Library

Your email was sent successfully. Check your inbox.

An error occurred while sending the email. Please try again.

Proceed reservation?

Export
Filter
  • Atomic, Molecular and Optical Physics  (6,266)
  • Nuclear reactions  (4,460)
  • Physical Chemistry  (3,728)
Material
Years
Keywords
  • 101
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 30 (1998), S. 799-803 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Collisional deactivation of I(2P1/2) by the title compounds was investigated through the use of the time-resolved atomic absorption of excited iodine atoms at 206.2 nm. Rate constants for atomic spin-orbit relaxation by CH3Cl, CH2Cl2, CHCl3, CCl3F, and CCl4 are 3.1±0.3×10-13, 1.28±0.08×10-13, 5.7±0.3×10-14, 3.9±0.4×10-15, and 2.3±0.3×10-15cm3 molecule-1 s-1, respectively, at room temperature (298 K).The higher efficiency observed for relaxation by CH3Cl, CH2Cl2, and CHCl3 reveals a contribution in the deactivation process of the first overtone corresponding to the C(SINGLEBOND)H stretching of the deactivating molecule (which lies close to 7603 cm-1) as well as the number of the contributing modes and certain molecular properties such as the dipole moment. It is believed that, for these molecules, a quasi-resonant (E-v,r,t) energy transfer mechanism operates. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 799-803, 1998
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 102
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 30 (1998), S. 831-837 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The time-resolved total emission of SO2 (B1B1→X1A1) at 354.9 nm were monitored following the direct excitation by a 266 nm laser pulse. A three-level model was proposed to deal with SO2 (X1A1, A1A2, B1B1) system. From a kinetic treatment of these measurements, the coupling coefficient, ξ, and the relaxation time, τ, relating to the high vibronic levels of A1A2 and B1B1 states were first obtained. It is found that ξ and τ values keep basically constant, reflecting the characteristics of the studied system. In addition, the quenching rate constants of SO2 (A1A2, B1B1) by some alkane and chloromethane molecules were measured at room temperature. The formation cross sections of complexes of SO2 (A1A2, B1B1) and quenchers were calculated by means of a collision complex model. It is shown that the dependence of the formation cross section of complex on the number of C(SINGLEBOND)H or C(SINGLEBOND)Cl bonds is generally in agreement with that of the measured quenching cross section. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 831-837, 1998
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 103
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Some relative rate experiments have been carried out at room temperature and at atmospheric pressure. This concerns the OH-oxidation of some oxygenated volatile organic compounds including methanol (k1), ethanol (k2), MTBE (k3), ethyl acetate (k4), n-propyl acetate (k5), isopropyl acetate (k6), n-butyl acetate (k7), isobutyl acetate (k8), and t-butyl acetate (k9). The experiments were performed in a Teflon-film bag smog chamber. The rate constants obtained are (in cm3 molecule-1 s-1): k1=(0.90±0.08)×10-12; k2=(3.88±0.11)×10-12; k3=(2.98±0.06)×10-12; k4=(1.73±0.20)×10-12; k5=(3.56±0.15)×10-12; k6=(3.97±0.18)×10-12; k7=(5.78±0.15)×10-12; k8=(6.77±0.30)×10-12; and k9=(0.56±0.11)×10-12. The agreement between the obtained rate constants and some previously published data has allowed for most of the studied compounds to point out a coherent group of values and to suggest recommended values. Atmospheric implications are also discussed. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 839-847, 1998
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 104
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constant of the title reaction is determined during thermal decomposition of di-n-pentyl peroxide C5H11O(—)OC5H11 in oxygen over the temperature range 463-523 K. The pyrolysis of di-n-pentyl peroxide in O2/N2 mixtures is studied at atmospheric pressure in passivated quartz vessels. The reaction products are sampled through a micro-probe, collected on a liquid-nitrogen trap and solubilized in liquid acetonitrile. Analysis of the main compound, peroxide C5H10O3, was carried out by GC/MS, GC/MS/MS [electron impact EI and NH3 chemical ionization CI conditions]. After micro-preparative GC separation of this peroxide, the structure of two cyclic isomers (3S*,6S*)3α-hydroxy-6-methyl-1,2-dioxane and (3R*,6S*)3α-hydroxy-6-methyl-1,2-dioxane was determined from 1H NMR spectra. The hydroperoxy-pentanal OHC(—)(CH2)2(—)CH(OOH)(—)CH3 is formed in the gas phase and is in equilibrium with these two cyclic epimers, which are predominant in the liquid phase at room temperature. This peroxide is produced by successive reactions of the n-pentoxy radical: a first one generates the CH3C·H(CH2)3OH radical which reacts with O2 to form CH3CH(OO·)(CH2)3OH; this hydroxyperoxy radical isomerizes and forms the hydroperoxy HOC·H(CH2)2CH(OOH)CH3 radical. This last species leads to the pentanal-hydroperoxide (also called oxo-hydroperoxide, or carbonyl-hydroperoxide, or hydroperoxypentanal), by the reaction HOC·H(CH2)2CH(OOH)CH3+O2→O(=)CH(CH2)2CH(OOH)CH3+HO2.The isomerization rate constant HOCH2CH2CH2CH(OO·)CH3→HOC·HCH2CH2CH(OOH)CH3 (k3) has been determined by comparison to the competing well-known reaction RO2+NO→RO+NO2 (k7). By adding small amounts of NO (0-1.6×1015 molecules cm-3) to the di-n-pentyl peroxide/O2/N2 mixtures, the pentanal-hydroperoxide concentration was decreased, due to the consumption of RO2 radicals by reaction (7). The pentanal-hydroperoxide concentration was measured vs. NO concentration at ten temperatures (463-523 K). The isomerization rate constant involving the H atoms of the CH2(—)OH group was deduced:\documentclass{article}\pagestyle{empty}\begin{document}$ k_{3}\rm =(6.4\pm 0.6)\times 