Differences between the absorptions of the 10R20 and 9P20 lines and in the resulting extents of decomposition indicate that the fraction of irradiated molecules which absorbs 9P20 radiation is smaller than the fraction which absorbs 10R20 radiation.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550181102
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  • 54
    Digitale Medien
    Digitale Medien
    Masthead (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986) 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550181201
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  • 55
    Digitale Medien
    Digitale Medien
    Kinetics of the oxidation of nitric oxide by chlorine and oxygen in nonaqueous media (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1289-1302 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The kinetics of the reaction between nitric oxide and chlorine have been investigated in both carbon tetrachloride and glacial acetic acid. The nitric oxide-oxygen reaction has been investigated in carbon tetrachloride.The appearance of product, NOCl or NO2, was monitored spectrophotometrically at a wavelength of 475 nm for NOCl and 343 nm for NO2. These measurements were performed using an Amino-Morrow stopped-flow apparatus equipped with a Beckman D U monochromator.The data for both the NO—Cl2 and NO—O2 systems could be fitted to the third-order integrated equation and the calculated rate constants were 2.75 × 103 M-2 s-1 and 2.79 × 106 M2 s-1, respectively, at 25.1°C.There was a noted increase in rate constants on changing the solvent from carbon tetrachloride to acetic acid.The likelihood of a termolecular encounter is inherent in the mechanism, however, no real evidence to substantiate either a direct termolecular or a series of two bimolecular steps has been obtained, although a -7 kcal for ΔH0 would support the latter.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550181107
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  • 56
    Digitale Medien
    Digitale Medien
    Rates and mechanisms of oxidation of ZnTPP by CCI3O2 radicals in various solvents (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1315-1321 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Trichloromethylperoxyl radicals were produced by pulse radiolysis of air saturated solutions containing CCl4. The rate constants for the reaction of CCl3O2 radicals with zinc tetraphenylporphyrin (ZnTPP) were determined in various solvents. They were found to vary between 3 × 107 and 3 × 109 M-1 s-1. The changes in rate constants result from complexation of ZnTPP with the different solvents, but did not correspond to changes in redox potential of ZnTPP. The rate constants were found to depend on the strength of the axial complexation, indicating an inner sphere mechanism whereby the radical binds to the metal prior to electron transfer.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550181203
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  • 57
    Digitale Medien
    Digitale Medien
    The kinetics and the mechanism of the thermal gas-phase reaction between bis(trifluoromethyl)trioxide, CF3O3CF3 and 1,1-dichlorodifluoroethylene, CF2CCI2 (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1323-1331 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The thermal addition of CF3O3CF3(T) to CF2CCl2(E) has been investigated between 49.6 and 69.5°C. The initial pressure of CF3O3CF3 was varied between 7 and 240 torr and that of CF2CCl2 between 4 and 600 torr. Four products of formula CF3O(E)j OOCF3, where j = 1 → 4 are formed. The sum of the products Σi = 14 CF3O(E)jOOCF3 is equal to the amount of trioxide decomposed.The reaction is homogeneous. Its rate is not affected by the total pressure and the presence of inert gas. It is a free radical telomerization with four basic steps: thermal decomposition of CF3O3CF3 into CF3O. and CF3O2., chain initiation by addition of CF3O. to olefin incorporated in, and telomeric radicals termination.The consumption of alkene is well represented by the equation: \documentclass{article}\pagestyle{empty}\begin{document}$$ - d[E]/dt = k_1 [T]\left\{ {1 + \sum\limits_{j = 1}^3 {\prod\limits_{i = 1}^j {[1 + (k_{t_1 } k_1^{1/2} /k_{gi} } k_t^{1/2})([T]^{1/2} /[E])]^{ - 1} } } \right\} $$\end{document} where (d[E]/d[T]) = \documentclass{article}\pagestyle{empty}\begin{document}$$ \bar n $$\end{document} is the mean chain length of telomerization. \documentclass{article}\pagestyle{empty}\begin{document}$$ \bar n $$\end{document} varies from 1.45 at 1.5 torr of E to 3.3 at 400 torr of E. Above this pressure E has no influence on \documentclass{article}\pagestyle{empty}\begin{document}$$ \bar n $$\end{document}.The estimated value of the constant for the addition of telomeric radicals to alkene is:\documentclass{article}\pagestyle{empty}\begin{document}$$ k_g \simeq 8.6 \pm 6.0 \times 10^4 \exp ( - 2300 \pm 200{\rm col mol}^{{\rm - 1}} /RT){\rm M}^{{\rm - 1}} {\rm s}^{{\rm - 1}} $$\end{document}
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550181204
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  • 58
    Digitale Medien
    Digitale Medien
    Effect of olefins on the thermal decomposition of propane part I. The model reaction (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 227-239 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Study of the thermal decomposition of propane at very low conversions in the temperature range 760-830 K led to refinement of the mechanism of the reaction.The quotient VCH4 + C2H4/VH2 + C3H6 characterizing the two decomposition routes connected with the 1- and 2-propyl radicals proved to depend linearly on the initial propane concentration. This suggested the occurrence of intermolecular radical isomerization: in competition with decomposition of the 2-propyl radical: The linearity led to the conclusion that the selectivity of H-abstraction from the methyl and methylene groups by the methyl radical is practically the same as that by the H atom. The temperature-dependence of this selectivity ( μ = kCH3/kCH2) was given by\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm \mu = }\frac{{k_3 }}{{k_4 }} = \frac{{k_1 }}{{k_2 }} = 10^{0.26 \pm 0.03} \exp ( - 7.24 \pm 0.45{\rm kJ mol}^{{\rm - 1}} /RT). $$\end{document} Further evaluation of the dependence gave the Arrhenius representation \documentclass{article}\pagestyle{empty}\begin{document}$$ \frac{{k_7 }}{{k_6 }} = 10^{ - 5.97 \pm 0.03} \exp (115 \pm 5.1{\rm kJ mol}^{{\rm - 1}} /RT){\rm mol}^{{\rm - 1}} {\rm dm}^{\rm 3} $$\end{document} for the ratio of the rate coefficients of the above isomerization and decomposition reactions.Steady-state treatment resulted in the rate equation of the process, comparison of which with measurements gave further Arrhenius dependences.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180208
