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  • 101
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pauling's formulas for the calculation of matrix elements for valence bond functions are derived using a simple substitutional process. The results generalize and simplify the formulas. In particular, the formulas do not depend upon orthogonality of atomic orbitals nor upon the nature of the choice of bond structures (canonical or not). The results are particularly adaptable to automatic computation.
    Additional Material: 1 Ill.
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  • 102
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 593-610 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The general formalism of the variational theory of the Faraday effect established in the first part of this paper is now applied to the actual computation of the Verdet constant of the hydrogen molecule, of water and of some saturated hydrocarbons. The numerical results have a correct order of magnitude and even, for hydrogen, are rather close to the experimental value.
    Additional Material: 2 Ill.
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  • 103
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 493-501 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Expansions in terms of the spherical coordinates of two particles are given for the interparticle distance and its inverse. The expansions are characterized in that each term is a product of analytical one-variable functions. While it is possible to find acceptable expansions for r12, those obtained for r12-1 exhibit extremely slow convergence, unacceptable for practical use. The same objections must be raised against related expansions of multi-centered molecular integrals.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
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  • 104
    Electronic Resource
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969) 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 105
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This article gives pointwise bounds for the wave functions of one-electron molecular systems.
    Type of Medium: Electronic Resource
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  • 106
    Electronic Resource
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 115-121 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The wave function of the HeHHe+ molecule has been calculated by means of the GENERAL SCF-MO-LC(LCGO) PROGRAM SYSTEM, taking all four electrons into account. The calculations were carried out for a number of linear equidistant, linear non-equidistant, and bent nuclear arrangements. The minimum energy of -5.7930 a.u. was found for a linear equidistant configuration with a He—H distance of 0.939 Å. The corresponding ionization energy was 37.9 eV. An estimation of the energy of formation of HeHHe+ from HeH+ and He based on SCF-calculations on HeH+ and He gave 7.9 kcal/mole. The frequencies of the normal vibrations were calculated.
    Additional Material: 2 Tab.
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  • 107
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 145-145 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 108
    Electronic Resource
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 169-184 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We discuss the properties of one version of the least squares (LS) method for the solution of the Schrödinger equation. These properties are exemplified by a number of calculations on the n1S and n3S states of helium, up to principal quantum number three, which are very much more accurate than previous LS calculations on helium. Particular attention is paid to the convergence properties of the LS procedure and we compare it with the simpler Rayleigh-Ritz (RR) procedure in the case when the RR matrix elements are evaluated numerically over the same quadrature mesh as used in the LS procedure. We conclude that although the LS procedure is capable of high accuracy it has no advantages which would justify its sole use in place of the RR procedure. However, it does have some advantages when used in conjunction with RR, in that it gives an estimate of the numerical accuracy of the RR energies.
    Additional Material: 6 Ill.
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  • 109
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 205-218 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The biorbital theory called also “identical geminals theory” is applied to the study of a number of conjugated molecules. All basic integrals are determined by means of the Pariser-Parr-Pople procedure. The biorbital theory reproduces about 40 per cent of the correlation energy of the ground state of the molecule; this number is raised to about 70 per cent for the lowest triplet state. The low lying excited states are well represented from the point of view of transition energy as well as from the point of view of symmetry. The occupation number matrix and the charge-bond order matrix are defined and discussed. The overall chemical description of conjugated molecules produced by the biorbital theory is similar to that produced by other theories of electronic structure of molecules. It is concluded that the biorbital theory provides a description the quality of which is, roughly speaking, about half way between those provided by the SCF-MO and complete CI theories, respectively.
    Additional Material: 10 Tab.
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  • 110
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    International Journal of Quantum Chemistry 3 (1969), S. 246-247 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 111
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 851-871 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Potential curves that show the energy dependence of hydrogen bonds between carbonyl and hydroxyl groups on the O—H bond length, on the distance between the molecules, and on the angle between the functional groups have been calculated with the CNDO/2 method. The results are presented for a small model system-formaldehyde/water - and for the dimer of formic acid. Good agreement is obtained with the available experimental data. The influence of the molecular geometry on the calculated results is discussed.
    Additional Material: 14 Ill.
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  • 112
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    International Journal of Quantum Chemistry 3 (1969), S. 889-891 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-butene has been investigated for different nuclear positions taking all 32 electrons into account, using the SCF-MO-LC(LCGO) method. The calculations show that the energy of the trans-form is 1.1 kcal/mol lower than that of the cis-form. The potential curve between these two forms is shown graphically. The ionization energy was estimated to be 9.0 eV.
    Additional Material: 1 Ill.
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  • 113
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 969-981 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A review is given of the current status of our work on electron transport properties and Fermi surfaces in simple metals. A simple classical model is proposed to extend existing theory to account for the effects of electron-impurity interactions on the behavior of magnetoacoustic absorption and the size and shape of the Fermi surface in the alkali metal potassium. The theoretical prediction is compared with measurements of the magnetoacoustic absorptionand Fermi surface diameters in potassium crystals of different impurity levels. An attempt is made to explain, on the basis of the theory of electron-impurity interactions, the decrease by 9% in the Fermi diameter and the departure by 53% in the phase factors of the impure potassium crystal. The results are compared with observations on a zone refined potassium crystal which satisfies the nearly-free-electron model.
    Additional Material: 3 Ill.
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  • 114
    Electronic Resource
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 945-968 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The long-range interaction energies for different dissociation products of the HeH+ molecule have been calculated using the Rayleigh-Schrödinger perturbation theory up to the third order in the energy. The calculations were carried out for the ground state (He(ls2) + H+), the first excited state (H(ls) + He+(ls)) and the second excited state Π(H(2pπ) + He+(ls)). The unperturbed states correspond to the dissociation products denoted in parentheses. Assuming the overlap to be zero, expanding the interaction potential in the inverse powers of the internuclear distance R and using the familiarly known perturbation-variational technique, the coefficients of various powers of R-1 in the energy expansion were evaluated. They correspond to different multipole-multipole interactions. The potential energy curves of all three states under consideration were calculated for large values of R. Also calculated were the multipole polarizabilities of the hydrogen atom in the is and 2pπ states and of the helium atom in the ground state.
    Additional Material: 4 Ill.
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  • 115
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 1027-1043 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The wave function defining a quantum-mechanical system is considered as the Laplace transform of some distribution and the consequent form of the Variational Principle derived; an integral equation defines the eigenfunctions of a certain subclass. The model of the hydrogen-like atom is used to test the theory; the eigenfunctions and associated energy levels of the ground and excited states are obtained for arbitrary values of the orbital quantum number.
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  • 116
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    International Journal of Quantum Chemistry 3 (1969), S. 569-580 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Vibronic coupling theory is used to construct the vibronic absorption spectrum of the ethylene dimer. It is shown that in this case an extended four-parameter form of the vibronic Hamiltonian should be considered. In addition to the commonly used three vibronic parameters, the difference between the ground and excited state force constants of the monomer is taken into account.Numerical calculations were performed for the dimer geometry resembling that of norbornadiene. Some comments on the interpretation of the absorption spectrum of norbornadiene are made.
    Additional Material: 2 Ill.
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  • 117
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 3 (1969), S. 611-619 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using a three dimensional free-electron model for the π-electron system the energies of the various singly and doubly excited configurations of benzene have been calculated. It has been found that the energies of the various singly excited configurations are in good agreement with the values obtained by Craig; whereas the energies of the doubly excited configurations are higher than those obtained by Craig. Therefore the configurational mixing for the doubly excited configurations is not necessary in this kind of model.
    Additional Material: 4 Tab.
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  • 118
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    International Journal of Quantum Chemistry 3 (1969), S. 663-681 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The full rotational symmetry of the hydrogen atom is lowered to that of the double group of Oh. This is done by a cubic field of electric dipoles. Symmetry-adapted spin orbitals have been calculated and with them the energies of the lowest states as functions of the distance from the dipoles to the atom, the dipole moment, and the size of the atoms forming the dipoles. The Hamiltonian used is obtained by starting with the Dirac equations and then making some simplifications and approximations.
    Additional Material: 10 Ill.
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  • 119
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    International Journal of Quantum Chemistry 3 (1969), S. 723-730 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Energy relations are derived for neutral atoms and isoelectronic sequences. It is shown that the field of the electrons at the position of the nucleus follows a very simple law and the diamagnetic shielding constant may be given in simple analytic form as a function of the atomic number.
    Additional Material: 2 Ill.
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  • 120
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    International Journal of Quantum Chemistry 3 (1969), S. 751-751 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 121
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    International Journal of Quantum Chemistry 3 (1969), S. 763-766 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is shown that the uncoupled approximation of Dalgarno with the approximate form of the Hartree-Fock operator gives no bound for the second order energy.
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  • 122
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    International Journal of Quantum Chemistry 3 (1969), S. 753-762 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The distribution of electronic charge in cubic boron nitride is investigated using the bond orbital wave functions recently calculated by Coulson and Doggett. Plots of the one-electron density function, in the (110) plane, are found to be insensitive to the choice of atomic basis functions, in contradistinction to the previously calculated effective atomic charges. A number of structure amplitudes are also calculated for each of the bond orbital wave functions.
    Additional Material: 5 Ill.
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  • 123
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    International Journal of Quantum Chemistry 3 (1969), S. 795-822 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The correspondence rules between the algebra of coupling coefficients of the special unitary group SU(2) and the associated algebra of a subgroup G of SU(2) are presented. The matrix elements of the irreducible representations of G are written in a convenient quantization scheme and different relations between these matrix elements and the Clebsch-Gordan coefficients of G are derived. Such a formalism is appropriate for numerous spectroscopic problems. As an example, it is applied to crystal field theory and electron paramagnetic resonance. General formulas from which a large number of results are rederived and generalized in a straightforward fashion are given. Numerical values of coupling coefficients for the tetragonal and cubic groups are listed in the Appendix.
    Additional Material: 8 Tab.
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  • 124
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    International Journal of Quantum Chemistry 3 (1969), S. 913-930 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A theory for handling non-orthogonal radial orbitals of two shells of atomic electrons based on the mathematical apparatus of irreducible tensor operators is presented. The general expressions for one- and two-electron operator matrix elements are given.
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  • 125
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    International Journal of Quantum Chemistry 3 (1969), S. 249-267 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Results obtained by various quantum-mechanical approaches in studying localized states on crystal surfaces are summarized and discussed. The one- and many-electron aspects of the problem are compared and shown to lead to similar results. Emphasis is laid upon localized chemisorption states on intrinsic semiconductors. The problem of the calculation of chemisorption heat on solid surfaces is also mentioned.
    Additional Material: 6 Ill.
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  • 126
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    International Journal of Quantum Chemistry 3 (1969), S. 873-879 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The system C2H5+ has been investigated as ethyl cation and as protonated ethylene using the SCF-MO-LC(LCGO) method. Equilibrium distances and angles have been estimated by different potential curves. No difference in total energy was found between the π- and the σ-complex.
    Additional Material: 4 Ill.
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  • 127
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    International Journal of Quantum Chemistry 3 (1969), S. 903-911 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is shown how the leading term for very large R of the Casimir-Polder potential, that is the term varying as R-7, arises in second-order perturbation theory applied to the interaction Hamiltonian - \documentclass{article}\pagestyle{empty}\begin{document}$ - \sum\limits_\sigma {\frac{1}{2}\alpha (\sigma){\rm E}^{ \bot ^2 } (\sigma)} $\end{document}. The generalization to anisotropic molecules is calculated and the angular dependence of the long range intermolecular potential in this case is given explicitly in terms of the principal polarizabilities and their corresponding directions of the two molecules.