10^{10}\hbox{exp}\{-(16,900\pm 700)\hbox{cal mol}^{-1}/RT\}s^{-1} $\end{document}or per H atom:\documentclass{article}\pagestyle{empty}\begin{document}$ k_{3\rm (H)}\rm =(3.2\pm 0.3)\times 10^{10}\hbox{exp}\{-(16,900\pm 700)\hbox{cal mol}^{-1}/RT\}s^{-1} $\end{document}The comparison of this rate constant to thermokinetics estimations leads to the conclusion that the strain energy barrier of a seven-member ring transition state is low and near that of a six-member ring. Intramolecular hydroperoxy isomerization reactions produce carbonyl-hydroperoxides which (through atmospheric decomposition) increase concentration of radicals and consequently increase atmospheric pollution, especially tropospheric ozone, during summer anticyclonic periods. Therefore, hydrocarbons used in summer should contain only short chains (〈C4) hydrocarbons or totally branched hydrocarbons, for which isomerization reactions are unlikely. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 875-887, 1998
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 105
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 30 (1998), S. 933-940 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the title reactions have been studied using the discharge-flow mass spectrometic method at 296 K and 1 torr of helium. The rate constant obtained for the forward reaction Br+IBr→I+Br2 (1), using three different experimental approaches (kinetics of Br consumption in excess of IBr, IBr consumption in excess of Br, and I formation), is: k1=(2.7±0.4)×10-11 cm3 molecule-1s-1. The rate constant of the reverse reaction: I+Br2→Br+IBr (-1) has been obtained from the Br2 consumption rate (with an excess of I atoms) and the IBr formation rate: k-1=(1.65±0.2)×10-13 cm3molecule-1s-1. The equilibrium constant for the reactions (1,-1), resulting from these direct determinations of k1 and k-1 and, also, from the measurements of the equilibrium concentrations of Br, IBr, I, and Br2, is: K1=k1/k-1=161.2±19.7. These data have been used to determine the enthalpy of reaction (1), ΔH298°=-(3.6±0.1) kcal mol-1 and the heat of formation of the IBr molecule, ΔHf,298°(IBr)=(9.8±0.1) kcal mol-1. © 1998 John Wiley & sons, Inc. Int J Chem Kinet 30: 933-940, 1998
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 106
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 30 (1998), S. 949-959 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Detailed modeling of the oxidation of n-octane and n-decane in the gas phase was performed by using mechanisms written by means of a software recently developed in our laboratory. This computer-aided design of mechanisms permits the automatic generation of detailed oxidation and combustion kinetic models in the case of paraffins and isoparaffins [1]. For n-octane, the predictions of the model were compared with experimental results obtained by Dryer and Brezinsky by means of a turbulent plug flow reactor (1080 K, 1 atm) [2]. The experimental study of Balès-Guéret et al., performed in a perfectly stirred reactor (922-1033 K, 1 atm) [3], was used as a basis of comparison for the modeling of the oxidation of n-decane. Considering that no fitting of any kinetic parameter was done, the agreement between the computed and the experimental values is satisfactory both for conversions and for the distribution of the products formed. This modeling has required improvement in the generation of the secondary reactions of alkenes, which are the main primary products obtained during the oxidation of these two alkanes in the range of temperature studied and for which reaction paths are detailed. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 949-959, 1998
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 107
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 62 (1997), S. 115-124 
    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: Some types of atomic vibrations in a chain of the DNA type constructed of G-C pairs were studied. These are the atomic vibrations of the lateral groups of guanine and N(3)H(1)H(2) of cytosine connected by the hydrogen bond h-b-1 and the vibrations of the centers of masses of bases in the direction parallel to bonds h-b-i, i = 1-3. The vibrations mix partially due to the dependence of the energy of the bond h-b-1 on its length and split into two bands because of the interaction between neighboring base pairs. It was shown that the excitation of the bond h-b-1 results in the splitting off of the two local vibrations and in a small deformation of the chain in the vicinity of the pair with the localized hydrogen bond. The law of the dispersion of band vibrations, values of the split-off frequencies, and degree of poly(dG)-poly(dC) chain deformation were determined. © 1997 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 108
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 62 (1997), S. 97-113 
    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: Restricted geometry optimizations at the ab initio SCF level with the 3-21G basis set were employed to investigate the conformation space of flavone acetic acid (FAA) and its related compounds. All the conformations are produced from a conformation which is, according to our previous work, probably the active conformation in terms of antitumor activity shown by these compounds. Detailed studies on FAA were carried out while only brief discussions are made on the analogs. The main results obtained are that (1) FAA is a very flexible molecule, e.g., with the energy barrier up to about 3 kcal mol-1 from the reference conformation, the important torsional angle τ1 can change from 27.0° to 117.0°, τ2 from -168.0° to 2.0°, and τ3 from -50.0° to 30.0°; (2) the hydrogen-bonding effect plays an important role in determining lower-energy conformations; (3) among all the FAA conformations considered, some are active and some are inactive; (4) it seems that the analogs will have similar behavior to FAA when the torsional angle τ3 is restricted to the values which are around the equilibrium values; and (5) the hypothesis put forward previously has been further developed in this work. Now, we postulate that efficient charge transfers will lower the energy and that proper charge transfers will activate the molecule. There are mainly two different types of charge transfer corresponding to two different types of conformation, which are specified in this article. © 1997 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 109