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  • 59
    Digitale Medien
    Digitale Medien
    Effects of olefins on the thermal decomposition of propane part III. Some remarks on the kinetics of decomposition (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 255-265 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Conditions of applicability of quasi-steady-state kinetic treatment have been investigated with respect to the explanation of the decomposition of propane and the influence of ethylene on this.From the measured rate of accumulation of ethane and from the relations between the kinetic equations describing product formation, the rate parameters of the initiation reactions were determined, for which the temperature-dependences \documentclass{article}\pagestyle{empty}\begin{document}$$ k_i = 10^{17,05 \pm 0.99} \exp ( - 356 \pm 11{\rm kJmol}^{{\rm - 1}} /RT)s^{ - 1} $$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{ie} = 10^{12.0 \pm 0.99} \exp ( - 225 \pm 15{\rm kJmol}^{{\rm - 1}} /RT){\rm mol}^{{\rm - 1}} {\rm dm}^{\rm 3} s^{ - 1} $$\end{document} were found.In the decomposition of propane under the examined conditions, the chain length exceeds 500. In response to ethylene the chain length significantly decreases, but even in this case the decomposition chains are long enough for it to be assumed that the ratios of radical concentrations are governed by the propagation steps.Calculations demonstrated that the actual radical concentration during a sufficiently short induction period approximates to the stationary concentration, so that it does not seriously affect the accuracy of the kinetic treatment.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180210
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  • 60
    Digitale Medien
    Digitale Medien
    Reaction of CF3 radicals with C2H6 (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 437-443 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The hydrogen transfer reaction between C2H6 and CF3 radicals, generated by the photolysis of CF3I, has been studied in the temperature range 298-617 K. The rate constant, based on the value of 1013.36 cm3 mol-1 s-1 for the recombination of CF3 radicals, is given by \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_2 = (11.90 \pm 0.09) - (33230 \pm 740)/19.145T $$\end{document} where k2 is in cm3 mol-1 s-1 and E is in J mol-1. These results are compared with those previously reported, and the following best value for k2 is recommended: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_2 = (11.94 \pm 0.07) - (33670 \pm 540)/19.145T $$\end{document}
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180403
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  • 61
    Digitale Medien
    Digitale Medien
    The influence of the effective potential on the strong collision limiting low-pressure rate coefficients (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 459-472 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The influence of the effective potential energy curves on the calculation of the strong collision limiting low-pressure rate coefficients of thermal dissociation-recombination reactions was analyzed in terms of the factorized formalism of Troe. An analysis of 26 reactions employing a Morse potential coupled with a quasitriatomic molecular model and an explicit account of the adiabatic zero-point barriers, as originallyproposed by Troe, was performed. A comparison between calculations realizedwith an exactly fitted looseness parameter, α, and with a standard value of α = 1.0 Å-1, indicates that the use of this last value is satisfactorily justified in the evaluation of thestrong collision limiting low-pressure rate coefficients. A study interms of restrictive relationships between the looseness and Morse parameters and ab initio, radial potentials (for CH4, CH3O2, and HO2) was also realized. The uncertainties in the evaluation of termolecular rate coefficients due to the lack of a complete knowledge of the long-range potentials are also briefly discussed.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180405
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  • 62
    Digitale Medien
    Digitale Medien
    Kinetics of the gas phase reaction of OH radicals with pyrrole and thiophene (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 487-496 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Absolute rate constants for the gas phase reaction of OH radicals with pyrrole (k1) and thiophene (k2) have been measured over the temperature ranges 298-440 and 274-382 K, respectively, using the flash photolysis-resonance fluorescence technique. The rate constants obtained were independent of the total pressure of argon diluent over the range 25-100 torr andwere fit by the Arrhenius expressions \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 = (2.7 \pm _{0.6} ^{0.8}) \times 10^{ - 11} \exp [(403 \pm 93)/T]{\rm cm}^{\rm 3} {\rm molecule}^{{\rm - 1}} {\rm s}^{{\rm - 1}} $$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$$ k_2 = (1.2_{ - 0.6} ^{ + 1.0}) \times 10^{ - 12} \exp [(584 \pm 217)/]{\rm cm}^{\rm 3} {\rm molecule}^{{\rm - 1}} {\rm s}^{{\rm - 1}} $$\end{document} with rate constants at 298 ± 2 K of k1 = (1.03 ± 0.06) × 10-10 cm3 molecule-1 s-1 and k2 = (8.9 ± 0.7) × 10-12 cm3 molecule-1 s-1. [These errors represent two standard deviations (systematic errors could constitute an additional ca. 10% uncertainty)]. These results are discussed with respect to the previous literature data and the atmospheric lifetimes of pyrrole and thiophene.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180407
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  • 63
    Digitale Medien
    Digitale Medien
    Kinetics of the solvolysis of the trans-dichlorobis(1,2-diaminoethane)-cobalt(III) Ion in water + urea mixtures (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 529-536 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Following the kinetic investigation of the solvolysis of a range of cobalt(III) complexes in mixtures of water + cosolvent wherethe cosolvent enhances the solvent structure and decreases the dielectric constant, kinetic data are now reported for such a solvolysis in water + urea where urea acts as a structure breaker and enhances the dielectric constant. A plot of log (rate constant) against reciprocal of the dielectric constant shows that differential effects of changes in solvent structure occur between the initial and the transition states and, as in theinvestigations using structure-enhancing cosolvents, the principal effect of change in solvent structure on the cobalt(III) cation occurs on the penta-coordinated ion in the transition state.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180503