    Additional Material: 1 Ill.
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  • 128
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    International Journal of Chemical Kinetics 1 (1969), S. 585-587 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 129
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    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 1 (1969) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 130
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    International Journal of Chemical Kinetics 1 (1969), S. 1-1 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 131
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    International Journal of Chemical Kinetics 1 (1969), S. 3-9 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: C—Cl and C—C bond energies in the chloroethanes and C—H, C—Cl, and C—C bond energies in the chloroethyl radicals are calculated from known heats of formation of chloroethanes and chloroethylenes and known C—H bond energies in chloroethanes.The results obtained show a dependence of bond energy on the isomeric structure of the molecules and radicals and on the type of bond broken (primary, secondary, or tertiary). Heats of formation and bond energies estimated from group property additivity rules are in close agreement with experimental values.
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  • 132
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    International Journal of Chemical Kinetics 1 (1969), S. 11-27 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study of the pressure dependence of the C5 products from the reaction of cis-butene-2 and methylene is reported. Methylene was produced by the photolysis of diazomethane with 4358 Å light at 23° or 56°, and by photolysis of ketene with 3200 Å radiation at 23° or 100°. The change with increasing pressure of the relative amounts of the characteristically “triplet products” (trans-1,2-dimethylcyclopropane, trans-pentene-2 (TP2), and 3-methylbutene-1 (3MB1)) and “singlet products” (cis-1,2-dimethylcyclopropane (CDMC) and cis-pentene-2 (CP2)) are discussed. The behavior is reminiscent of that found in 3CH2-cis-butene-2 systems and can be interpreted in terms of the rapid rate of rearrangement of an initial triplet diradical product component, due to 3CH2, relative to the slower rate and readier collisional stabilization of an initial vibrationally-excited dimethyl cyclopropane product component, due to 1CH2. Relative rates of reactions of 1CH2 with allylic CH:vinyl CH:C=C in the neat liquid were, for diazomethane, 1:1.1:7.2 and, for ketene, 1:1.2:6.7.
    Additional Material: 13 Ill.
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  • 133
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The use of iodine monochloride (ICl) as a thermal source of chlorine atoms in known concentration is discussed with particular reference to the suppression, by large excesses of iodine, of the chain processes normally associated with chlorine atom reactions. The kinetics and mechanism of the reaction of ICl with hydrogen are presented in a study covering the temperature range 205-337°C, and the pressure ranges: ICl, 6-20 torr; I2, 3-13 torr; and H2, 9-520 torr. The reaction, followed spectrophotometrically in a static system, is shown to be homogeneous, first order in ICl and in H2, and inverse half-order in I2, over several half-lifetimes of the ICl, yielding HCl as the sole product. The rate data obtained in this work for the reaction are combined with the critically evaluated results of other workers in an Arrhenius plot covering the temperature range 286-730°C, and three orders-of-magnitude in the rate constant, yielding the results, log k1/(1/mole sec) = 10.68-5.26/θ, where θ = 2.303RT in kcal/mole. This value of k1 is lower by a factor of about two than that proposed in a recent review by Fettis and Knox, and is clearly at variance by a factor of two or more with the most recent data of Clyne and Stedman.
    Additional Material: 3 Ill.
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  • 134
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The temperature-jump method has been used to determine the nickel(II)- and cobalt(II)-arginine complexation kinetics. In the pH range studied, the neutral form of the ligand, HL, is the attacking, as well as the complexed, ligand species. The reactions reported on are of the type where n = 1, 2, 3 and M is Ni or Co. At 25° and ionic strength 0.1M the association rate constants are: for nickel(II) k1 = 2.3 × 103(±20%), k2 = 2.4 × 104(±20%), k3 = 3.5 × 104(±40%) M-1 sec-1; for cobalt(II) k1 = 1.5 × 105(±20%), k2 = 8.7 × 105(±20%), k3 = 2.0 × 105(±40%) M-1 sec-1. Arginine binds to metal ions less well than homologous chelating agents due to the electrostatic repulsion arising from the positively charged terminus of the zwitterion. Kinetically, the effect appears in the association rate constants with nickel reactions more strongly influenced than cobalt.
    Additional Material: 2 Ill.
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  • 135
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The spectrophotometric determination of the rate of iodine atom catalyzed geometrical isomerization of diiodoethylene in the gas phase from 502.8 to 609.1°K leads to a rate constant for the bimolecular reaction between I and trans-diiodoethylene of log kt-c(M-1 sec-1) = 8.85 ± 0.12 - (11.01 ± 0.30)/θ. Estimates of the entropy and enthalpy change for the addition of I atoms to trans-diiodoethylene (process a.b) lead to log Ka.b(M-1) = -2.99 - 4.0/θ, and thus to log kc (sec-1) = log kt-c - log Kab = 11.8 -7.0/θ for the rate constant for rotation about the single bond in the adduct radical. The theory for calculation of the rotation rate constant is presented and it is shown that while the exact value depends on the barrier height, a value of 6.8 kcal/mole for this quantity leads to log k (sec-1) = 11.8 -6.7/θ. The activation energy points to a better value of the group contribution to heat of formation of the group C-(I)2(H)(C) than one based on bond additivity.
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  • 136
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    International Journal of Chemical Kinetics 1 (1969), S. 69-87 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title reactions have been investigated in a fast flow system at pressures of about 2 torr and temperatures between 12 and 132°C. The following Arrhenius equations are derived for reaction (2) where the units of k2 are l/mole sec and of E2, cal/mole, and the limits are the 95% confidence limits assuming random errors.These equations are in good agreement with those which can be derived from previous investigations.
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  • 137
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    International Journal of Chemical Kinetics 1 (1969), S. 105-111 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction between carbon monoxide and atomic oxygen was studied in a gas flow over a temperature range of 136 to 230°C at atmospheric pressure. The rate constant of this reaction, considered to be one for a second-order reaction, was found to decrease with increasing temperature and to depend on the ratio of O2 to CO that was varied from 0.11 to 2.69. A conclusion was made that under the experimental conditions the reaction was third order The rate constant of this reaction was determined for a mixture of O2 and CO and it was found that the efficiency of O2 as particle M is four times that of CO.
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  • 138
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    International Journal of Chemical Kinetics 1 (1969), S. 113-126 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rates of solvolysis of benzyl chloride and of substituted benzyl chlorides have been measured in an acetone-water mixture (acetone mole fraction 0.147) at pressures ranging from atmospheric to 1 kbar. Pressure studies have also been made for p-methyl benzyl chloride in various acetone-water mixtures. Measurements have also been made of the partial molar volumes of the reactants. The plots of log k against pressure are fitted to a second-degree polynomial in P, and values of ΔV
    Additional Material: 5 Ill.
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  • 139
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The method of molecular-modulation spectrometry for studying photochemical reactions has been applied to methyl nitrite photolysis. The infrared absorption of the nitroxyl radical HNO has been observed in the gas phase at 3300 cm-1. Under the present experimental conditions the steady-state concentration of HNO under steady illumination was 1.1 × 1012 particles/cc, and the observed modulation amplitude was 4.5 × 1010 particles/cc. At 25°C and 1 atm of nitrogen, the cross section for infrared absorption by HNO at 3300 cm-1 is 1.7 × 10-19 cm2. The rate constant ratio b/c was found to be 8.0. From the literature value of the rate constant d , the observed rate constant for the reaction is e = (5 ± 1) × 10-11 cc/particle sec.
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  • 140
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    International Journal of Chemical Kinetics 1 (1969) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 141
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The spectrophotometric determination of the rate of pyrolysis of 1,2-diiodoethylene from 305.8 to 435.0° (with additional data on the addition of iodine to acetylene from 198.1 to 331.6°) has resulted in the observation of both a (in part heterogeneous) unimolecular process (A), and an iodine atom catalyzed process (B). For the homogeneous unimolecular process, log (kA/sec-1) ≈ 12.5-46/θ would appear to be reasonable, while log (kB/M-1 sec-1) = 11.8-23.9/θ, where θ = 2.303RT in kcal/mole.It is suggested that a donor-acceptor complex intermediate may explain the observed rate constant of process B and analogous reactions in other systems.
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  • 142
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    International Journal of Chemical Kinetics 1 (1969), S. 133-146 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal isomerization of the title compounds was studied in the vapor phase. Over the temperature range from 445.1 to 477.5°K, 1,4-dimethylbicyclo[2.2.0]hexane underwent a homogeneous unimolecular reaction to 2,5-dimethyl-1,5-hexadiene, the rate constants being represented by the equation: k = 1.86 × 1011 exp (-31000 ± 1800/RT) sec-1. Over the temperature range from 630.0 to 662.2°K, 1,4-dimethylbicyclo[2.1.1]-hexane also underwent a unimolecular isomerization to the same product, the rate constants being given by the equation: k = 8.91 × 1014 exp (-56000 ± 900/RT) sec-1. The pyrolysis of 1,4-dimethylbicyclo[2.1.0]pentane gave 1,3-dimethylcyclopentene-1 and 2,4-dimethyl-1,4-pentadiene in the ratio of 9:1. The former reaction was influenced by surface effects but the latter was not. The rate constants for the formation of 2,4-dimethyl-1,4-pentadiene fitted the equation: k = 1.66 × 1017 exp (-57400 ± 3100/RT) sec-1. The effect of the two methyl groups at the bridgehead positions in these molecules in influencing the rate of decomposition is discussed in terms of the non-bonded repulsive forces between the substituents.
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  • 143
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    International Journal of Chemical Kinetics 1 (1969), S. 157-170 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Isotope effects, general acid catalysis, and relative reactivities show that proton transfer to one of the unsaturated carbon atoms is rate determining for the acidolysis of unsaturated alkylmercuric halides. For compounds, R1R2C=CHHgX, substitution of CH3 for H at R1 or R2 leads to an acceleration of a factor of ∼ 30. This relatively small acceleration, the relative facility of the reactions, and the magnitude of the Br- catalytic terms, suggests an olefin-mercuric halide complex as the product of the rate-determining step, rather than a simple carbonium ion.The Brøonsted catalysis law is obeyed with a variety of carboxylic acids, giving an ∝ of 0.69 ± 0.04, but acids of other structures give substantially deviant catalytic coefficients, in a pattern similar to that generated by other A-SE2 reactions. The acetic acid catalytic coefficient is larger by a factor of 102 than that predicted if it were due to specific hydronium ion-general base catalysis instead of true general acid catalysis.The overall solvent isotope effect, kH/kD, is 2.55 ± 0.10. The competitive isotope effect, κH/κD, is 6.84 ± 0.06. Taken with a model in which the proton is transferred directly from the H3O+ unit of the aquated proton to the substrate, these are sufficient to successfully predict the rate at all intermediate isotopic compositions.