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 62 (1997), S. 13-21 
    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: An analysis of the anisotropic Heisenberg model is carried out by solving the Bethe ansatz solution of the model numerically as a function of the anisotropy parameter for finite N. A brief introduction to the limit of the infinite chain is presented. The energy for a few special limiting cases of the anisotropy parameter in the Hamiltonian are worked out. Numerical results for finite cycles as well as for the infinite chain are given. Comparison can then be made with the case of finite increasing N. © 1997 John Wiley & Sons, Inc.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 110
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 62 (1997), S. 23-27 
    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: An ab initio study on the reaction of the ground state (3D) and the excited state (1D) of Sc+ with methane was performed. Reaction channels on the singlet and triplet potential surface (PES) and the reaction mechanism are examined and discussed. Three regions of the potential surface was studied: the molecular complex, the C(SINGLE BOND)H insertion products, and the transition states for the reaction. Comparisons between singlet and triplet PESs show that the excited state (1D) of Sc+ has more reactivity with methane than does the ground state (3D) due to the spin quantum number conservation with the more stable insertion intermediate. © 1997 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 111
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 62 (1997), S. 1-11 
    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: Roothaan-Hartree-Fock (RHF) calculations are carried out for the ground states of the atoms from helium to xenon using a minimal basis set of Slater-type functions whose principal quantum numbers are allowed to take variationally optimal noninteger values. The resulting energies are substantially superior to those obtained previously under the usual restriction that principal quantum numbers be positive integers. The energy lowering relative to the single-zeta wave functions of Clementi and co-workers ranges from 0.0066 Eh in He to 11.2 Eh in Xe. Our results are superior to those obtained by Höjer using a minimal basis set of unconventional binomially screened basis functions. Noninteger principal quantum numbers benefit d-orbitals the most; physically realistic negative d-orbital energies are obtained in all cases including those transition-metal atoms for which a conventional single-zeta STF basis leads to positive d-orbital energies. © 1997 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 112
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 62 (1997), S. 47-53 
    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 MELD program is employed to evaluate the Slater average potential v(r) felt by an electron at the point r within an atom. The characteristic radius R of the atom is then defined by the classical turning point equation v(R) = -I, where I denotes the first ionization potential of the atom. The atomic radii defined in this way have a close correlation with the van der Waals atomic radii. © 1997 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 113
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 62 (1997), S. 29-45 
    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 H2 interaction with the Pd dimer and trimer were studied using multiconfigurational self-consistent field (MC-SCF) calculations with the relativistic effective core potential (RECP); the correlation energy correction was included in the extended multireference configuration interaction (MRCI), variational and perturbative to second order. Here, we considered the Pd2 first six states: 3Σ+u, 1Σ+g, 3Πg, 3Δxy, 1Σ+u, and 3Σ+g. For them, the four geometrical approaches included were the side-on H2 toward Pd2, for the hydrogen molecule in and out the Pd dimer plane; the perpendicular end-on H2 toward Pd2; and the perpendicular end-on Pd2 to H2. The Pd2 ground state is 3Σ+u, which only captures H2 in the C2v end-on approach, softly relaxing the H(SINGLE BOND)H bond. The closed-shell 1Σ+g captures the H2 molecule in all the approaches considered: The side-on approach of this state presents deep wells and relaxes the H(SINGLE BOND)H bond, and the end-on approach captures H2 with a relatively longer H(SINGLE BOND)H distance and also a deep well. The 3Πg state was the only one which did not capture H2. For the triangular Pd3 clusters, H2 was approached in the C2v symmetry in and out of the Pd3 plane. In the triangular case, H2 was absorbed in both spin states, with deep wells and relaxing the H(SINGLE BOND)H distance. The linear Pd3 singlet and triplet states capture outside of the Pd3 and break the H(SINGLE BOND)H bond. © 1997 John Wiley & Sons, Inc.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 114
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 62 (1997), S. 77-88 
    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: Highly accurate upper bounds for several 2Pe states of the Li isoelectronic series obtained by extensive Hylleraas-Cl calculations are given. The best value for the 22Pe state (1s2p2) of Li is -5.21373920 au. The evaluation of the occurring integrals is given explicitly. Additionally, we present some expectation values and isotope energies of the Li isoelectronic series. © 1997 John Wiley & Sons, Inc.