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  • 64
    Digitale Medien
    Digitale Medien
    Rate constants and kinetic isotope effects for hydrogen/deuterium abstraction by chlorine atoms from the chloromethyl group in CH2ClCH2Cl, CD2ClCD2Cl, CH2ClCHCl2, and CH2ClCDCl2 (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 513-527 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The abstraction of hydrogen and deuterium from 1,2-dichloroethane, 1,1,2-trichloroethane, and two of their deuterated analogs by photochemically generated ground state chlorine atoms has been investigatedin the temperature range 0-95°C using methane as a competitor. Rate constants and their temperature coefficients are reported for the following reactions Over the temperature range of this investigation an Arrhenius law temperature dependence was observed in all cases. Based on the adopted rate coefficient for the chlorination of methane [L.F. Keyser, J. Chem. Phys., 69, 214 (1978)] \documentclass{article}\pagestyle{empty}\begin{document}$$ k_r /{\rm cm}^{\rm 3} {\rm s}^{{\rm - 1}} = (1.65 \pm 0.32) \times 10^{ - 11} \exp [ - (1530 \pm 68)/T] $$\end{document} which is commensurate with the present temperature range, the following rate constant values (cm3 s-1) are obtained: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 = (4.93 \pm 0.96) \times 10^{ - 11} \exp [ - (1087 \pm 68)/T] $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_2 = (2.92 \pm 0.57) \times 10^{ - 11} \exp [ - (1362 \pm 68)/T] $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_3 = (2.39 \pm 0.57) \times 10^{ - 11} \exp [ - (1750 \pm 68)/T] $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_4 = (1.68 \pm 0.33) \times 10^{ - 11} \exp [ - (1965 \pm 68)/T] $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_5 = (1.22 \pm 0.24) \times 10^{ - 11} \exp [ - (1948 \pm 68)/T] $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_6 = (1.47 \pm 0.28) \times 10^{ - 11} \exp [ - (1910 \pm 68)/T] $$\end{document} The observed pure primary, and mixed primary plus α- and β3-secondary kinetic isotope effects at 298 K are k3/k6 = 2.73 ± 0.08, and k1/k2 = 4.26 ± 0.12, respectively. Both show a normal temperature dependence decreasing to k3/k6 = 2.39 ± 0.06 and k1/k2 = 3.56 ± 0.09 at 370 K. Contrary to some simple theoretical expectations, the kinetic isotope effect for H/D abstraction decreases with increasing number of chlorine substituents in the geminal group in a parallel manner to the trend established previously for C1-substitution in the adjacent group. The occurrence of a β-secondary isotope effect, k4/k5, is established; this effect suggests a slight inverse temperature dependence.
    Zusätzliches Material: 7 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180502
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  • 65
    Digitale Medien
    Digitale Medien
    High temperature kinetics of the thermal decomposition of the lower alkanoic acids (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 575-596 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The thermal decomposition of propanoic acid dilute in argon has beenstudied in a single-pulse shock tube over the temperature range of 1100-1500 K and over the pressure range of 14-18 atm. The decomposition kinetics have been satisfactorily computer modelled by means of afree radical mechanism involving H and OH chains.Recent single-pulse shock tube product analyses of acetic acid decomposition have been computer modelled using a free radical mechanism for decarboxylation coupled to a unimolecular dehydration reaction.A comparison between the thermal decomposition kinetics of the C1—C3 alkanoic acids is made. The present studies do notprovide evidence for the participation of transition states involving a pentavalent carbon atom in the pyrolyses of the lower alkanoic acids.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180508
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  • 66
    Digitale Medien
    Digitale Medien
    Masthead (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986) 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180601
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  • 67
    Digitale Medien
    Digitale Medien
    Mutual isomerization of cyclopentyl and 1-Penten-5-y1 radicals (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 623-637 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Unimolecular reactions of mutual isomerization of cyclopentyl and 1-penten-5-yl radicals have been investigated by chemical activation. The radicals were generated by adding energized hydrogen atoms (EH about 23 kcal mol-1) to the double bond of either cyclopentane or 1,4-pentadiene. Based on the extensive steady-state RRKM calculations employing the experimental data from this work as well as from the literature, the threshold energies for the cyclopentyl ring opening and closure are 32 ± 0.3 and 16.2 ± 0.3 kcal mol-1, respectively. The entropy of activation for the ring opening is close to zero.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 68
    Digitale Medien
    Digitale Medien
    Acetaldehyde oxidation in the negative temperature coefficient regime: Experimental and modeling results (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 655-688 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Acetaldehyde oxidation has been studied in experiments at temperatures of 553 and 713 K carried out in a low pressure, static reactor and in numerical modeling calculations using a detailed chemical kinetic reaction mechanism. The results of the experimental study were used to construct and validate the reaction mechanism, which was then used to examine acetaldehydeoxidation in the negative temperature coefficient regime between 550 and 900 K. This mechanism was also tested against independent measurements of acetaldehyde oxidation carried out by Baldwin, Matchan, and Walker. The overall rate of reaction and the properties of the negative temperature coefficient regime were found to be sensitive to the competition between radical decomposition reactions and the addition of molecular oxygen to acetyl and methyl radicals, including particularly \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_{\rm 3} + {\rm O}_2 + {\rm M = CH}_{\rm 3} {\rm O}_{\rm 2} + {\rm M} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_{\rm 3} {\rm CO} + {\rm M = CH}_{\rm 3} {\rm + CO} + {\rm M} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_{\rm 3} {\rm CO} + {\rm O}_{\rm 2} {\rm = CH}_{\rm 3} {\rm CO}_{\rm 3} $$\end{document} During these experiments, an upper limit to the rate of decomposition ofCH3O2H was measured at 553 K. Implications of the results for future kinetic modeling of engine knock are discussed.