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  • 144
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    International Journal of Chemical Kinetics 1 (1969), S. 171-191 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of azomethane-d6 has been studied. There is a short chain reaction, and measurements have been made of the rate of production of N2, CD4, and C2D6. A mechanism is suggested which accounts for these results fairly well. A comparison is made with some similar results of Forst for azomethane. Measurements have also been made of the reaction inhibited by NO. It is believed that the N2 production, extrapolated to zero NO pressure, measures the rate of the initial step CD3N2CD3 → 2 CD3 + N2. This has an activation energy at high pressures of 50.7 kcal per mole and an Arrhenius A·factor of 1015.49 sec-1. This is to be compared to values of 55.5 and 1017.3 found by Forst and Rice for CH3N2CH3 → 2 CH3 + N2. The pressure fall-off behavior for CD3N2CD3 → 2 CD3 + N2 has also been investigated and compared to the theoretical curves, which seem to fit satisfactorily except at the lowest pressure, where experimental errors may be large. Unexpectedly, the fall-off curve crosses that for CH3N2CH3 → 2 CH3 + N2. It is suggested that the extrapolation to zero NO pressure may not be entirely correct in the CH3N2CH3 case where the chain is longer than with CD3N2CD3. It is believed that the decomposition of azomethane-d6 is a better example for unimolecular-rate theory than is that of azomethane.
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  • 145
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    International Journal of Chemical Kinetics 1 (1969), S. 193-207 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: t-Butylperoxy α-phenylisobutyrate (I) decomposes thermally by concerted formation of carbon dioxide, t-butoxy, and cumyl radicals. Radical pair return in the solvent cage therefore does not affect the observed rate of decomposition, but is readily determined by means of galvinoxyl and other scavengers. In a series of 15 solvents the rate constant varies over a 2.8 fold range, being fastest in aromatic solvents. In the same solvent series the relative rates of diffusion and combination of radicals, measured by the cage effect, change by tenfold and are largely determined by the viscosity of the solvent. In all solvents of η 〉 8 mP, the reciprocal of the cage effect is a linear function of (T1/2/η), as recently observed for trifluoromethyl and methyl radicals [16]. This property of the cage effect provides a test by which it can be distinguished from other processes that reduce the efficiency of free-radical production from an initiator.
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  • 146
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    International Journal of Chemical Kinetics 1 (1969), S. 279-282 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
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  • 147
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of ozonation of C2H4 and C2H2 have been studied in the gas phase from -40 to -95°C (C2H4) and +10 to -30°C (C2H2). The O3 concentrations were near 10-4 M, and the hydrocarbons were present in 2- to 25-fold excess. A few experiments with propylene were also carried out. The reactions were followed by observing the rate of decay of O3 absorption at 2537 Å. Reaction stoichiometries and effects of added O2 were investigated. The second-order rate constant for C2H4 was log k(M-1 sec-1) = (6.3 ± 0.2) - (4.7 ± 0.2)/θ (θ = 2.3RT). The rate was independent of the presence of excess O2. Rate measurements for C3H6 were less accurate because of aerosol interference. Combined with room temperature measurements of other workers, the C3H6 rate constant was log k(M-1 sec-1) = (6.0 ± 0.4) - (3.2 ± 0.6)/θ. The C2H2 rate constant was log k(M-1 sec-1) = (9.5 ± 0.4) - (10.8 ± 0.4)/θ. In the case of C3H6 the major product was propylene ozonide. Ethylene did not yield the ozonide, and the products of the O3-C2H4 and O3-C2H2 reactions were not identified. Pre-exponential factors for the olefin reactions are consistent with a five-membered ring transition state formed by 1,3 dipolar cycloaddition of O3. For C2H2, however, the much higher observed A factor suggests a different mechanism. Possible transition states for the O3-C2H2 reaction are discussed.
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  • 148
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    International Journal of Chemical Kinetics 1 (1969) 
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 149
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methods are presented for rapidly estimating the entropies and heat capacities of free radicals from the known S0 and Cp0 of structurally similar compounds. The methods consist of estimating the differences due to changes in mass, vibration frequencies, spin, symmetry, and changes in rotational barriers. Tables of contributions to S0 and Cp0 by different frequencies over the temperature range 300-1500°K are presented to facilitate the tabulation of the above differences. Conjugated radicals, such as benzyl and allyl, are included. It is shown that the greatest uncertainties in the estimates arise from uncertainties in the barriers to rotation in the radicals.The results are applied to kinetic data on the pyrolysis of branched hydrocarbons and the reverse reactions of radical recombination. Major discrepancies exist in these data which can be nearly reconciled by postulating improbably high rotational barriers of 8 kcal for CH3 rotation in isopropyl and t-butyl radicals.It is shown that radical thermochemistry can be fitted into group schemes and tables of groups values are given for the rapid estimation of ΔHf0, S0, and Cp0 for different organic radicals, including those containing sulfur, oxygen, and nitrogen.
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  • 150
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of the reaction CH2I2 + HI ⇆ CH3I + I2 has been followed spectrophotometrically from 201.0 to 311.2°. The rate constant for the reaction fits the equation, log (k1/M-1 sec-1) = 11.45 ± 0.18 - (15.11 ± 0.44)/θ. This value, combined with the assumption that E2 = 0 ± 1 kcal/mole, leads to ΔHf298° (CH2I, g) = 55.0 ± 1.6 kcal/mole and DH298° (H—CH2I) = 103.8 ± 1.6 kcal/mole.The kinetics of the disproportionation, 2 CH3I ⇆ CH4 + CH2I2 were studied at 331° and are compatible with the above values.
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  • 151
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several hydrocarbons have been pyrolyzed in a single pulse shock tube. Rate parameters for the main bond breaking step have been found to be \documentclass{article}\pagestyle{empty}\begin{document}$$ k\left\{{{\rm iC}_3 {\rm H}_7 {-\!-} {\rm CH}\left({{\rm CH}_3} \right){\rm CH} {\raise1pt\hbox{$\Relbar \kern-4pt{\Relbar}$}} {\rm CH}_2 \longrightarrow {\rm iC}_3 {\rm H}_7 \cdot + \cdot {\rm CH}\left({{\rm CH}_3} \right){\rm CH} {\raise1pt\hbox{$\Relbar \kern-4pt{\Relbar}$}} {\rm CH}_2} \right\} = 10^{15.70} \exp \left({{{- 32,500} \mathord{\left/ {\vphantom {{- 32,500} T}} \right. \kern-\nulldelimiterspace} T}} \right)\sec ^{- 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k\left\{{{\rm iC}_3 {\rm H}_7 {-\!-} {\rm C}\left({{\rm CH}_3} \right)_2 {\rm C}_2 {\rm H}_5 \longrightarrow {\rm iC}_3 {\rm H}_7 \cdot + \cdot {\rm C}\left({{\rm CH}_3} \right)_2 {\rm C}_2 {\rm H}_5} \right\} = 10^{16.15} \exp \left({{{- 35,900} \mathord{\left/ {\vphantom {{- 35,900} T}} \right. \kern-\nulldelimiterspace} T}} \right)\sec ^{- 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k\left\{{{\rm C}_2 {\rm H}_5 {-\!-} {\rm C}\left({{\rm CH}_3} \right)_2 {\rm C}_2 {\rm H}_5 \longrightarrow {\rm C}_2 {\rm H}_5 \cdot + \cdot {\rm C}\left({{\rm CH}_3} \right)_2 {\rm C}_2 {\rm H}_5} \right\} = 10^{16.57} \exp \left({{{- 38,800} \mathord{\left/ {\vphantom {{- 38,800} T}} \right. \kern-\nulldelimiterspace} T}} \right)\sec ^{- 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k\left\{{{\rm iC}_3 {\rm H}_7 {-\!-} {\rm CH}_2 {\rm C}_6 {\rm H}_5 \longrightarrow {\rm iC}_3 {\rm H}_7 \cdot + \cdot {\rm CH}_2 {\rm C}_6 {\rm H}_5} \right\} = 10^{15.23} \exp \left({{{- 34,800} \mathord{\left/ {\vphantom {{- 34,800} T}} \right. \kern-\nulldelimiterspace} T}} \right)\sec ^{- 1} $$\end{document} In combination with similar studies carried out earlier and through application of the well-established experimental rule (kr2(AB)/kr(AA)kr(BB))1/2 ∼ 2 where A and B are radicals and the rate constants are for the combination of these radicals, rate parameters for the thermal decomposition of all the hydrocarbons formed from any pair of the following radicals: methyl, ethyl, isopropyl, t-butyl, t-amyl, allyl, methylallyl, and benzyl have been calculated. The available calculated and experimental values of the decomposition rate constants are in excellent agreement. It appears that, with the possible exception of reactions involving the ejection of methyl radicals, the frequency factors per bond are nearly constant, depending only upon the type of carbon-carbon bond that is being broken. These values are all lower than those expected from the radical recombination rates.Heats of formation of ethyl, t-amyl, benzyl, methylallyl, n-propyl, s-butyl, isobutyl, neopentyl, and 3-pentyl radicals have been derived.Rate parameters for the decomposition of some simple ketones and ethers have also been estimated.
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  • 152
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the photoinitiated reductions of methyl iodide and carbon tetrachloride by tri-n-butylgermanium hydride in cyclohexane at 25°C have been studied and absolute rate constants have been measured. Rate constants for the combination of CH3ċ and CCl3ċ radicals are equal within experimental error and are also equal to the values found for the self-reactions of most non-polymeric radicals in low viscosity solvents, i.e. ∼1-3 × 109 M-1 sec-1.Rate constants for hydrogen atom abstraction by CH3ċ and CCl3ċ radicals are both ∼1-2 × 105 M-1 sec-1. Tri-n-butyltin hydride is about 10-20 times as good a hydrogen donor to alkyl radicals as is tri-n-butylgermanium hydride.The strength of the germanium-hydrogen bond, D(n-Bu3Ge-H) is estimated to be approximately 84 kcal/mole.
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  • 153
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    International Journal of Chemical Kinetics 1 (1969), S. 353-356 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 154
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    International Journal of Chemical Kinetics 1 (1969), S. 325-337 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the thermally and radiation initiated chain reaction between trichloroethylene and cyclopentane to produce 1,1-dichlorovinylcyclopentane and hydrogen chloride have been investigated in the temperature range 250-360°C at high pressure in the gas phase. The rate governing step in the chain is (k3 = 3.3 × 109 exp -(4800/RT) cc mole-1 sec -1). The rate of the unimolecular decomposition of trichloroethylene is 1.4 × 1014 exp -(61,200/RT) sec-1.
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  • 155
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    International Journal of Chemical Kinetics 1 (1969), S. 297-314 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas phase, nitric oxide catalyzed positional isomerization of 3-methylene-1,5,5-trimethylcyclohexene (MTC) into 1,3,5,5-tetramethyl-1,3-cyclohexadiene (TECD) has been studied for temperatures ranging between 296° and 425°C. The major reaction was first order with respect to nitric oxide and to MTC.The major side product, mesitylene, usually amounted to less than 10% of the TECD isomer formed. Only at high temperatures and large conversions has up to 20% been observed.Conditioned pyrex or quartz vessels coated with KCl have been used. The nitric oxide catalyzed isomerization is apparently a homogeneous process, as demonstrated by the insensitivity of the observed rate constants towards a 15-fold increase in the surface to volume ratio of the reaction vessels. However, a residual, presumably heterogeneous, thermal isomerization of the starting material could not be eliminated. Good mass balances were obtained for both NO and hydrocarbons.After correcting for the thermally induced conversion the observed rate constants for the nitric oxide catalyzed isomerization yield log k1 (1 mole-1 sec-1) = (10.7 ± 0.2) - (37.3 ± 0.9)/θ where θ is 2.303 × 10-3 RT (kcal mole-1). Plotting log k1 versus the ratio of the starting materials (MTC/NO)0 it was found that for temperatures ≥ 365°C the rate constants were systematically too high.Using extrapolated values for the higher temperature range yields the more reliable corrected Arrhenius equation log k1corr = 8.6 - 31.7/θ. The reaction mechanism is outlined and the implications with respect to the stabilization energy generated in the MTCċ radical intermediate and the activation energy of the backreaction MTCċ + HNO are discussed.Using for the activation energy E-1 of the backreaction (Rċ + HNO) a literature value of 9.2 ± 0.9 kcal mole-1 reported for the cyclohexadiene—1,3—system, this yields 23.4 ± 2 kcal mole-1 for the stabilization energy in the methylenecyclohexenyl radical, which is to be compared with the corresponding values for the allyl (10.2 ± 1.4), methallyl (12.6 ± 1) pentadienyl (15.4 ± 1) and cyclohexadienyl (24.6 ± 0.7) radicals.The pre-exponential factor agrees well with the value of (8.4 ± 0.2) reported by Shaw and co-workers for the similar reaction of NO with 1,3-cyclohexadiene. It is noteworthy that HNO, acting as sole hydrogen donor in the system, is surprisingly stable under the reaction conditions used. Nitrous oxide, HCN, H2O and N2 are observed in the product mixture of experiments carried out to high conversions at higher temperatures.