    Additional Material: 11 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 115
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 62 (1997), S. 67-76 
    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 importance of the hybridization displacement charge (HDC) in describing molecular electrostatic potential (MEP) maps was demonstrated by studying six molecules; pyrazine N-oxide, para-nitropyridine, 5-nitropyrimidine, 3-nitropyridazine, N2, and N2O. It is shown that continuously distributed HDC-corrected Löwdin charges reproduce the MEP features of these molecules, most of which have competing electrophilic sites, in agreement with ab initio results. Further, it is found that for homonuclear diatomic molecules MEP minima can be located properly using HDC-corrected Löwdin (or HDC-corrected Mulliken) continuously distributed charges, but these features cannot be obtained using the conventional Löwdin (or Mulliken) charges. It was shown that the order of molecular electric field (MEF) values near the different electrophilic sites becomes changed when one moves away from the molecules. Thus, pyridine-type nitrogen atoms are the preferred binding sites close to the molecules, while at large distances, effects of oxygen atoms of the NO groups become dominant. © 1997 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 116
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 62 (1997), S. 55-65 
    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 compare geometry configurations, vibrational properties, and electronic structures of (HF)2 in a free state and inside argon atom shells Arn. For the first stage, molecular dynamics calculations for the (HF)2 · Ar62 heterocluster are performed with the help of model potentials HF(SINGLE BOND)HF, Ar(SINGLE BOND)Ar, and Ar(SINGLE BOND)HF. Then, ab initio quantum chemistry analysis is carried out for the smaller systems (HF)2 · Ar15 and (HF)2 · Ar6 when keeping the argon atoms closest to the trapped dimer. We conclude that the hydrogen-bonded complex (HF)2 gains some extra stability inside the argon shells, originating primarily from a decrease of intermolecular distance RFF. Electronic structure calculations are in accord with the changes in dynamical properties, namely, a noticeable increase in the vibrational frequency assigned to the F(SINGLE BOND)F stretching mode (+25 cm-1) and decrease in rms deviations for the corresponding coordinate δFF. In addition to these changes, the argon atoms of the nearest solvent shell donate a small fraction of electron charge which is spent for an increase of population of the antibonding orbital σ*Hf(SINGLE BOND)Ff of the free monomer unit and shift orbital energies primarily of the lone-pair fluorine species. These shifts are greater than the changes due to geometry alterations and the possible inaccuracies of the calculation scheme. © 1997 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 117
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 62 (1997), S. 89-96 
    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 presented a calculation of the total and partial decay widths of vibrational predissociation (VP) of the HeI2 molecule for low initial vibrational excitations from the lowest van der Waals (vdW) state with total angular momentum J = 0. A time-dependent golden rule wave-packet method was employed in our numerical calculations for the decay widths. The computed total decay widths, lifetimes, and rates of VP are in fairly good agreement with those extrapolated from the experimental data available. Predicted total decay widths as a function of initial vibrational levels exhibit a highly nonlinear behavior. These results demonstrate that a quantum mechanical decay mode for low vibrational excitation remains as well. The total propagation time needed in the time-dependent golden rule wave-packet calculations is much shorter than is the lifetime of the predissociation of HeI2. It is shown that the final-state interaction between the fragments is important for determining the final rotational-state distribution (partial decay width). We find that the major peak position in the final rotational-state distribution shifts to lower rotational energy levels with increase of the initial vibrational quantum number, which is evidently different from that for higher vibrational levels. This fact can be clearly explained by the dependence of the amount of kinetic energy released to the product degrees of freedom on the initial vibrational state. © 1997 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 118
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 62 (1997), S. 239-244 
    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 calculate the resonant and antibound state energies for a Morse potential with a centrifugal barrier using Siegert boundary conditions. Starting with a complex wave number k (purely imaginary for bound and antibound states), we integrate numerically from the origin up to a matching point using Numerov's method. The inward integration is performed using the corresponding (first-order) Riccati equation. The complex eigenvalues are found by matching the two logarithmic derivatives. We find narrow shape resonances within the well, above the dissociation limit, and broad resonances above the centrifugal barrier. Antibound states are found even with J = 0. © 1997 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 119
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 62 (1997), S. 245-259 
    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: An efficient expansion method for the evaluation of VB matrix elements is introduced. The overlaps of VB wave functions of N electrons can be treated as algebrants, i.e., generalized determinants, of N × N matrices. An algebrant can be expanded with subalgebrants of lower orders in a successive way. By choosing Rumer spin bases and appropriately arranging the expansion, it is found that the number of unique subalgebrants involved in the expansion increases in a quite moderate way with N. In contrast to the traditional symmetric group approach, which explicitly utilizes all N! representation matrices, the new strategy incorporates the group theoretical factors in a simple way in the successive expansion. As only the unique subalgebrants are further expanded, the computational effort required by the new strategy scales in a very acceptable manner with the increasing number of electrons. © 1997 John Wiley & Sons, Inc. Int J Quant Chem 62: 245-259, 1997
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 120
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 62 (1997), S. 261-264 
    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: Characters of irreducible representations (irreps) of the symmetric group corresponding to the two-row Young diagrams, i.e., describing transformation properties of N-electron eigenfunctions of the total spin operators, have been expressed as explicit functions of the number of electrons N and of the total spin quantum number S. The formulas are useful in various areas of theory of many-electron systems, particularly in designing algorithms for evaluation of spectral density moments. © 1997 John Wiley & Sons, Inc.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 121
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 62 (1997), S. 273-278 
    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: Analytical solutions to the Yukawa-like screened Coulomb nuclear attraction and electron repulsion molecular basic integrals, as well as to the basic integrals required to compute the virial coefficient, over Gaussian basis functions, are derived and cast into a practical closed form, suitable to interface with modern codes for the calculation of molecular electronic structure. © 1997 John Wiley & Sons, Inc.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 122
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 62 (1997), S. 265-272 
    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: Numerical experiments with a nonlinear (λχ4) oscillator which has its harmonic frequency changing randomly with time reveal certain interesting features of its dynamics of quantum evolution. When λ = 0, the level populations are seen to oscillate. But, as the nonlinear coupling is switched on (λ 〉 0), a threshold is reached at λ = λc when the evolution is seen to be characterized by an abrupt transition dominantly to the highest available state of the unperturbed (initial) oscillator. It is shown that this transition probability is maximized at a particular value of λ. The time threshold for this transition decreases with increasing nonlinear coupling strength. The numerically obtained structures of the underlying quantum-phase spaces of the linear and nonlinear random oscillators are examined. Possible use of these results in a problem of chemical origin is explored. © 1997 John Wiley & Sons, Inc.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 123
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 62 (1997), S. 291-296 
    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 geometries and S-H, S-S, and S-C bond dissociation energies for hydrogen sulfide, hydrogen disulfide, methanethiol, dimethyl disulfide, and dimethyl disulfide were calculated with both ab initio (ROHF and MP2), hybrid (BHandH, BHandHLYP, Becke3LYP and Becke3P86), and nonlocal (BLYP and BP86) density functional theory (DFT) methods. In all studies the 6-31 + G(d) basis set is used. The computed results are compared to the experimentally obtained values, targeting the selection of a suitable ab initio or DFT method for the study of these systems. © 1997 John Wiley & Sons, Inc.