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180606
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  • 69
    Digitale Medien
    Digitale Medien
    The thermodynamic state of the hot gas behind reflected shock waves: Implication to chemical kineticsThis research was supported by the Division of Chemical Sciences, United StatesDepartment of Energy, Washington, D.C., under Contract No. DE-AC02-76CH00016 (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 409-436 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Procedures are discussed to correct for nonideality in a shock tube used in the reflected mode in conjunction with flash photolysis and atomic resonance absorption to measure chemical kinetics of atoms at high temperatures. Experimentally, pressure time profiles for the incident and reflectedshock regions are made close to the location of the observation windows through which absorbance is measured. The corresponding temperatures are calculated from the adiabatic equation of state. Justification for this procedure is provided by extending Mirels' boundary layer theory to take intoaccount interaction of the reflected wave with the flowing gas in the free stream and in the boundary layer. These theoretical methods are described for calculating the thermodynamic and hydrodynamic states behind the reflected wave from initial values of pressure and temperature and the measured velocity of the incident wave. The implication of these results to kinetic measurements at high temperature is discussed.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180402
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  • 70
    Digitale Medien
    Digitale Medien
    An Ab initio determination of the rate constant for H2 + CN → H + HCNWork performed under the auspices of the Office of Basic Energy Sciences, Division of Chemical Sciences, US Department of Energy, under Contract W-31-109-Eng-38 (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 473-486 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The reactants, products, and saddle point for the reaction H2 + CN → H + HCN have been studied by ab initio calculations. The computed structures, frequencies, and energetics are compared directly to available measurements and, indirectly, to experimental rateconstants. The theoretical rate constants used in the comparison are calculated with conventional transition state theory. By reduction of the computed reaction barrier to 4.1 kcal mol,-1 good agreement with experimental rate constants is obtained over a 3250-K temperature range. This computed rate constant is well represented by the form 4.9 × 10-18 T2.45 e-1, 126/T over the temperature range of 250 K-3500 K. Substantial reaction rate curvature is found due to low-frequency bending modes at the saddle point. The results for this reaction are compared to other abstraction reactions involving H atom transfer to identify correlations between reaction exothermicity and both abstraction barriers and reaction rate curvature.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180406
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  • 71
    Digitale Medien
    Digitale Medien
    Rate constants of O2(1Δg) (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 505-512 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The rate constants of O2(1Δg) with aliphatic alcohols, terpenes, unsaturated hydrocarbons, chlorinated hydrocarbons, oxygen, and diamines have been studied in thepresence of NO2. The rate constants for oxygen, 1,2-ethane diamine, and 1,2-propane diamine are (9.9 ± 0.4) × 102, (8.7 ± 0.7) × 104, and (1.4 ± 0.3) × 104 1/mol/s, respectively. The rate constants for all other compounds are less than the oxygen rate constant.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180409
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  • 72
    Digitale Medien
    Digitale Medien
    Gas phase kinetic and thermochemical data for endo- and exo-5-monosubstituted bicyclo[2.2.2]Oct-2-Enes (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 537-545 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The thermal reactions of endo- and exo-5-Y bicyclo[2.2.2]oct-2-enes (NYBO and XYBO) where Y = methyl, ethyl, and isopropyl have been studied in the gas phase between 567 and 695 K. For both isomers they are parallel first-order retro-Diels-Alder reactions with elimination of ethene (E) and monosubstituted ethene (YE).The observed Arrhenius parameters are used to discuss the mechanism and to estimate the heats of formation and the entropies of NYBO and XYBO. Group values are proposed for estimation of these thermochemical data for compounds of the same type by means of the methods of Benson.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180504
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  • 73
    Digitale Medien
    Digitale Medien
    Estimations of OH radical rate constants from H-atom abstraction from C—H and O—H bonds over the temperature range 250-1000 K (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 555-568 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Rate constants for overall H-atom abstraction by hydroxyl radicals from C—H and O—H bonds are estimated for alkanes, haloalkanes, aldehydes, ketones, ethers, alcohols, nitriles, and nitrates over thetemperature range 250-1000 K. These estimated rate constants utilize the modified Arrhenius expression K = A'T2e-E'/T in combination with the recommendations given in the recent review and evaluation of OH radical kinetics of Atkinson [1]. This estimation procedure gives good agreement, generally to within better than a factor of 2, of the estimated rate constants with theserecommendations.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180506