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  • 156
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    International Journal of Chemical Kinetics 1 (1969), S. 339-351 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The following Arrhenius parameters have been determined for the hydrogen-abstraction reactions: R + (CH3)4Si → RH + (CH3)3SiCH3 TextRTemp. (°K)E (kcal/mole)Log A (mole-1 cc sec-1)Log k(400°K) (mole-1 cc sec-1)CF3330-4337.23 ± 0.0911.90 ± 0.057.95CH3396-47610.23 ± 0.3611.55 ± 0.185.68CD3396-49610.36 ± 0.1211.84 ± 0.066.20C2H5423-52211.40 ± 0.4811.88 ± 0.225.68The activation energies are in keeping with the strengths of the bonds formed during the reaction. By comparison with the activation energies for the analogous reactions of neopentane it is estimated that D((CH3)3SiCH2—H) ≃ 97 kcal/mole.The A factors for the above series of reactions fall within the range predicted by transition-state theory for this type of process and the validity of previous results of Kerr, Slater, and Young is seriously in doubt.
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  • 157
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    International Journal of Chemical Kinetics 1 (1969), S. 357-359 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 158
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    International Journal of Chemical Kinetics 1 (1969) 
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 159
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    International Journal of Chemical Kinetics 1 (1969), S. 391-399 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the presence of elementary iodine, isobutyl iodide (2-methyl-1-iodopropane) undergoes isotopic exchange and also decomposes with production of additional iodine. Both reactions are approximately first order in isobutyl iodide and half order in iodine molecules. In degassed hexachlorobutadiene at 160°, the rate constants for exchange and decomposition are 7.5 × 10-6 and 11.4 × 10-6 (liter/mole)1/2sec-1, respectively. The decomposition is probably initiated by iodine atom abstraction of a β hydrogen atom, but comparison with rates for related compounds indicates that this hydrogen abstraction does not contribute significantly to the mechanism of exchange.
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  • 160
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics and mechanism of the reaction between iodine and dimethyl ether (DME) have been studied spectrophotometrically from 515-630°K over the pressure ranges, I2 3.8-18.9 torr and DME 39.6-592 torr in a static system. The rate-determining step is, where k1 is given by log (k1/M-1 sec-1) = 11.5 ± 0.3 - 23.2 ± 0.7/θ, with θ = 2.303RT in kcal/mole. The ratio k2/k-1, is given by log (k2/k-1) = -0.05 ± 0.19 + (0.9 ± 0.45)/θ, whence the carbon-hydrogen bond dissociation energy, DH° (H—CH2OCH3) = 93.3 ± 1 kcal/mole. From this, ΔH°f(CH2OCH3) = -2.8 kcal and DH°(CH3—OCH2) = 9.1 kcal/mole.Some nmr and uv spectral features of iodomethyl ether are reported.
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  • 161
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    International Journal of Chemical Kinetics 1 (1969), S. 371-380 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Arrhenius parameters have been determined for the hydrogen-abstraction reactions: R + SiHCl3 + RH + SiCl3 TextRTemp (°K)E(kcal/mole)Log A(mole-1 cc sec-1)Log k(400°K) (mole-1 cc sec-1)CF3323-4615.98 ± 0.0611.77 ± 0.038.50CH3333-4434.30 ± 0.0810.83 ± 0.044.48C2H5314-4135.32 ± 0.0711.54 ± 0.048.63The trend in activation energies ECH3 〈 EC2H5 〈 ECF3 is interpreted as indicating a polar effect in the reaction of CF3 with SiHCl3 and the similar reactivities of all three radicals appear to be due to the high exothermicity of the reactions.The A Factors for the reactions are normal for hydrogen abstraction reactions of free radicals. The previous results of Kerr, Slater, and Young for CH3 abstracting an H atom from SiHCl3 have been amended.
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  • 162
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    International Journal of Chemical Kinetics 1 (1969), S. 361-370 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Stable nitroxide radicals and ESR techniques have been used to investigate rotational and translational motions of molecules in the liquid state. It is found that for hydrocarbons and molecules with low polarity the rotational frequencies are about an order of magnitude faster than translational encounters. Arrhenius parameters are reported for the rates of both types of processes. A scheme is given for the relation of these motions to radical recombination in solution and also to reactions requiring activation energy. The consequences of this scheme are examined.Such important properties as hydrodynamic fluidity, thermal conductivity, processes of extraction and solution, occurring in the liquid phase as well as at the interface are determined by mobility of particles in the liquid. The problem of molecular mobility is of essential significance for the kinetics of chemical and chemico-physical processes in the liquid phase.Application of both ESR techniques and stable nitroxide radicals for kinetic studies of molecular motions in liquids and the correlation between molecular mobility and the kinetic parameters of liquid-phase radical reactions have been studied in the present paper.
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  • 163
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    International Journal of Chemical Kinetics 1 (1969) 
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 164
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    International Journal of Chemical Kinetics 1 (1969), S. 413-425 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis of pentafluoroacetone has been investigated in the 3130 Å region, from room temperature to 360°C. The ΦCO varies from 0.7 to 0.9 over this range, and the decomposition is represented by CF2HCOCF3 → CF2H + CO + CF3. The disproportionation/combination ratio for CF3 and CF2H (→ CF3H + CF2) radicals is found to be 0.09. Arrhenius parameters for hydrogen atom abstraction from the ketone are log10A = 12.7 (units are mole-1 cc sec-1) and E = 14.3 kcal mole-1 for CF2H, and log10A = 12.1 and E = 11.8, for CF3 radicals. At low pressures HF elimination reactions are observed from the vibrationally excited fluoroethanes, C2F5H* and C2F4H2*, formed in the system. A rough estimate of the activation energy for the process C2F5H → C2F4 + HF of 60-65 kcal mole-1 is made.
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  • 165
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The activating effects of a number of unsaturated groups and a cyclopropyl group have been evaluated in a solvent free system by determining the absolute rate constants, and energies and entropies of activation in the vapor phase pyrolysis of secondary and tertiary esters of the type RC(R′CH3) OAc where R′ = H or CH3 and R = c-Pr, i-Pr, CH3, CH2=CH, CH2=CHCH2, C6H5; the cyclopropyl showed only a moderate activating effect. The results are in contrast to the very significant activating effect of a cyclopropyl group in solvolysis of cyclopropylcarbinyl derivatives. Apparently marked activation by this group occurs only when a highly developed positive center forms adjacent to it. The lack of marked activation by the cyclopropyl group supports a mechanism for ester pyrolysis which involves a modest, but detectable, charge separation in the transition state [2] but questions a mechanism in which an intimate ion-pair was proposed [3].
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  • 166
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas phase reaction I2 + HCOOCH3 → HI + CH3I + CO2 has been studied spectrophotometrically in a static system over the pressure ranges I2 (6-39 torr) and HCOOMe (28-360 torr). In the temperature range 293-356°, the initial rate of disappearance of I2 is first order in [HCOOMe] and half-order in [I2]. The rate determining step is where k1 is given by \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} \left({k_1 /{\rm M}^{- 1} \sec ^{- 1}} \right) = \left({9.6 \pm 0.3} \right) - \left({22.4 \pm 0.8} \right)/\theta $$\end{document} where θ = 2.303 RT in kcal/mole. This activation energy gives a carbonyl C—H bond strength of 92.7 kcal/mole. At 356° there was no evidence of abstraction of a methoxy hydrogen, so a lower limit of 100 kcal/mole may be placed on this C—H bond strength. These ester C—H bond strengths are discussed in relation to comparable values in aldehydes and ethers.
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  • 167
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    International Journal of Chemical Kinetics 1 (1969), S. 439-450 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The relative rates of addition of difluorocarbene to a series of methyl-substituted olefins have been determined and correlated with similar data for dichlorocarbene, chlorofluorocarbene and ground-state oxygen atoms. The electrophilic nature and stabilization of difluorocarbene by the fluorine substituents is discussed. Relative activation energies for the difluorocyclopropane-forming reaction have been estimated and correlated with properties of the olefins as derived from molecular orbital theory.
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  • 168
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    International Journal of Chemical Kinetics 1 (1969), S. 451-458 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Data on the kinetics of S2F10 pyrolysis, which gives SF4 + SF6, have been reinterpreted to give a value for the equilibrium constant of S2F10 ⇆ SF4 + SF6. This, together with statistical estimates of the entropy and heat capacity of S2F10, can be used to give for this reaction values of ΔH298° = 19.7 ± 1.0 kcal/mole and ΔS300° = 47.6 ± 2 gibbs/mole. ΔHf°(S2F10) = -494 kcal/mole. A compatible mechanism is shown to be S2F10 ⇆ 2SF5 (fast); 2SF5 ⇆ SF6 + SF4 (slow) with step 2 rate-determining. The overall, best first order rate constant is proposed as kmeas = 1017.42-43.0/θ sec-1 = K1k2, where θ = 2.303RT in kcal/mole.Independent measurements of δHf° and S° for the SF5 radical, permits the evaluation of the equilibrium constant K1 = 108.92-(27.1 ± 6)/θ l./mole-sec and yields k2 = 108.50-15.9/θ l./mole-sec. The observed homogeneous catalysis by NO and CHCl = CHCl can be explained in terms of a direct abstraction of F from S2F10 : C + S2F10 → CF + S2F9, followed by S2F9 → SF5 + SF4 and SF5 + CF ⇆ SF6 + C (C ≡ NO or C2H2Cl2).
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  • 169
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    International Journal of Chemical Kinetics 1 (1969), S. 479-481 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 170
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    International Journal of Chemical Kinetics 1 (1969), S. 473-477 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas phase isomerization of 1,1-dimethyl-2-vinylcyclopropane to cis-2-methylhexa-1,4-diene has been studied in a static system. The isomerization is homogeneous and kinetically first order. The rate constants were independent of initial reactant pressure in the range 0.6 to 2 torr and of added nitrogen up to 180 torr. Rate constants determined at 10 temperatures in the range 200 to 254°C fitted the Arrhenius equation k = 1011.41±0.02 exp (-33,540 ± 47 cal/RT) sec-1The low A factor and activation energy are consistent with a concerted 1,5-hydrogen migration via a “tight” cyclic transition complex.