    Additional Material: 7 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 124
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 63 (1997), S. 1065-1078 
    ISSN: 0020-7608
    Keywords: very precise eigenvalues ; very accurate grid method ; general solution for Schrödinger equations ; rapidly convergent treatment for helium eigenvalues ; superconvergence ; optimization of grids ; treatment of continuum ; Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An extension to the theory of Schrödinger equations has been made which enables the derivation of eigenvalues from a consideration of a very small part of geometric space. The concomitant unwanted continuum effects have been removed. The theory enables very convergent or “superconvergent” calculations. In the case of the helium ground state, E=-2.90372437703411987 Eh was obtained from 251 terms. The result is comparable to that from the largest variation calculations so far carried out reinforced by extrapolation techniques. The theory is extensible to atoms and molecules irrespectively of the number of electrons or nuclear centers. In these cases, the advantage of “superconvergent” calculations will be more pronounced than in the case of helium.   © 1997 John Wiley & Sons, Inc. Int J Quant Chem 63: 1065-1078, 1997
    Additional Material: 9 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 125
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 63 (1997), S. 1079-1089 
    ISSN: 0020-7608
    Keywords: large-order perturbation theory ; lie algebra ; three-body problem ; symbolic computations ; helium atom ; Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The method of o(4, 2) operator replacements is generalized. As a result, the series whose limiting values when the variable goes to  +∞ should correspond to the two-electron atom energies now have rational coefficients. This generalization allows one also to compute the series for the case of singlet S symmetry, a case which could not be considered in the previous original formulation of the method. Series with rational coefficients for the helium singlet and triplet S ground-state energy are calculated up to order 41 and 45, respectively. Moreover, symbolic computations also allow one to give the first few coefficients of these series for arbitrary values of the nuclear charge Z. Finally, a new method for analytic continuation to the limit  +∞ is presented for the energies of the helium singlet and triplet ground states.   © 1997 John Wiley & Sons, Inc. Int J Quant Chem 63: 1079-1089, 1997
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 126
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 63 (1997), S. 1099-1106 
    ISSN: 0020-7608
    Keywords: metathesis reactions ; bond order ; free valence ; minimum energy path ; nonsynchronization ; Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A few simple atom-transfer reactions (i.e., Ȧ+X-A→A-X+Ȧ) are studied by quantum mechanical ab initio methods. Emphasis is given to the detailed analysis of density matrices rather than to the energetics. Results reveal that during these reactions a small free valence always develops on the migrating atom at the transition state. The barriers in these reactions arise from the greater extent of bond cleavage in the reactant than that of bond formation in the transition state. Analysis of bond orders estimated from bond lengths using Pauling's relation also leads to the fact that the bond-cleavage process is more advanced than is the bond-formation process in these reactions.   © 1997 John Wiley & Sons, Inc. Int J Quant Chem 63: 1099-1106, 1997
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 127
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 63 (1997), S. 1107-1122 
    ISSN: 0020-7608
    Keywords: relativistic pseudopotentials ; heavy atoms ; method of molecular calculation ; electronic structure ; Gaussian approximation ; Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Gaussian expansions of the generalized relativistic effective core potential (GRECP) components are reported for elements Hg through Rn. The accuracy of the analytical GRECPs is estimated by calculations of atomic transition energies with the numerical one-configurational wave functions in comparison with Dirac-Fock calculations. The results of the corresponding calculations with the RECPs of other groups are also given. An “averaged error” in the reproduction of the transition energies without the change of the occupation number of the 5d-shell is an order of magnitude smaller than that for the RECPs of other groups. As is demonstrated for the transitions with the change of the occupation number of the 5d-shell in mercury, the largest absolute error of the GRECP is only 1.5-2 times smaller than that of the energy-adjusted pseudopotential (PP) or the RECP of Ross et al. with the same space of explicitly treated electrons. However, the dispersion of these errors is 19⋅10-4 au for the energy-adjusted PP, 35⋅10-4 au for the RECP of Ross et al. and only 4⋅10-4 au for the GRECP. One-configurational spin-averaged calculations of the molecular properties for HgH and HgH+ are carried out and compared with the corresponding results of Häussermann et al.   © 1997 John Wiley & Sons, Inc. Int J Quant Chem 63: 1107-1122, 1997
    Additional Material: 17 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 128
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 63 (1997), S. 1123-1131 
    ISSN: 0020-7608
    Keywords: MD simulations ; liquid surface ; formamide ; molecular orientation ; molecular surface density ; Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular dynamics simulations of liquid formamide(HCONH2) were carried out using the GROMOS software. The formamide molecule is represented by all of its atoms with all internal degrees of freedom. In contrast to other simulations dealing with bulk properties, this study focuses on the interface liquid-vacuum for the first time. We show that the molecular plane is tilted out of the surface, exposing the HCO group to the vacuum.   © 1997 John Wiley & Sons, Inc. Int J Quant Chem 63: 1123-1131, 1997
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 129
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 62 (1997), S. 279-289 