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  • 74
    Digitale Medien
    Digitale Medien
    Effects of Olefins on the Thermal Decomposition of Propane Part IV. Influence of Propylene (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 301-312 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: On the basis of the thermal decomposition of mixtures of propylene and propane with molar ratios of 0.0-0.33 in the temperature range 779-812K, the influencing functions describing the inhibition by propylene of the decomposition of propane were determined. The rate-reducing effect is explained mainly by the reactions \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm C}_{\rm 3} {\rm H}_{\rm 6} + {}^.{\rm R} \longrightarrow {}^.{\rm C}_{\rm 3} {\rm H}_{\rm 5} + RH $$\end{document} (in which .R = .H, .CH3 and 2-Ċ3H7) and also by the addition reactions \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm C}_{\rm 3} {\rm H}_{\rm 6} + {}^.{\rm H} \to 1 - {\rm \dot C}_{\rm 3} {\rm H}_{\rm 7} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ \to 2 - {\rm \dot C}_{\rm 3} {\rm H}_{\rm 7}. $$\end{document} It was established that the bulk of the allyl radicals formed \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm C}_{\rm 3} {\rm H}_{\rm 8} + {}^.{\rm C}_{\rm 3} {\rm H}_{\rm 5} \to 1 - {\rm \dot C}_{\rm 3} {\rm H}_{\rm 7} + {\rm C}_{\rm 3} {\rm H}_{\rm 6} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ \to 2 - {\rm \dot C}_{\rm 3} {\rm H}_{\rm 7} + {\rm C}_{\rm 3} {\rm H}_{\rm 6} $$\end{document} participate in the chain step, but, due to their lower reactivity, they restore the decomposition chain more slowly than the original radicals do.From the characteristic change in the ratio υCH4/υH2, the rate ratios of hydrogenabstraction reaction by radicals from propylene and propane could be determined. In these reactions there was no significant difference between the selectivities of the radicals. For an interpretation of the changes, the decomposition mechanism must be completed with the reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm C}_{\rm 3} {\rm H}_{\rm 6} + 2 - {\rm \dot C}_{\rm 3} {\rm H}_{\rm 7} \to 1 - {\rm \dot C}_{\rm 3} {\rm H}_{\rm 7} + {\rm C}_{\rm 3} {\rm H}_{\rm 6}. $$\end{document}Evaluation of the influencing curves revealed that the initiation reactions \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm C}_{\rm 3} {\rm H}_{\rm 6} + {\rm C}_{\rm 3} {\rm H}_{\rm 6} \to {}^.{\rm C}_{\rm 3} {\rm H}_{\rm 5} + {}^.{\rm C}_{\rm 3} {\rm H}_{\rm 7} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm C}_{\rm 3} {\rm H}_{\rm 8} + {\rm C}_{\rm 3} {\rm H}_{\rm 6} \to {}^.{\rm C}_{\rm 3} {\rm H}_{\rm 7} + {}^.{\rm C}_{\rm 3} {\rm H}_{\rm 7} $$\end{document} must be taken into account.By parameter estimation we have determined the rate ratios characterizing the above initiation reactions, the unimolecular decomposition of propane, hydrogen abstraction by radicals from propane and propylene, intermolecular isomerization of the 2-propyl radical via propane and propylene, and abstraction of propane hydrogens by the ethyl and methyl radicals; these are given in Tables II.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180304
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  • 75
    Digitale Medien
    Digitale Medien
    Gas-phase thermolysis of sulfur compounds. Part VIII. Chloromethyl allyl, cyanomethyl allyl, 1-cyanoethyl allyl and neopentyl allyl sulfides (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 355-362 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The pyrolyses of four alkyl allyl sulfides with substituents on the α—C atom of the alkyl moiety have been studied in a stirred-flow system over the temperature range 340-400°C and pressures between 2 and 12 torr. The only products formed are propene and thioaldehydes. The reactions showed first-order kinetics with the rate coefficients following the Arrhenius equations: Chloromethyl allyl sulfide: \documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{{\rm - 1}}) = 10^{10.74 \pm 0.23} \exp ( - 144 \pm 3){\rm kJ/mol}RT $$\end{document} Cyanomethyl allyl sulfide: \documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{{\rm - 1}}) = 10^{10.20 \pm 0.19} \exp ( - 129 \pm 2){\rm kJ/mol}RT $$\end{document} 1-cyanoethyl allyl sulfide: \documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{{\rm - 1}}) = 10^{11.09 \pm 0.18} \exp ( - 141.5 \pm 2.2){\rm kJ/mol}RT $$\end{document} Neopentyl allyl sulfide: \documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{{\rm - 1}}) = 10^{10.54 \pm 0.24} \exp ( - 144 \pm 3){\rm kJ/mol}RT $$\end{document}The effects of these and other substituents on the reactivity is discussed in relation with the stabilization of a polar six-centered transition state. The results support a non-concerted mechanism where the 1-5 α—H atom shift is assisted by its acidic character.
    Zusätzliches Material: 5 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180308
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  • 76
    Digitale Medien
    Digitale Medien
    Competing Channels in Infrared Multiple Photon Decomposition (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 379-398 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Infrared multiple photon decompositions (IRMPD) with more than one reactive pathway can provide significantly more kinetic information than can single-channel photolyses. The rates of the competing unimolecular reactions and the rate of photon absorption are interrelated, so that knowledge of one yields information about the others. The goals and pitfalls of IRMPD experiments on several well-studied classes of reactants are reviewed.