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  • 171
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    International Journal of Chemical Kinetics 1 (1969), S. 459-472 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The intramolecular elimination of isobutene from 2-d1-triisobutylaluminum has been studied in the gas phase for temperatures ranging between 102.4 and 184.6°C. The reaction is apparently homogeneous and obeys the first order rate law, yielding the following Arrhenius relationship: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log \,k_{{\rm el}im} \left( {\sec ^{ - 1} } \right) = 11.1 - {{27.2} \mathord{\left/ {\vphantom {{27.2} {\theta \,{\rm where}\,\theta \,{\rm equals}\,4.58 \times 10^{ - 3} }}} \right. \kern-\nulldelimiterspace} {\theta \,{\rm where}\,\theta \,{\rm equals}\,4.58 \times 10^{ - 3} }}T\left( {{}^ \circ {\rm K}} \right)\,{\rm in}\,{\rm units}\,{\rm of}\,{{{\rm kcal}} \mathord{\left/ {\vphantom {{{\rm kcal}} {{\rm mole}{\rm .}}}} \right. \kern-\nulldelimiterspace} {{\rm mole}{\rm .}}} $$\end{document} Excess ethylene was added to the starting material in order to avoid complications from the backreaction. The cyclic 4-center nature of the transition state proposed earlier has been unequivocally demonstrated by deuterium labelling. Mass-spectral analyses show that the isobutene formed contains no deuterium. The hydrolyses products of the mixed trialkylaluminum formed during the reaction consist of monodeuteroethane and 2-d1-isobutane. The observed negative entropy of activation of ∼12 cal/°-mole agrees with prediction and implies a reasonably tight transition state structure. Combined with the corresponding data for the non deuterized Al(i-bu)3 reported earlier, these data result in a primary kinetic deuterium isotope effect of kH/kD = 1.3 × 100.6/θ corresponding to a ratio of the isotopic rate constants of 3.7 at 25°C. This result is in excellent agreement with a predicted value of 1.4 × 100.7/θ and it is in line with literature data on similar reactions involving cyclic transition state complexes.
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  • 172
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    International Journal of Chemical Kinetics 1 (1969), S. 483-486 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 173
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    International Journal of Chemical Kinetics 1 (1969), S. 487-492 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 174
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    International Journal of Chemical Kinetics 1 (1969) 
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    Keywords: Chemistry ; Physical Chemistry
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    Topics: Chemistry and Pharmacology
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  • 175
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    International Journal of Chemical Kinetics 1 (1969), S. 493-494 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 176
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 177
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    International Journal of Chemical Kinetics 1 (1969), S. 499-508 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gas phase bond isomerization of allyl fluoride, allyl chloride and allyl bromide, catalyzed by HBr and ultraviolet light, has been studied in the temperature range of 150-250° and at pressures of 3.5 to 50 mm. The reactions are very clean, first order in allyl halide and HBr, and have a light intensity exponent of unity. A quantum yield for allyl chloride of 3200 indicates a chain reaction. Dilution with inert gases is almost without effect, indicating that excited state intermediates are not involved. A small wall effect is observed. The evidence indicates a free radical reaction, involving hydrogen abstractions by bromine atoms, with replacement at the other end of the allylic radical.
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  • 178
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    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By photolyzing (CF2H)2CO and (CFH2)2CO the hydrogen atom abstraction reactions of CF2H radicals with (CF2H)2CO, H2, D2, CH4, C2H6, n—C4H10 and iso—C4H10, and the reactions of CFH2 radicals with (CFH2)2CO and n—C4H10, have been studied. Arrhenius parameters for these reactions are compared with related systems. From a knowledge of the activation energies for the forward and reverse reactions a value of the bond dissociation energy, D(CF2H—H) = 97.4 ± 1.3 kcal mole-1 at a mean temperature of 543°K is obtained. This value is subject to much uncertainty due to possible compensation effects in the Arrhenius parameters. These effects are discussed for this and the other reactions, and the data suggest that D(CF2H—H) is approximately 100 kcal mole-1, and that D(CFH2—H) is very similar. Other literature data tend to confirm these approximate values.
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  • 179
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    International Journal of Chemical Kinetics 1 (1969), S. 527-539 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This review presents in tabular and graphical form rate data on the reactions of atomic oxygen (O3P) with methane and ethane. The reliability of these data is discussed and suggested values of the rate constants are given over specified temperature intervals. Specific values are given for 298 and 1000°K.
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  • 180
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    International Journal of Chemical Kinetics 1 (1969), S. 581-583 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 181
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    International Journal of Chemical Kinetics 1 (1969), S. 551-569 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A detailed kinetic model of the HCl chemical laser produced by the flash photolytically initiated H2—Cl2 explosion is described, and the results of computer calculations on such a system are discussed. It is shown that currently accepted values of the various rate constants, supplemented in a few cases by reasonable estimates of previously unmeasured rate constants, are adequate to approximate the observed laser behavior of this system. It is also shown that the chemistry of such a system is extremely complex, and exhibits a high degree of coupling between one reaction and another; therefore, great care is required to extract kinetic data from the optical behavior of such laser systems. It is further argued that different hydrogen halide lasers may behave quite differently from each other, depending on the relative magnitudes of the various rate constants involved.
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  • 182
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    International Journal of Chemical Kinetics 1 (1969), S. 541-549 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal dissociation of COS was investigated in shock waves with argon as carrier gas. The concentration was varied between 0.05 and 0.5% COS in argon, the total density from 2.5 × 10-5 mole/cm3 to 2.5 × 10-3 mole/cm3. Temperatures between 1500°K and 3100°K were applied.For the reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm COS}\left({^1 \Sigma} \right)\mathop {\longrightarrow}\limits^{K_{\rm 1}} {\rm CO}\left({^1 \Sigma ^ +} \right) + {\rm S}\left({^3 P} \right) $$\end{document} the rate constant was found to be \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{10} \approx 10^{14.2} \exp - \left({\frac{{61000}}{{RT}}} \right) \quad\quad ({\rm cm}^3 {\rm mole}^{- 1} \sec ^{- 1}) $$\end{document} in the low pressure range of the unimolecular reaction and \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{1\infty} \approx 10^{11.6} \exp - \left({\frac{{61000}}{{RT}}} \right) \quad\quad (\sec ^{- 1}) $$\end{document} in the high pressure range.
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  • 183
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    International Journal of Chemical Kinetics 1 (1969), S. 571-580 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The addition of methyl radicals to tetrafluoroethylene in the gas phase has been studied over the temperature range 80-180°C, using a material balance method. \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_{\rm 3} + {\rm C}_2 {\rm F}_{\rm 4} \to {\rm CH}_3 {\rm C}_2 {\rm F}_4 $$\end{document}Arrhenius parameters of 1011.95±0.23 (mole-1 cm3 sec-1) and 5.7 ± 0.4 (kcal/mole) have been measured for the addition reaction.Electrophilic reagents such as O or CF3 appear to react almost equally readily with ethylene and tetrafluoroethylene but methyl radicals add much more rapidly to tetrafluoroethylene than to ethylene, the difference in reactivity being principally due to an activation energy difference of ∼2 kcal/mole.
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  • 184
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    Calcified tissue international 2 (1968), S. 237-241 
    ISSN: 1432-0827
    Keywords: Carbonate ; Bone ; Fish ; Apatite
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé D'après la littérature, il semble que les poissons soient obligées d'hyperventiler en CO2, pour recevoir suffisamment d'oxygène. Ils présenteraient par suite une quantité faible de bicarbonate circulant. Dans cet ordre d'idée, les arêtes de truites et de carpes ont été analysés pour établir si la composition du minéral osseux traduit la faible concentration en bicarbonate sérique. Le contenu en CO2 d'arêtes de poissons n'est pas significativement différent de celui des os normaux de mammifères. Des crîstaux d'apatite synthétique, préparés dans des conditions identiques de T, μ et (HCO 3 − ), ne contiennent que 1/7ème à 1/8ème du CO2 d'arêtes de poissons. Ces résultats indiquent que la composition des liquides dans l'os ne réfléchit pas simplement la composition du sérum circulant, ainsi qu'on l'admet généralement.
    Abstract: Zusammenfassung Es ist in der Literatur berichtet worden, daß Fische, um genügend Sauerstoff zu erhalten, einen Überschuß von Kohlensäure einatmen müssen und folglich einen niedrigen Gehalt an Bicarbonaten im Kreislauf aufweisen. Knochen von Forellen und Karpfen wurden analysiert, um festzustellen, ob ihre Mineralsalzzusammensetzungen die niedrigen Serum-bicarbonate-konzentrationen wiederspiegeln. Die Resultate zeigten keinen wesentlichen Unterschied zwischen dem Carbonatgehalt der Knochen von Fischen und Säugetieren. Synthetische Apatitkristalle, die unter ähnlichen Bedingungen von T, μ und HCO3 bereitet wurden, wiesen nur 1/7–1/8 des Carbonatgehaltes der Fischknochen auf. Diese Ergebnisse deuten zweifellos darauf hin, daß zwischen der Zusammensetzung der Gewebeflüssigkeit der Knochen und des Serums kein einfacher Zusammenhang besteht.
    Notes: Abstract It has been reported in the literature that fish, to get sufficient oxygen, must overventilate with respect to CO2 and therefore exhibit a low circulating level of bicarbonate. Accordingly, the bones of trout and carp were analyzed to learn if the composition of their bone mineral reflects the low serum level of bicarbonate. It was found that the CO2 content of fish bone is not significantly different from that of normal mammalian bone. Synthetic apatite crystals, made under comparable conditions of T, μ, and (HCO 3 − ) were found to contain only 1/7th to 1/8th the CO2 of fish bone. These data strongly suggest that the composition of the fluids in bone does not reflect, in a simple way, the composition of the circulating serum as is generally assumed.
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    Calcified tissue international 2 (1968), S. 262-270 
    ISSN: 1432-0827
    Keywords: Bone ; Exchange ; Radioisotopes ; Ions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Une hypothèse, destinée à rendre compte de façon semi-quantitative, des grandes variations de temps nécessaire à équilibrer, au niveau du squelette, divers produits radioactifs, introduits dans le torrent circulatoire, est mise au point. Cette hypothèse est basée sur le fait que 3 facteurs interviennent dans les échanges osseux: a) la vitesse de perfusion de l'os, b) la concentration ionique du plasma, et c) la concentration ionique de l'os. Partant de cette hypothèse et de résultats publiés dans la littérature, “des temps de cyclage” sont calculés par Cl−, Na+, K+ et Ca++. Ils varient selon quatre ordres de grandeur (de 10 min pour Cl− à 64 jours Ca++, chez le rat). Ces résultats ont été vérifiés pour des échanges de22Na et de45Ca dans une colonne d'apatite minéralin vitro. Des échanges de36Cl et de42K ont été étudiésin vivo au niveau du fémur de rat. La disparition sanguine du22Na a été suivie chez l'Homme. Enfin des résultats d'échanges de45Ca, au niveau de molaires de rat, publiés dans la littérature, ont été recalculés. Dans chaque cas, les résultats expérimentaux ont confirmé les prédictions de l'hypothèse du cyclage.