    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: Testosterone (17β-hydroxy-4-androsten-3-one) was studied by the semiempirical AM1 and PM3 and ab initio STO-3G*, 3-21G*, and 6-31G* methods. The goals were to compare those methods and to know the electronic structure of the hormone. Full geometry optimization was performed, and two crystal conformers (T1 and T2), and experimental dipole moment in solution were used for comparison. One conformer with a dipole moment similar to the solvated conditions was generated. Total energy, entalphies, dipole moments, charges, electrostatic potentials, and highest occupied molecular orbitals (HOMO) and lowest unoccupied molecular orbital (LUMO) were calculated. Root-mean-square (RMS) index of the theoretical molecules against T1 and T2 showed best results with the 3-21G* and 6-31G* methods, while AM1 gave better energies than PM3. Dipole moments were directed toward the OH group and the botton face of the A ring. The frontier orbitals were located along the C4-C5 π bond, particularly the LUMO was split between C4 and C5, predicting the action of enzymes at C5 yielding to 5α and 5β-reduced androgens. Electrostatic potentials might be also of biological importance since they are coincidental with the dipole-moment orientation. Finally, it is interesting that the solvatedlike conformer, its properties, and the OH group laid between the same group of T1 and T2 and with a total energy between the crystals and the gas phase or in vacuo conditions. This results might also explain the biology of testosterone and use them to model the hormone-receptor interaction. © 1997 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 130
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 62 (1997), S. 297-302 
    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 mechanism and kinetics for the decomposition of β-hydroxypropaldehyde, primary and secondary β-hydroxyketones, were studied by using ab initio RHF/6-31G and RHF/6-31G* methods. The activation barriers of these reactions were refined to be 39.57, 40.10, and 36.80 kcal mol-1 at the MP2/ /RHF/6-31G* level, respectively. The calculated results show that each decomposition is a concerted process with hydrogen transferring and bond breaking via a six-membered cyclic transition state. The thermal rate constants of the decomposition of primary and secondary β-hydroxyketones were obtained by calculating microcanonical probability fluxes through each transition state. It is theoretically confirmed that methyl substitution at the hydroxyl carbon of β-hydroxyketones causes a small enhancement in rates. The theoretical investigations of the mechanism and the rate constants are in agreement with the experimental results. © 1997 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 131
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 62 (1997), S. 303-314 
    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: He I photoelectron (PE) spectra of four carboxylic acids and five esters are measured. Semiempirical and ab initio quantum chemical calculations are used for the interpretation of the spectra. The complex approach which uses empirically established relationships (the dependence of valence electron ionization energies on proton affinities in the gas phase, on the core level ionization energies, and on the structure) was developed. © 1997 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 132
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 62 (1997), S. 315-322 
    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: Two alternative dehydration reactions C(OH)4 → (HO)2CO + H2O and C(OH)4 + H2O → (HO)2CO + 2H2O are studied by ab initio Becke3LYP/6-311 + G** and MP2/6-31G** methods. Calculated energy and geometry characteristics of intermediates and transition states predict a catalytic effect of one water molecule and the exothermism of the transformations. Relevant HF/6-311 + G**, HF/6-31G**, HF/6-31G, and HF/3-21G calculations were performed for comparison. © 1997 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 133
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 62 (1997), S. 323-328 
    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: Simple molecular orbital calculations are employed in searching electronic parameters which may characterize the chemical carcinogens. Using frontier orbitals, the carcinogen-DNA bond formation is described as an electron transfer from the highest occupied molecular orbital (HOMO) of DNA to the lowest unoccupied molecular orbital (LUMO) of the carcinogen. Analysis of the DNA bases units shows that the electron donation occurs preferentially at the guanine site. The calculated low LUMO energy of several carcinogens indicate correctly the electrophilic character of these compounds. The difference between the carcinogen and the ultimate carcinogen is analyzed. Epoxides, free radicals, alkylating agents, and other metabolite forms are studied. A reasonable correlation is found between the LUMO energy and the carcinogenic function. © 1997 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 134
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 203-208 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constant for the CF3 + NO2 reaction (k2) was measured at room temperature in the range of total pressures 300-600 torr. The measurements were performed using the ruby-laser-induced pulsed photodissociation of CF3NO in the presence of NO and NO2 in combination with time-resolved detection of the absorption of He(SINGLE BOND)Ne laser radiation by CF3NO. The use of the CF3 + NO reaction as a reference gives k2 = (3.2 ± 0.7) × 10-11 cm3/s. Analysis of the end products of the CF3 + NO2 reaction shows that the contribution of the association reaction channel, which leads to the formation of CF3NO2, is rather significant (about 30% total yield). A reaction mechanism is suggested to account for the products observed. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 203-208, 1997.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 135