    Zusätzliches Material: 5 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180310
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  • 77
    Digitale Medien
    Digitale Medien
    Masthead (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986) 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180401
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  • 78
    Digitale Medien
    Digitale Medien
    On the rates of decarbonylation of hydroxyacetyl and other acyl radicals (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 791-800 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The rate of decarbonylation of the hydroxyacetyl radical in acetonitrile is measured by effect modulated ESR spectroscopy and found to be log (KD/s-1) = (11.0 ± 1.5)-(2.3RT)-1 (37 ± 8)kJ/mol. The result is shown to be reasonably well connected with a variety of decarbonylation data known for other acyl species by asimple Evans-Polanyi relation.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180706
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  • 79
    Digitale Medien
    Digitale Medien
    The explosive reaction of carbon monoxide and oxygen at 973 and 1048 K (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 801-817 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Conditions leading to an explosive reaction of carbon monoxide and oxygen in the presence of small amounts of water have been examined at temperatures of 973 and 1048 K. Carbon monoxide and water were formed in the presence of oxygen by reaction with a thin film of carbon deposited on a quartz vessel. The carbon provided a reactive and reproducible surface, giving aconsistent rate of termination and thus allowing a quantitative descriptionof the conditions at the explosion in the region of the first limit. Calculations of the rates of the various branching and termination reactions at the onset of the explosion showed that the simple mechanism described earlier was still adequate to explain the reaction at temperatures up to 1050 K. From experiments with inert gases the transition from the first explosion limit to the region of the second explosion limit was demonstrated.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180707
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  • 80
    Digitale Medien
    Digitale Medien
    Masthead (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986) 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180501
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  • 81
    Digitale Medien
    Digitale Medien
    Rate constants for the reactions of isobutyl, neopentyl, cyclopentyl, and cyclohexyl radicals with molecular oxygen (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 547-554 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Rate constants have been measured for the reactions of four hydrocarbon radicals with O2 in the gas phase at room temperature. Laserflash photolysis was used to generate low concentrations of radicals. A photoinization mass spectrometer followed the radical loss as a function of time. The measured pseudo first-order decay rate of the radical and the absolute oxygen concentration were combined to give the absolute rate constants (in units of 10-12 cm3 molec-1 s-1): isobutyl (2.9 ± 0.7); neopentyl (1.6 ± 0.3); cyclopentyl (17 ± 3); and cyclohexyl (14 ± 2). The cycloalkyl radicals have rate constants similar to those of other secondary radicals. However, the isobutyl and neopentyl radicals react more slowly than similar primary radicals. These new rate constants are compared in Figure 2 with the recently published correlation of reactive cross section with radical ionization potential.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180505
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  • 82
    Digitale Medien
    Digitale Medien
    Kinetics of the reactions of naphthalene, 2-methylnaphthalene, and 2,3-dimethylnaphthalene with OH radicals and with O3 at 295 ± 1 K (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 569-573 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The kinetics of the gas-phase reactions of naphthalene, 2-methylnaphthalene, and 2,3-dimethylnaphthalene with O3 and with OH radicals have been studied at 295 ± 1 K in one atmosphere of air. Upper limit rate constants for the O3 reactions of 〈3 × 10-19, 〈4 × 10-19, and 〈4 × 10-19 cm3 molecule-1 s-1 were obtained for naphthalene, 2-methylnaphthalene, and 2,3-dimethylnaphthalene, respectively. For the OH radical reactions, rate constants of (in units of 10-11 cm3 molecule-1 s-1) 2.59 ± 0.24, 5.23 ± 0.42, and 7.68 ± 0.48 were determined for naphthalene, 2±methylnaphthalene, and 2,3-dimethylnaphthalene, respectively. These data show that under atmospheric conditions these naphthalenes will react mainly with the OH radical, with life-times due to this reaction ranging from ca. 11 h for naphthalene to ca. 4 h for 2,3-dimethylnaphthalene.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180507
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  • 83
    Digitale Medien
    Digitale Medien
    The photooxidation of allyl chloride (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 597-608 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The photooxidation of allyl chloride was studied by irradiation either in 100-L Teflon bags or in a 22.7-m3 Teflon smog chamber in the presence of added NOx. In the absence of added hydrocarbons, the reaction involves a Cl atom chain, which leads to a highly reactive system. A reaction mechanism is presented to account for the following photooxidation products: chloroacetaldehyde, formaldehyde, 1,3-dichloroacetone, 3-chloroacrolein, acrolein, glyoxal, chloroperoxyacetyl nitrate, and peroxypropenyl nitrate. The rate constant for OH reaction with allyl chloride at 298 K was measured by a relative rate method under conditions where the Cl atom chain length was small and was found to be kOH = 1.7 × 10-11 cm3 molecule-1 s-1. The rate constant for O3 reaction with allylchloride at 298 K was found to be kO3 = 1.5 × 10-18 cm3 molecule-1 s-1.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180509
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  • 84
    Digitale Medien
    Digitale Medien
    Spectrophotometric measurement of rates of hexacyanoferrate (III) reactions (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 651-653 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180605
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  • 85
    Digitale Medien
    Digitale Medien
    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
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 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.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 86
    Digitale Medien
    Digitale Medien
    Pyrolysis of acetylene-vinylacetylene mixtures between 400 and 500°C (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 701-718 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Acetylene and vinylacetylene mixtures were pyrolyzed at 400-500°C in the absence and presence of O2 or NO. The major product of the interaction between C2H2 and C4H4 is polymer, but benzene is also produced. Both the C2H2 removal and C6H6 formation rates arefirst-order in C2H2 and C4H4. The rate coefficients are \documentclass{article}\pagestyle{empty}\begin{document}$$ \log (k\{ {\rm C}_{\rm 2} {\rm H}_{\rm 2} \}, M^{ - 1} {\rm s}^{{\rm - 1}}) = 6.26 \pm 0.20 - (70.6 \pm 3.6)/2.3RT $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ \log (k\{ {\rm C}_{\rm 6} {\rm H}_{\rm 6} \}, M^{ - 1} {\rm s}^{{\rm - 1}}) = 8.65 \pm 0.39 - (125.9 \pm 5.4)/2.3RT $$\end{document} where R is the ideal gas constant in kJ/mol-K. Benzene formation occurs by two processes: a concerted molecular mechanism (≃60%) and a singlet diradical mechanism (≃40%).