    Abstract: Zusammenfassung Es wurde eine Hypothese aufgestellt, um auf semi-quantitative Weise die breite Variabilität der Zeit zu erklären, die benötigt wird, um im Skelett ein Gleichgewicht von verschiedenen radioaktiven in den Kreislauf eingeführten Substanzen herzustellen. Diese Hypothese beruht auf der Annahme, daß der geschwindigkeitsbeschränkende Faktor beim Knochenaustausch durch 3 Variablen definiert ist: a) das Maß der Knochenperfusion, b) die Konzentration der Ionen im Plasma und c) die Konzentration der Ionen im Knochen. Auf Grund dieser Annahme und gestützt auf Angaben aus der Literatur wurden die “cycling times” für Cl−, Na+, K+ und Ca++ berechnet. Diese variieren in 4 Größenordnungen, beispielsweise von 10 min für Cl− bis zu 64 Tagen für Ca++ bei der Ratte. Diese Annahmen wurden für den Austauschin vitro von22Na und45Ca in Apatitmineral in einer Säule geprüft. Der Austausch von36Cl und von42K wurdein vivo am Rattenfemur studiert. Die Abnahme von22Na im menschlichen Blut wurde ebenfalls verfolgt. Schließlich wurden Literaturangaben über den Austausch von45Ca in Rattenbackenzähnen überprüft. Die Versuchsresultate kamen dabei sehr nahe an die auf Grund des “cycling concept” erwarteten. Einige der Zusammenhänge dieser Befunde werden kurz besprochen.
    Notes: Abstract An hypothesis has been developed to explain in a semi-quantitative fashion the wide variations in time required for the equilibration in the skeleton of various radioactive substances when they are introduced into the circulation. The basis for the hypothesis rests on the assumption that three variables define the rate-limiting step in bone exchange: a) the rate of perfusion of bone, b) the concentration of the ion plasma, and c) the concentration of the ion in bone. Using this idea and data from the literature, “cycling times” were calculated for Cl−, Na+, K+, and Ca++. They were found to vary by four orders of magnitude (from 10 min for Cl− to 64 days for Ca++ in the rat). These predictions were tested for22Na- and45Ca-exchange in a column of apatite mineralin vitro. In vivo 36Cl- and42K-exchange in rat femur was studied. The blood disappearance of22Na in man was also examined. Finally, data in the literture of45Ca-exchange in the rat molar was redrawn. In every case, experimental results closely approximated the predictions of the cycling concept. Some of the implications of these findings are briefly discussed.
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  • 186
    ISSN: 1432-0827
    Keywords: Bone ; Glycosaminogloycans ; Hyperparathyroidism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Les glycosaminoglycanes de l'os compact ont été identifiés, par la méthode de précipitation au chlorure de cetylpyridinium, chez le chien normal et des chiens soumis à 20 ou 30 U.S.P. d'extrait parathyroïdien pendant 5 et 3–4 jours. Les concentrations d'héxosamines totales ainsi que les héxosamines, en rapport avec les glycoaminoglycanes acides, précipités par chlorure de cetylpyridinium, sont déterminées. En outre, la répartition du glycosaminoglycane de la zone d'ossification épiphysaire ainsi que l'incorporation du35S-sulfate dans les glycosaminoglycanes du tissu osseux et du cartilage épiphysaire, après administration de35S-sulfatein vivo, ont été étudiées. Dans l'os compact, les héxosamines, en rapport avec les glycosaminoglycances acides, constitutent environ un tiers de la concentration totale en héxosamine et environ 0,05–0,06% du poids sec total. Le constituant principal des glycosaminoglycances acides osseux est formé par le chondroitine-4-sulfate. Ce dernier est plus riche en sulfate et présente un poids moléculaire plus élevé que le chondroitine sulfate du cartilage épiphysaire, qui, selon des travaux antérieurs, présente des caractéristiques infra-rouges du chondroitine-4-sulfate et du chondroitine-6-sulfate, avec prédominance du premier. Les poids moléculaires du chondroitine sulfate osseux varient surtout d'environ 45000 et 56000. L'acide hyaluronique constitute une faible fraction des glycosaminoglycanes osseux. Des différences marquées de l'activité spécifique des fractions de cohondroitine sulfate de l'os et du cartilage épiphysaire, à poids moléculaires variables, on tété notées de façon répétée. L'administration d'extrait parathyroïdien à des chiens n'a pas d'effet sur les poids moléculaires en chondroitine sulfate de l'os ou du cartilage épiphysaire. Elle n'influence pas non plus les concentrations en héxosamines totales ou en glycosaminoglycances acides. Dans ces tissus, il ne se produit pas d'effect de stimulation ou de dépression concernant l'incorporation de35S-sulfate dans le chondroitine sulfate our sur la séparation moléculaire de molécules transformées en sulfates et/ou de molécules synthétiques de sulfate chondroitine.
    Abstract: Zusammenfassung An normale Hunden und an Hunden die unter 5 respektive 3–4 Tagen 20 oder 30 U.S.P./kg Parathyreoidea-Extract erhalten hatten, wurden im kompakten Knochen die Glykosaminoglykane unter Anwendung der Cetylpyridiniumchlorid-Fällungsmethode identifiziert und die Konzentration des Total-Hexosamins und des Hexosamins, entsprechend den Cetylpyridiniumchlorid fällbaren sauren Glykosaminoglykanen, wurde bestimmt. Außerdem wurden das Glykosaminoglykanmuster der Epiphysenplatte und der Einbau von35S-Sulfat in die Glykosaminoglykane des Knochengewebes und des Epiphysenknorpels nach Zufuhr von35S-Sulfatin vivo studiert. Im kompakten Knochengewebe macht des Hexosamin, entsprechend den sauren Glykosaminoglykanen, ungefähr ein Drittel der totalen Hexosaminkonzentration und ungefähr 0,05–0,06% des totalen Trockengewichtes aus. Der Hauptanteil der sauren Glykosaminoglykane im Knochen war Chondroitin-4-Sulfat. Dieses war in höherem Grad sulfatiert und hatte ein höheres Molekülgewicht als das Chondroitinsulfat der Epiphysenplatte, welches, in Übereinstimmung mit früheren Untersuchungen, Infrarot spektra kennzeichnend für sowohl Chondroitin-4-sulfat als auch für Chondroitin-6-sulfat, das Erstere überwiegend, hatte. Das Molekülgewicht des Hauptanteiles des Knochen-Chondroitinsulfates lag zwischen ungefähr 45000–56000. Ein kleiner Teil der Knochen-Glykosaminoglykane war Hyaluronsäure. Sowohl im Knochengewebe als auch im Epiphysenknorpel wurde in verschiedenen Fraktionen des Chondroitinsulfates, mit unterschiedlichem Molekülgewicht, grße und regelmäßig reproduzierbare Unterschiede in der spezifischen Aktivität gefunden. Behandlung der Hunde mit Parathyreoideaextrakt gab keinen Ausschlag in den Molekülgewichten des Chondroitinsulfates, weder des Knochens noch des Epiphysenknorpels. Ebenso wurde kein eindeutiger Effekt auf die Konzentration des totalen Hexosamins oder der sauren Glykosaminoglykane gefunden. Kein offenbarer, weder anregender noch senkender, Effekt auf den Einbau von35S-Sulfat in das Chondroitinsulfat oder in der molekularen Verteilung der neulich sulfatierten und/oder synthetisierten Moleküle des Chondroitinsulfates dieser Gewebe wurde gefunden.
    Notes: Abstract In normal dogs and in dogs treated with 20 or 30 U.S.P. parathyroid extract for 5 and 3–4 days, respectively, the glycosaminoglycans of compact bone tissue were identified using the cetylpyridinium chloride precipitation method, and the concentrations of total hexosamines and the hexosamines corresponding to cetylpyridinium chloride precipitable acid glycosaminoglycans were determined. Further, the glycosaminoglycan pattern of the epiphyseal plate and the incorporation of35S-sulphate into the glycosaminoglycans of bone tissue and epiphyseal cartilage after administration of35S-sulphatein vivo was studied. In compact bone tissue, the hexosamines corresponding to acid glycosaminoglycans constuted approximately one third of the total hexosamine concentration and approximately 0.05–0.06% of the total dry weight. The main component of the acid glycosaminoglycans in bone was chondroitin-4-sulphate. This was sulphated to a higher degree and also of a higher molecular weight than thechondroitin sulphate of the epiphyseal cartilage, which in accordance with earlier investigations was found to have infrared characteristics of both chondroitin-4-sulphate and chondroitin-6-sulphate, with the former dominating. The molecular weights of the main part of bone chondroitin sulphate ranged from approximately 45,000 to 56,000. A small component of the bone glycosaminoglycans was hyaluronic acid. Large regularly recurring differences in the specific activity of fractions with differences in molecular weight in the condroitin sulphate of bone tissue and epiphyseal cartilage were noted. Treatment of the dogs with parathyroid extract gave no effect on the molecular weights of the chondroitin sulphate of the bone matrix or of the epiphyseal cartilage. Nor was there any unequivocal effect on the concentrations of total hexosamines or on the acid glycosaminoglycans. No evident stimulatory or depressant effect on the incorporation of35S-sulphate into the chondroitin sulphate or in the molecular distribution of newly sulphated and/or synthesized molecules of the condroitin sulphate within these tissues occurd.
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  • 187
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    Anatomy and embryology 127 (1968), S. 66-71 
    ISSN: 1432-0568
    Keywords: Bone ; Intervertebral disc ; Epiphyses ; Photography/Instrumentation ; Infrared rays
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Summary Photographing with the aid of short-wave infra-red light has been used for improved photographic demarcation of hyaline cartilage from connective tissue and fibrous cartilage in specimens from children. This improved effect seems to be the result of a particularly high permeability to infra-red light rays in the hyaline cartilage of children.
    Notes: Zusammenfassung Das Photographieren mit kurzwelligem infrarotem Licht wurde zur verbesserten photographischen Begrenzung des hyalinen Knorpels gegenüber dem Bindegewebe und dem fibrösen Knorpel bei Präparaten von Kindern benutzt. Der Effekt scheint auf eine speziell hohe Durchlässigkeit beim hyalinen Knorpel des Kindes für die infrarote Strahlung zurückzuführen zu sein.
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  • 188
    ISSN: 1432-0568
    Keywords: Bone ; Femur ; Density ; Strength ; Man
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Die Corticalisdichte des Femurschaftes nimmt bei den untersuchungten Männern (398 Probekörper) und Frauen (337 Probekörper) mit zunehmendem Alter ab. Die Beziehung zwischen dem Quadrat der aus Röntgenbildern densitometrisch ermittelten Dichte und dem Alter in Jahren ist nicht linear. Die mittlere Dichte des Femurschaftes und die Dichtespektren in den Schaftquerschnitten sind sowohl bei verschiedenen Individuen als auch auf der rechten und linken Körperseite der gleichen Person different. Die Dichtespektren der drei proximalen Schaftquerschnitte sind im Mittel gleich aber von den zwei distalen verschieden. Die mittlere Materialverteilung in der Corticalis von 8 Femora wird dargestellt (Abb. 4). Zwei Dichte-Festigkeitsfunktionen werden für Personen unter bzw. über 67,8 Jahren berechnet und die Linearität der Regressionen der Festigkeitsquadrate auf die Dichtequadrate nachgewiesen. Die Beziehung zwischen Dichte und Bruchfestigkeit ist in beiden Altersgruppen gleich, aber bei gleicher Knochendichte ist die Bruchfestigkeit der Probekörper in der zweiten Altersgruppe geringer als in der ersten. Unterschiede in der Bruchfestigkeit können nur zu 40 bzw. 42% auf Unterschiede in der Knochendichte zurückgeführt werden, d. h. die Festigkeit des Knochens ist zwar dem Kalksalzgehalt proportional, aber darüber hinaus verbleibt ein bedeutender, aus Röntgenbildern nicht zu ermittelnder Rest an Bruchfestigkeitsunterschieden.