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 219-224 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction between the radical cation derived from 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) and phenols follows a kinetic law given by \documentclass{article}\pagestyle{empty}\begin{document}$$ d[ABTS^{\buildrel{+}\over{\cdot}}]/dt=k [ABTS^{\buildrel{+}\over{\cdot}}]^2[PhOH]/[ABTS] $$\end{document} with stoichiometric coefficients between one and two. The rate constant is almost unrelated to the structure of the phenol, while the number of ABTS radicals scavenged by each phenol molecule increases with para-substitution. These results are explained in terms of a fast, reversible electron transfer \documentclass{article}\pagestyle{empty}\begin{document}$$ ABTS^{\buildrel{+}\over{\cdot}}\,+PhOH {\buildrel{\longrightarrow}\over{\longleftarrow}} ABTS + PhO\bullet+H^{+} $$\end{document} followed by the self-combination of the phenoxy radicals and/or their reaction with another ABTS derived radical action. The relative rate of these processes determine the value of the stoichiometric coefficient. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 219-224, 1997.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 136
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 237-243 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for H atom attack on GeH4 and GeD4 have been measured in pulsed photolysis experiments in which H atoms were produced by the mercury-sensitized photolysis of H2 and monitored by Lyman-α absorption. The values obtained for GeD4 in the temperature range 293-550 K may be represented by the expression \documentclass{article}\pagestyle{empty}\begin{document}$$ k_D=(0.99\pm 0.10)\times 10^{-10}\,exp[(-1114\pm 37)/T] $$\end{document} Combination of the rate constants for GeH4 measured in this work with those previously determined in this laboratory gives, for the temperature range 293-455 K, \documentclass{article}\pagestyle{empty}\begin{document}$$ k_H=(0.89\pm 0.08)\times 10^{-10}\,exp[(-879\pm 31)/T] $$\end{document} The kinetic isotope effect indicated by these expressions is given by \documentclass{article}\pagestyle{empty}\begin{document}$$ k_H/k_D=(0.90\pm 0.12)\,exp[(-235\pm 48)/T] $$\end{document} which yields \documentclass{article}\pagestyle{empty}\begin{document}$ k_H/k_D=2.0 \pm 0.4 hbox{ at 300 K.} $\end{document}. This is the first determination of the kinetic isotope effect for radical attack on a Ge(SINGLE BOND)H bond.The present results for the reaction of H atoms with GeH4 have been combined with previously reported data, and the best value for the rate constant over the temperature range 210-473 K is recommended to be \documentclass{article}\pagestyle{empty}\begin{document}$$ k_D=(1.18\pm 0.08)\times 10^{-10}\,exp[(-981\pm 22)/T] $$\end{document} © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 237-243, 1997.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 137
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 261-267 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A continuous flow-through reactor with a thin layer of solid particles (size ranging from 100 to 300 μm) was used to obtain a deeper knowledge on the mechanism of dissolution of UO2 under oxidizing conditions. Using this methodology the dissolution rate of uranium dioxide was determined at three different oxygen partial pressures (5, 21, and 100% in nitrogen) and as a function of pH (between 3 and 12) in a noncomplexing medium.From the results of these experiments the following rate equation was derived: \documentclass{article}\pagestyle{empty}\begin{document}$$ (3 〈 pH 〈 6.7)\,r\,(mol\cdot s^{-1}\cdot m^{-2})\,=\,(3.5 \pm 0.8) \cdot 10^{-8} \cdot [H^{+}]^{0.37\pm 0.01}\cdot[O_2]^{0.31\pm 0.02} $$\end{document} In addition, XPS characterizations were performed to determine the U(IV)/U(VI) ratio on the solid surface at different experimental times and conditions. These results showed that at acidic conditions (pH below 6.7) the final solid surface presents a stoichiometry close to UO2, while at alkaline conditions the final solid surface average composition is close to UO2.25. This information was integrated with the results of the leaching experiments to present a model for the mechanism of dissolution of uranium dioxide under the experimental conditions. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 261-267, 1997.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 138
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 289-293 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rates, Arrhenius parameters, and Hammett substituent constants are obtained for the gas-phase thermal elimination of ethyl benzoate (1) and ethyl 2 - thienyl -  (2), 3 - thienyl -  (3), 2 - furyl -  (4), 3 - furyl -  (5), 4 - pyridyl -  (6), 3 - pyridyl -  (7), and 2 - pyridylcarboxylate (8) esters. The log A/s-1 and the Ea/kJ mol-1 values of these esters averaged 13.60 and 216.3, respectively. The present results are compared with data previously reported for the corresponding isopropyl and t-butyl analogues, and the findings are rationalized in terms of a plausible transition state for the elimination pathway. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 289-293, 1997.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 139
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 311-316 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The aquation kinetics of [Co(NH3)5Cl]2+ in dicarboxylate media containing 10% (v/v) acetone is measured in the temperature range of 35-60°C. A new empirical correlation between the rate coefficient, kobs, and the stoichiometric concentration of the dicarboxylate ligand (CL) has been established and a reaction mechanism is proposed. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 311-316, 1997.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 140
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 131-138 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetics of the interaction of Cd(II)-histidine complex with ninhydrin has been carried out at pH 5.02 (acetic acid-sodium acetate buffer) under varying conditions of reactant concentrations, temperature, and surfactant concentrations. The order of the reaction with respect to Cd(II)-histidine complex was unity while it was fractional with respect to ninhydrin. On the basis of these studies a mechanism has been proposed. In the absence of the surfactants, the reaction followed rate equation: \documentclass{article}\pagestyle{empty}\begin{document}$$ {1\over k_{\rm obs}}={1\over k}+{1\over k K_t{\rm [Ninhydrin]}} $$\end{document} while, in presence of surfactants, the following rate equation was obeyed: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_\Psi={{k_W+K_mK_s[D_n]}\over{1+K_s[D_n]}} $$\end{document} Anionic micelles of sodium dodecyl sulphate catalyze the reaction with the rate reaching a maximum at ca. 0.10 mol dm-3 surfactant. The surfactant decreases activation enthalpy and makes it more negative. Cationic micelles of cetyltrimethylammonium bromide strongly inhibit the reaction and increase the activation enthalpy but make the activation entropy more positive than the SDS micelles. Added salts (KNO3 and NaCl) inhibit the catalysis, and the effect is more with the latter. The rate constants, binding constants with surfactants, and the index of cooperativity have been evaluated. © 1997 John Wiley & Sons, Inc.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 141