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180608
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  • 87
    Digitale Medien
    Digitale Medien
    A comparative study of the PK(II) and LSTH potential energy surfaces for the H3 system (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1087-1100 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Recent dynamical computations on the LSTH and PK(II) potential energy surfaces are analyzed in terms of different properties of the surfaces. Differences in the bend level structure of resonances are found tobe due to the weaker vibrational force constant at the saddle point of the LSTH surface. The importance of including van der Waals wells in the potential energy surface is demonstrated by analysis of quantal resonances in thecollinear Mu + D2 reaction.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180915
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  • 88
    Digitale Medien
    Digitale Medien
    Rates of addition of tert-butyl and pivaloyl radicals to acrylonitrile measured by modulated ESR and μSR spectroscopy (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1113-1122 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: For the rate constant of addition of tert-butyl radicals to acrylonitrile at T = 300 K in solution modulated ESR spectroscopy and muon spin rotation yield 106 M-1 s-1 and 2.4 × 106 M-1 s-1. The addition of pivaloyl radical to acrylonitrile proceeds with Arrhenius parameters log A/M-1 s-1 = 7.7 and Ea = 11.5 kJ/ mol. The results are discussed in terms of polar effects in radical addition reactions.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550181002
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  • 89
    Digitale Medien
    Digitale Medien
    Kinetic evidence for the occurrence of trianionic tetrahedral intermediate in the hydroxide ion-catalyzed cleavage of 1, 2-benzisothiazolin-3-one-1, 1-dioxide (saccharin) (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1151-1161 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The kinetics of hydrolytic cleavage of saccharin has been studied at 60°C within the [ŌH] range of 0.1 to 3.0 M. The observed pseudo first-order rate constants, kobs, follow an empirical relationship: kobs = B[ŌH] + [C[ŌH]]2. The B and C terms are attributed to the formation of dianionic and trianionic tetrahedral intermediates on the reaction path. It is concluded that the ionized form of saccharin is the major reacting species under the present experimental conditions. The positive ionic strength effect and the negative effect of 1,4-dioxan on the rate of hydrolysis favor the proposed reaction mechanism. The analysis of the observed activation parameters indicates that the increase in the contribution of C term to kobs causes the slight increase in both ΔH* and ΔS*. A significantly large negative value of ΔS* favors the proposed mechanism.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550181005
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  • 90
    Digitale Medien
    Digitale Medien
    The Heterogeneous Reaction of Ozone on Carbonaceous SurfacesThis work was supported in part by the US Department of Energy, Contract No. DE-AC03-78-EV10121 and by the University of Colorado, CIRES, Boulder, CO. (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1133-1149 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Ozone, O3, reacts with a carbon sample at room temperature. Clean carbon samples show a half to one and a half order of magnitude increased initial rate constant (k0) for O3 loss relative to repetitively exposed carbon samples. The ozone loss rate and therefore the rate constant reaches steady state (kss) on the time scale of tens of minutes, upon exposure to a characteristic dose of 8 × 1017 molecules for a 30-mg carbon sample independent of the flow rate. This characteristic dose closely corresponds to a monolayer of adsorbed ozone molecules on the carbon sample. Both k0 and kss decrease with increasing flow rate of O3 into the reactor, and the loss rate is found to depend on [O3]. When the loss rate is plotted against the steady state concentration of O3, a saturation plot results which is proportional to the surface coverage, θ, at a given [O3].This interpretation rests upon a Langmuir type kinetics model with an assumed first-order dependence of the loss rate constant. The “sticking coefficients” track the rate constants and are on the order of 10-3 to 10-5 depending on the carbon sample, dose, and flow rate. Furthermore, ko depends on the length of the dark period (absence of O3 exposure) and is larger the longer time the sample has had to recuperate from previous O3 exposures up to a period of 150 s. This surface relaxation is thought of as a time-dependent change in surface coverage taking place in the dark period and is therefore an indication of a slow surface diffusion/reaction that can be separated from the adsorption-desorption kinetics. The mass balance shows that for every ozone molecule that is lost on the surface, an oxygen molecule is found. This adsorbed odd oxygen is then responsible for product formation, which comprises the volatile components CO and CO2 to an extent of 20 to 40% of the odd oxygen deposited on the surface. The difference is thought to be in a preoxidized state on the carbon sample, which evolves CO and CO2 upon heat treatment.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550181004
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  • 91
    Digitale Medien
    Digitale Medien
    Masthead (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986) 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550181101
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  • 92
    Digitale Medien
    Digitale Medien
    Kinetics of the reactions of halogenated methyl radicals (CF3, CF2Cl, CFCl2, and CCl3) with molecular chlorine (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1193-1204 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The kinetics of four gas-phase reactions involving halogenated methyl radicals (R = CF3, CF2Cl, CFCI2, and CCI3) with molecular chlorine have been studied using a tubular reactor coupled to a photoionization mass spectrometer. The radicals were homogeneously generated by the pulsed photolysis of precursor molecules at 193 nm. The subsequent decays of the radical concentration were monitored in real-time experiments as a function of Cl2 concentration to obtain the rate constants of these R + Cl2 reactions. Where possible, the rate constants were measured as a function of temperature to determine Arrhenius parameters. Apparent discrepancies between these measured rate constants for CF3 and CCl3 with Cl2 and ones obtained in prior indirect studies are explained. The higher activation energies for these R + Cl2 reactions compared to that of the CH3 + Cl2 reaction are attributed in part to the different polarities of the transition states formed.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550181008
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  • 93
    Digitale Medien
    Digitale Medien
    Kinetics and mechanism of the decomposition of N-bromoalcoholamines in aqueous solution (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1249-1258 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The decomposition reactions of N-bromodiethanolamine, N-bromoethylethanolamine, and N-bromomethylethanolamine in aqueous solution have been studied kinetically under various experimental conditions. The results support a proposed reaction mechanism in which the rate controlling step is assumed to be the formation of an imine which is then hydrolyzed to the final decomposition products.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550181104
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  • 94
    Digitale Medien
    Digitale Medien
    Importance of enolate anions in the high-pressure kinetics of nitroalkanes and nitroaromatics (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1205-1214 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We review and systematize experimental evidence concerning the extreme high-pressure kinetics of condensed phase nitroalkanes and nitroaromatics. This systematization suggests that enolate aci anions of the nitroalkanes and enolate aci-quinone anions of the nitroaromatics are important in the initial high-pressure kinetics of such systems. Kinetic data from experiments which observed the effect of: (1) small amounts of chemical additives, (2) substitution for protons, (3) difference in chemical isomer, (4) exposure to ultra-violet light, and (5) application of very high pressure can all be rationalized within the framework of our hypothesis. We suggest a static high-pressure ultra-violet absorption spectroscopy experiment on nitromethane that would test the proposed hypothesis.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550181009
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  • 95
    Digitale Medien
    Digitale Medien
    A comparison of various methods for calculating unimolecular reaction rate constants (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1259-1276 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A test of the Kassel quantum expressions for unimolecular rate constants and densities of vibrational states is described. Rate constants are calculated for nine reactions previously used in such tests, over a wide range of temperatures and pressures. The Kassel expression using the geometric mean of the molecular vibration frequencies is generally found to give better results than that using the arithmetic mean.