    Notes: Summary The x-ray determined density of the compact femoral shaft bone is negatively correlated with age (r=−0.2829) in 398 male and 337 female specimens of cortical bone. The regression of density on age is non-linear. The differences in mean density of the femoral shaft and the density spectra of the shaft cross sections are significant between individuals and between left and right femora in individuals. the density spectra of the 4 proximal cross sections of the shaft are equal, but different from the 2 distal ones. the mean distribution of bone material in the corticalis of 8 femora is presented diagrammatically in Fig. 4. Two density strength functions were calculated by the method of least squares for individuals younger and older than 67.8 years respectively and the linearity of the 2 regression lines are shown in an analysis of variance. An analysis of covariance revealed no significant differences between the slopes of the 2 regressions but a significant difference in elevation; that is, the breaking strength of specimens of equal density is different in the two age groups (lower in the older one), but this difference is equal in all density intervals. Only 40 or 42% of strength variation is due to density variation.
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  • 189
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    Anatomy and embryology 127 (1968), S. 1-24 
    ISSN: 1432-0568
    Keywords: Bone ; Femur ; Density ; Strength ; Man
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Untersucht wurden 40 Femora (meist Paare vom selben Individuum) von 12 Frauen und 12 Männern. Aus jedem Knochen wurden in 5 gleichmäßig über die Schaftlänge verteilten Höhen Querschnittsscheiben entnommen, und von diese Röntgenaufnahmen angefertigt. In jeder Aufnahme wurde die Strahlenabsorption in der Corticalis an der Vorderseite, Hinterseite, medial und lateral gemessen. Daraus wurde die Dichte, bezogen auf einen Vergleichskörper aus Aluminium, in g/cm3 Aluminium berechnet. An denselben Stellen, deren Dichte bekannt war, wurden Probekörper gewonnen und deren Druckfestigkeit gemessen. Ergebnisse. 1. Materialdichte (Röntgenstrahlenabsorption) und Festigkeit der Femurschaftcorticalis stehen in Zusammenhang. 2. Beide nehmen von der Schaftmitte gegen die Gelenkenden hin ab. 3. Strahlenabsorption (Dichte) und Festigkeit sind über den Knochenquerschnitt ungleichmäßig verteilt, sie sind medial und lateral relativ größer als vorn und hinten. 4. In der Crista femoris nimmt die Dichte von innen nach außen zu. 5. Aus diesen Befunden wird abgeleitet, daß die funktionelle Anpassung des Knochens an seine mechanische Beanspruchung nicht nur in einer Änderung der Querschnittsfläche, sondern auch in einer lokalen Änderung seiner Materialdichte besteht.
    Notes: Summary 200 cross sections of 40 femora (mostly pairs of the same individual) of 12 women and 12 men were examinated. On x-ray photographs of each specimen, density measurements were made in 4 sites: posterior, anterior, medial, and lateral. after densitometry, the compressive strength was determined on samples from the same sites. Conclusions: 1. Bone density (x-ray absorption) and strength are correlated. 2. They decrease from the middle of the shaft to both ends. 3. Density and strength are distributed inhomogeneously over the cross section, being relatively higher in the medial and lateral regions. 4. In the crista femoris, density increases from the centre to the outer surface. 5. From these facts is derived, that functional adaptation of the bone on its mechanical stresses is reached not only by adaptation of the cross section area, but also by local change of density.
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  • 190
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    Calcified tissue international 2 (1968), S. 165-176 
    ISSN: 1432-0827
    Keywords: Mineral ; Exchange ; Bone ; Isotope ; Radioactive-Autoradiography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Des produits marqués variés (urée, Cl−, K+, Na+, HCO 3 − , PO 1 3− , Ca++) sont administrés à des groupes de rats jeunes et âgés. Les résultats pour Mg++ sont empruntés à ceux trouvés dans la littérature. Une heure et demic plus tard, des fragments d' os longs sont prélevés et nettoyés minutieusement. La concentration de ces substances marquées et non marquées est déterminée. L'intervalle de temps choisi est utilisé afin de permettre l'équilibre de la phase aqueuse de l'os, tout en réduisant les échanges de surface, la recristallisation, la diffusion solide et la croissance ou la résorption. Avec des intervalles de temps fixes, avec les mêmes espèces ainsi que des specimens osseux et des techniques identiques, une comparaison des échanges entre les divers es substances dans l'os a pu être effectuée. Les résultats ont pu être répartis en trois groupes: a) échange total (urée, Cl− et K+); b) échange partiel, diminuant de façon variable avec l'âge (Na+, CO2 et Mg++); et c) échange faible (Ca++ et PO 4 3− ). La classification classique de sequelette «accessible» et «non accessible» parait peu conforme et dépend des conditions et de la nature de la substance étudiée. Un concept général des échanges osseuxin vivo devrait être élaboré. Des calculs concernant la concentration apparente des divers electrolytes au niveau de la phase aqueuse de l'os montrent qu'elle a une concentration nettement différente de celle du plasma. La concentration du potassium y est, en particulier, remarquablement élevée.
    Abstract: Zusammenfassung Gruppen von jungen und alten Ratten erhielten Injektionen von verschiedenen markierten Substanzen (Harnstoff, Cl−, K+, Na+, HCO 3 − , PO 4 3− , Ca++). Die Angaben für Mg++ wurden der Literatur entnommen. 11/2 Std später wurden die Diaphysen der behandelten Tiere gewonnen, sorgfältig gereinigt und deren Gehalt an kalten und radioaktiven Substanzen bestimmt. Dieser Zeitpunkt wurde gewählt, um ein Gleichgewicht innerhalb der wäßrigen Phase des Knochens sicherzustellen und ein gleichzeitiges Mitwirken des Oberflächenaustausches, der Rekristallisation, der festen Diffusion, des Wachstums oder der Resorption möglichst einzuschränken. Wurden Variablen wie Zeit, Rattenart, Knochenproben und Methodik festgelegt, so konnten eindeutige Vergleiche hinsichtlich des Austausches dieser verschiedenen Substanzen im Knochen gezogen werden. Die erhaltenen Resultate konnten in drei Kategorien eingeteilt werden: a) vollständiger Austausch (Harnstoff, Cl−, K+); b) teilweiser Austausch, je nach Alter unterschiedlich abnehmend (Na+, CO2 und Mg++); c) minimaler Austausch (Ca++ und PO 4 3− ). Offenbar ist die klassische Einteilung in “verfügbares” und “nichtverfügbares” Skelet zweideutig und abhängig von den Bedingungen sowie von den Ionen oder Substanzen, die für den Versuch gewählt wurden. Es liegt auf der Hand, daß ein neues, allgemeingültiges Konzept für den Knochenaustauschin vivo dringend benötigt wird. Berechnungen der scheinbaren Konzentration der verschiedenen Elektrolyte in der Knochenflüssigkeit ergaben, daß die wäßrige Phase des Knochens eine deutlich andere Zusammensetzung als die Plasmaflüssigkeit hat. Insbesondere konnte in der Knochenflüssigkeit eine bemerkenswert hohe Kaliumkonzentration festgestellt werden.
    Notes: Abstract Groups of young and old rats were injected with a variety of labelled substanzes (urea, Cl−, K+, Na+, HCO 3 − , PO 4 3− , Ca++). Data for Mg++ were taken from the literature. One and a half hours later, compact shafts of long bones were removed and cleaned scrupulously, and analyses were performed for both “cold” and isotopic concentrations of substances. This time point was chosen to insure equilibration of the aqueous phase of bone while minimizing contributions from surface exchange, recrystallization, solid diffusion, growth or resorption. With fixed variables of time, species, bone specimen, and methodology, uambiguous comparisons of the exchange in bone could be made between the many substances studied. The exchange data could be divided into three categories: a) complete exchange (urea Cl−, and K+); b) partial exchange, decreasing variably with age (Na+, CO2, and Mg++); and c) minimal exchange (Ca++ and PO 4 3− ). Clearly the traditional classification of “available” and “unavailable” skeleton is ambiguous and determined by the conditions and the ion or substance chosen for study. Clearly also, a new overall concept of bone exchangein vivo is badly needed. Calculations of the apparent concentration of the various electrolytes in bone water reveal that the aqueous phase of bone has a composition markedly different from plasma water. In particular, the concentration of potassium in bone water was found to be remarkably high.
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  • 191
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    Calcified tissue international 2 (1968), S. 343-352 
    ISSN: 1432-0827
    Keywords: Nucleation ; Mineralization ; Bone ; Collagen ; Apatite
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Nous avons utilisé de la collagène d'os de mounton et de tendons de queues de rats et des cristaux d'apatite pour étudier dans un système modèle la catalysation de la nucléation et la déposition de minéral dans un tampon métastabile. La collagène d'os de mouton se trouvait être un bon catalysateur, tandis que des expériences antérieures ont démontré que la collagène de tendons de queues de rats était un catalysateur très faible. Le phase rapide de la déposition de l'apatite dans la collagène se termine aussitôt que le contenu du minéral a attaint au plus 50 à 60 pour cent, bien que la supersaturation du tampon est encore bien èlevée. Les résultats montrent que dans un tel système modèle la quantité du depôt minéral est réglée par des facteurs semblables à ceux qui opèrent pendant la calcification biologique.
    Abstract: Zusammenfassung Kollagen aus Schafsknochen und Rattenschwanzsehnen und Apatitkeime wurden verwendet in einem Modell-System zur Untersuchung der katalytischen Nukleation und der Fällung von Mineral in einem metastabilen Calciumphosphatpuffer. Kollagen aus Schafsknochen war ein guter Katalysator für die Nukleation, während in früheren Versuchen sich herausstellte, daß Rattenschwanzkollagen ein ganz schlechter Katalysator ist. Die schnelle Phase der Apatitfällung im Kollagen war beendet, wenn der Mineralgehalt bis zu 50–60% angestiegen war, obwohl der Puffer noch stark übersättigt war. Die Resultate weisen daraufhin, daß die Menge des gefällten Minerals in einem solchen Modell-System von ähnlichen Faktoren reguliert wird wie die biologische Verkalkung.
    Notes: Abstract Sheep bone collagen, rat tail tendon collagen and apatite seeds were used in a model system to study nucleation catalysis and mineral deposition in a metastable calcification buffer. Sheep bone collagen was shown to be a good nucleation catalyst, while earlier experiments have shown that rat tail tendon collagen was a very poor catalyst. The rapid phase of apatite deposition in the collagen was terminated as soon as a mineral content of not more than 50–60 per cent was reached, although the buffer was still highly supersaturated. The results suggest that the amount of mineral deposited in such a model system is regulated by factors similar to those operating in biological calcification.
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  • 192
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    Calcified tissue international 2 (1968), S. 77-82 
    ISSN: 1432-0827
    Keywords: Bone ; Metabolism ; Ascorbic Acid ; Tissue Culture
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Du tissu osseux, cultivé pendant 5 jours dans un milieu chimiquement défini, présente une augmentation de la consommation en O2 et une diminution de la production d'acide lactique lorsqué de l'acide lactique (50 μg/mI) est présent dans le milieu de culture. Ces paramètres ont été mesurés pendant des incubations de courte durée, en cultures de tissus. En n'ajoutant de l'acide lactique qu'au dernier jour de culture ou pendant les 4 premiers jours, et non le dernier jour, les valeurs en O2 et en acide lactique sont identiques à celles observées lorsque la vitamine est présente pendant 5 jours. Des produits similaires à l'acide ascorbique (50 μg/ml), administrés pendant 5 jours donnent des résultats identiques à ceux de la vitamine C. Une expérience préliminaire pour évaleur la vitesse d'oxydation de l'acide ascorbique dans le milieu de culture a permis de montrer que la vitamine doit être remplacée quotidiennement lorsque les cultures sont traitées avec 20% d'O2 et plus fréquemment avec des concentrations d'O2 plus élevées. Les changements dans le métabolisme énergétique, liés à l'acide ascorbique et observés dans cette étude, indiquent que la vitamine pourraît être un facteur important de stimulation du métabolisme squelettique aérobique.