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550181105
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  • 96
    Digitale Medien
    Digitale Medien
    Gas phase reaction of heptafluoroisopropyl radicals with carbon tetrachloride (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 41-47 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The reaction was investigated in the gas phase over the range 80-225°C using the photolysis of heptafluoroisopropyl iodide as the source of radicals. The rate constant, based on the value of 1013.36 cm3 mol-1 s-1 for the recombination of i-C3F7 radicals, is given by \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log(}{{k_3 } \mathord{\left/ {\vphantom {{k_3 } {{\rm cm}^{\rm 3} }}} \right. \kern-\nulldelimiterspace} {{\rm cm}^{\rm 3} }}{\rm mol}^{ - 1} {\rm s}^{ - 1}) = (13.10 \pm 0.20) - {{(14000 \pm 280)} \mathord{\left/ {\vphantom {{(14000 \pm 280)} \theta }} \right. \kern-\nulldelimiterspace} \theta } $$\end{document} where θ = 2.303 RT/cal mol-1. Arrhenius parameters for chlorine abstraction from CCl4 by CF3, C2F5, n-C3F7, and some hydrogenated radicals are compared.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180105
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  • 97
    Digitale Medien
    Digitale Medien
    Kinetics and mechanism of electron transfer via bridge metal-ion (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 13-29 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The kinetics and mechanism of electron transfer between stable verdazyl radicals via bridge Mn(II), Co(II), Ni(II), Cu(I), and Zn ions have been studied in the range 280-330 K using the stopped-flow technique. It was found that the kinetic features of the reactions could be described in terms of the Marcus theory. The reorganization energy of the inner coordination sphere (ICS) of intermediate complexes was estimated from the reported data on the energy of release of various ligands from the ICS of similar complexes. The rest of the kinetic parameters (solvent reorganization energy, transmission coefficients, enthalpy, and entropy of activation) were determined from Marcus equations and from plots of rate constant versus temperature, “standard” free energy, and polarity of the medium. It was also found that the reactions under consideration are nonadiabatic and the transmission coefficient value depends on the mean lifetimes of ligands in the ICS.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180103
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  • 98
    Digitale Medien
    Digitale Medien
    Pyrolysis of [5-14C]-1-pentene-evidence for homoallylic rearrangements at 873 K (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 159-163 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: It was found that the pyrolysis of [5-14C]-1-pentene gives radioactive 1,3-butadiene. This result can be explained in terms of a sequence of free radical rearrangements of 1-penten-3-yl radicals. From this and additional information on isotope distribution in butadiene formed from different deuterated 1-pentenes, we conclude that homoallylic rearrangement of 1-penten-4-yl and 2-penten-5-yl radicals is the dominant route for their consumption.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180203
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  • 99
    Digitale Medien
    Digitale Medien
    Kinetics of the solvolysis of the trans-chloroazidobis(diaminoethane)cobalt (III) ion in water + t-Butyl Alcohol Mixtures (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 215-226 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The kinetics of the solvolysis of the ion trans-[Coen2N3Cl]+ have been investigated at several temperatures in mixtures of water with t-butyl alcohol with concentrations of the latter ranging up to 50 vol% or a mol fraction of 0.16. Values for the enthalpy and entropy of activation show sharp changes with changing solvent composition which can be correlated with extrema in the physical properties of the mixture concerned with sharp changes in solvent structure. Plots of log(rate constant) against the reciprocal of the dielectric constant and against the Grunwald-Winstein Y factor are both curved. The application of a free energy cycle shows that the effect of changes in solvent structure on the solvolysis dominates on the cobalt(III) cation in the transition state over that on the cation in the initial state.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180207
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  • 100
    Digitale Medien
    Digitale Medien
    Gas phase decomposition and isomerization reactions of 2-pentoxy radicals (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 329-344 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The rate of decomposition of 2-pentoxy radical to acetaldehyde and n-propyl radical has been studied in the presence of NO in competition with nitrite formation at and above 200 kPa pressure over the temperature range of 363-413 K. The rate coefficient for the decomposition is given as log(kla/s-1) = (14.2 ± 0.4) - (13.8 ± 0.8) kcal mol-1/RT ln 10. Isomerization of 2-pentoxy radical by 1,5-hydrogen shift has been investigated in the range 279-385 K in competition with the decomposition in a static system, with methyl radicals present in high concentration to ensure trapping of the isomerized free radicals. The rate coefficient for isomerization is given as log(k3/s-1) = (11.1 ± 0.7) - (9.5 ± 1.1) kcal mol-1/RT ln 10. The implications of the results for atmospheric chemistry are discussed.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180306
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