    Notes: Abstract Bones cultured for 5 days in a chemically defined medium showed an increased O2 consumption and decreased lactic acid production when ascorbic acid (50 μg/ml) was present in the culture medium. In this and the following experiments these parameters were measured in short-term incubations following tissue culture. Adding ascorbic acid for only the final day of culture or for the first 4 days and not the final day gave O2 and lactic acid results similar to those obtained when the vitamin was present for all 5 days. Ascorbic acid analogs (50 μg/ml) added for 5 days also exhibited results similar to those for vitamin C. A preliminary experiment to evaluate the oxidation rate of ascorbic acid in the culture medium established that the vitamin must be replenished daily when cultures are gassed with 20% O2 and more frequently with higher O2 concentrations. The ascorbic acid-dependent changes in energy metabolism seen in this study suggest that the vitamin may be an important factor in stimulating skeletal aerobic metabolism.
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  • 193
    ISSN: 1432-0827
    Keywords: Collagen ; 14C-Proline ; Growth ; Bone ; Teeth
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Zusammenfassung Das Ausmaß, bis zu welchem Austausch- und Wiederverwendungsprozesse der mineralen Tracer die Messungen des mineralen Skelett-Auf- und Abbaues beeinflussen können, wurde ausgewertet; zu diesem Zweck wurde die Geschwindigkeit des Auftretens und Verschwindens von85Sr und von14C-Prolin-Hydroxyprolin in Knochen und Zähnen von wachsenden Ratten während der 12 auf die simultane parenterale Injektion dieser Tracer folgenden Tage verglichen. Der Ausdruck für die relative Geschwindigkeit des Kollagen-Auf- und Abbaues, bei welchem im Gegensatz zum Mineralmetabolismus kein Mitwirken des Austauschphänomens vermutet wird, basiert auf der Umwandlung von14C-Prolin zu14C-Hydroxyprolin; die spezifische Aktivität des letzteren wurde bestimmt. Aus der spezifischen Aktivität des Minerals sowie jener des Kollagens konnten die Geschwindigkeit und die Art des Wachstums der untersuchten Proben ersehen werden, d.h.schnelles Wachstum und ein kurzes Zeitintervall zwischen Bildung und Resorption des Gewebes imKnochen der Metaphyse, die auch die knorpelige Wachstumsplatte enthält, und andererseitslangsames Wachstum und längeres Zeitintervall (länger als die 12 Tage des Experimentes) zwischen Bildung und Resorption des Gewebes imKnochen der Diaphyse und in den Schneidezähnen. Immerhin fiel die spezifische Aktivität des Kollagen/Mineral-Anteils im Knochen der Metaphyse während dem 4–12tägigen Zeitintervall auf die Hälfte, im Gegensatz zum Knochen der Diaphyse und der Schneidezähne, bei welchen während dieser Zeitspanne kein Unterschied in diesem Verhältnis beobachtet wurde. Diese Ergebnisse zeigen, daß Kollagen in der Wachstumszone der Metaphyse durch Resorption verschwindet, bevor es ganz mineralisiert ist, und daß der Austausch ein relativ unwichtiger Faktor in der Kinetik auf lange Sicht des Knochenminerals ist.
    Notes: Abstract The extent to which exchange and reutilization processes of mineral tracers affect skeletal mineral accretion and resorption measurements was evaluated by comparing the rates of appearance and disappearance of85Sr and14C-proline-hydroxyproline in bones and teeth in growing rats for 12 days following simultaneous parenteral injection of these tracers. Expressions for the relative rates of collagen synthesis and breakdown, which unlike mineral metabolism are considered not to be complicated by exchange phenomena, were based on14C-proline conversion to14C-hydroxyproline; the specific activity of the latter was determined. Both the mineral and the collagen specific activities reflected the rates and patterns of growth of the samples assayed; rapid growth and a short interval of time between formation and resorption of tissue in themetaphyseal bone which contains the cartilagineous growth plate, slow growth and an interval of time between formation and resorption of tissue indiaphyseal bone and incisor teeth which is longer than the 12 days of the experiment. However, in metaphyseal bone the specific activity collagen/mineral ratio dropped by one half during the 4–12 day interval in contrast to diaphyseal bone and incisor teeth in which no change in this ratio was observed during this period of time. The data indicate that collagen in the metaphyseal growth zone is removed by resorption before it has become fully mineralized, and that exchange is a relatively unimportant factor in the long term kinetics of bone mineral.
    Type of Medium: Electronic Resource
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  • 194
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    Electronic Resource
    Springer
    Calcified tissue international 2 (1968), S. 177-182 
    ISSN: 1432-0827
    Keywords: Microradiography ; Bone ; Dentin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Les couches de matrice osseuse entourant les lacunes des osteocytes qui sont apparemment hypermineralisees (radioopaques), peuvent etre eliminees des microradiographies au moyen d'une agitation continue au cours de developpement. Il en va de meme des bordures radioopaques situees le long des felures artificielles dans les coupes. Les structures reellement hypermineralisees, telles que la dentine peritubulaire, les lignes cementantes es les bords internes des osteones ne sont pas modifiees par le traitement.
    Abstract: Zusammenfassung Das Auftreten einer hypermineralisiert erscheinenden Schicht von Knochengewebe um die Knochenhoehlchen, aber auch dasjenige von dichter erscheinenden Rändern an künstlich erzeugten Spalten in den Gewebsschnitten, konnte verhindert werden durch stetiges Agitieren während der Entwicklung der Historadiogramme. Dagegen hatte die gleiche Behandlung keinen Einfluß auf das Sichtbarbleiben anderer, wirklich hypermineralisierter Gebilde, z. B. der Ränder der Zahnbeinkanälchen, Knochenkittlinien, und Binnensäume von Osteonen.
    Notes: Abstract Apparently hypermineralized (radiopaque) layers of bone matrix surrounding osteocyte lacunae, as well as radiopaque edges along artificial cracks in the sections, could be eliminated from microradiographs by continuous agitation during development. Other hypermineralized structures, such as peritubular dentin, cementing lines and the inner edges of osteons, persisted and were not artefacts of development.
    Type of Medium: Electronic Resource
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  • 195
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    Archives of toxicology 23 (1968), S. 245-249 
    ISSN: 1432-0738
    Keywords: Bone ; Strontium poisoning ; Parathormone ; Kidney ; Knochen ; Strontiumvergiftung ; Parathormon ; Niere
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Die Restitution des strontiumgeschädigten Skelets wachsender Sprague Dawley Ratten ist von einem Anstieg der dialysablen Strontium- und Calciumfraktion des Serums begleitet. Die Ergebnisse legen eine Beeinflussung der renalen Manipulation von Kationen bei Knochenschädigungen durch Fremdmetalle nahe.
    Notes: Summary Restitution of skeletal damage caused by strontium in growing Sprague Dawley rats is accompanied by an increase in the dialysable serum fractions of strontium and calcium. The results suggest that the renal manipulation of cations is influenced in bone lesions caused by foreign metals.
    Type of Medium: Electronic Resource
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  • 196
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 2 (1968), S. 563-563 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 197
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 2 (1968), S. 651-662 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On propse comme une modification de la méthode SCF-MO-LCGO, une méthode qualitative et on traite le naphthaléne comme illustration. Les rèsultats de ce calcul sont en bon accord avec l'experience. On discute les avantages de la mèthode proposée pour les calculs de la chimie quantique.
    Abstract: Eine Modifikation des SCF-MO-LCGO-Verfahrens in Form einer qualitativen ab initio Methode wird angegeben und als testrechnung auf Naphthalin angewendet. Die Ergebnisse stehen im Einklang mit der Erfahrung. In diesem Zusammenhang wird das Verfahre in den allgemeinen Rahmen gestellt und seine Möglichkeiten diskutiert.
    Notes: A modification of the SCF-MO-LCGO method is proposed in the form of a qualitative ab initio method. Naphthalene is treated as a test case; good agreement between calculated and experiemental results is obtained. The capabilities of the method for quantum-chemical calculations are discussed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 198
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On présente une discussion de la factorisation de l'équation séculaire à l'aide des constantes du mouvement, et on obtient des formules qui lient les facteurs résultants aux traces de certains opérateurs. Ces traces-ci sont indépendantes de la base de l'espace vectoriel, ce qui implique que les facteurs de l'équation séculaire le sont aussi. Les résultats sont employés aussi au cas de factorisation à l'aide d'un groupe de symétrie fini.
    Abstract: Es wurde eine Diskussion von der Faktorisierung der Säkulargleichung mittels der Bewegungskonstanten gegeben. Formeln wurden hergeleitet, die resultierenden Faktoren mit den Spuren gewisser Operatoren in Verbindung bringt. Die Spuren sind von der Basis des Vektorraums unabhängig und dafür haben auch die Faktoren der Säkulargleichung dieselbe Eigenschaft. Die Resultate wurden auch auf die Faktorisierung mittels einer endlichen Symmetriegruppe angewendet.
    Notes: A discussion of the factorization by constants of the motion of the secular equation is given and formulas are obtained which relate these factors to the traces of certain operators. These traces are independent of the specific basis in the vector space, and, hence, so are the factors of the secular equation. The results are also applied to the case of factoring by a finite symmetry group.
    Type of Medium: Electronic Resource
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  • 199
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 2 (1968), S. 739-739 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 200
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Les coéfficients de Clebsch-Gordan pour le couplage de deux moments cinétiques sont déduits à l'aide des opérateurs de projection, introduits par Löwdin. La déduction est faite en deux étapes; d'abord pour le cas principal k = m et après pour le cas général avec une valeur arbitraire de m. Deux déductions différentes sont décrites pour le cas principal, l'une directe et l'autre basée sur une formule récursive. Le cas général est obtenu du cas principal à l'aide d'un opérateur M-.
    Abstract: Die Clebsch-Gordan-Koeffizienten für die Kopplung zwei Drehimpulsmomente wurden mittels der Löwdinschen Projektionsoperatormethode hergeleitet. Die Herleitung wurde in zwei Stufen ausgeführt, erst für den sogenannten Prinzipalfall k = m und dann für den allgemeinen Fall mit einem willkürlichen Wert von m. Zwei verschiedene Herleitungen wurden für den Prinzipalfall gegeben, von denen die eine direkt ist und die andere auf einer Rekursionsformel gegründet ist. Der allgemeine Fall wurde von dem Prinzipalfall mit einem M--Operator erhalten.
    Notes: The Clebsch-Gordan coefficients for the coupling of two angular momenta are derived by using the projection operator technique, developed by Löwdin. The derivation is done in two steps; first for the so-called principal case, i.e. k = m, then for the general case with an arbitrary m. Two different derivations are given for the principal case, a direct one and one based on a recursion procedure. The general case is obtained from the principal case with a step-down operator.
    Type of Medium: Electronic Resource
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