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 225-230 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the oxidation of formate, oxalate, and malonate by |NiIII(L1)|2+ (where HL1 = 15-amino-3-methyl-4,7,10,13-tetraazapentadec-3-en-2-one oxime) were carried out over the regions pH 3.0-5.75, 2.80-5.50, and 2.50-7.58, respectively, at constant ionic strength and temperature 40°C. All the reactions are overall second-order with first-order on both the oxidant and reductant. A general rate law is given as - d/dt|NiIII(L1)2+| = kobs|NiIII(L1)2+| = (kd + nks |R|)|NiIII(L1)2+|, where kd is the auto-decomposition rate constant of the complex, ks is the electron transfer rate constant, n is the stoichiometric factor, and R is either formate, oxalate, or malonate. The reactivity of all the reacting species of the reductants in solution were evaluated choosing suitable pH regions. The reactivity orders are: kHCOOH 〉 kHCOO-; kH2ox 〉 kHox- 〉 kox2-, and kH2mal 〉 kHmal- 〈 kmal2- for the oxidation of formate, oxalate, and malonate, respectively, and these trends were explained considering the effect of hydrogen bonded adduct formation and thermodynamic potential. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 225-230, 1997.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 142
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 245-251 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constant for the NH3 + NO2 rlhar2; NH2 + HONO reaction (1) has been kinetically modeled by using the photometrically measured NO2 decay rates available in the literature. The rates of NO2 decay were found to be strongly dependent on reaction (1) and, to a significant extent, on the secondary reactions of NH2 with NOX and the decomposition of HONO formed in the initiation reaction. These secondary reactions lower the values of k1 determined directly from the experiments. Kinetic modeling of the initial rates of NO2 decay computed from the reported rate equation, - d[NO2]/dt = k1[NH3][NO2] based on the conditions employed led to the following expression: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 = 10 ^{11.39\pm 0.16}\,e^{-(12620\pm 240)/T}\,cm^3 mole^{-1} s^{-1} $$\end{document} This result agrees closely with the values predicted by ab initio MO [G2M//B3LYP/6-311 G(d,p)] and TST calculations. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 245-251, 1997.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 143
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 269-274 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Na2(Mo2vO4EDTA).4H2O crystals have been prepared in pure form. Kinetics for the oxidation of the compound by S2O82- have been studied spectrophotometrically in dilute sulphuric acid medium. The effects of hydrogen ion concentration, metal ion concentration, S2O82- ion concentration, and temperature on the process have been studied. Rate equations have been derived to explain the experimental observations. On the basis of the observations, suitable mechanisms have been suggested. The kinetic parameters E*, ΔH≠, and ΔS≠ of the process have also been determined. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 269-274, 1997
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 144
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 295-298 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rates of gas-phase elimination reactions of methyl benzoylformate (1) and 3-hydroxy-3-methyl-2-butanone (2) were obtained at T = 600 K. The two substrates undergo unimolecular first-order elimination for which the Arrhenius equations are, respectively, log k = 13.2 - 53270/(4.574 × 600) for (1) and log k = 12.4 - 53060/(4.574 × 600) for (2). The products of pyrolysis of (1) are benzaldehyde, formaldehyde and CO, while those of (2) are acetaldehyde and acetone. The kinetics of the elimination reactions show benzoylformic acid to be 106-fold more reactive than (1), and pyruvic acid ca. 105-fold more reactive relative to (2); an indication of the rate-controlling part played by the acidity of the hydrogen atom involved in the elimination process of the present compounds in this particular type of reaction. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 295-298, 1997.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 145
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 317-321 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The transformation kinetics of a series of liquid-crystallines based on 1,4-phenylene 4-n-alkybenzoate-4-allyloxybenzoate (PABAOB) was studied by nonisothermal methods using differential scanning calorimetry. These determinations led to the values of activation energy of transformation from 691.3 to 628.3 kJ/mol, respectively. The values of the Avrami exponent n were from 3.0 to 2.6. The values of transformation activation energy decreased with the ascending of alkyl. The result shows that the process of transformation of PABAOB is a constant number of nuclei growing in three dimensions at constant rate and the crystal growth being controlled probably by a diffusion process. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 317-321, 1997
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 146
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 523-525 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for three dimethylbenzaldehydes and two trimethylphenols have been determined for the OH reactions at 298±2 K and atmospheric pressure using a relative rate method. The OH reaction rate constants were placed on an absolute basis using the literature rate constant for 1,2,4-trimethylbenzene of (3.25±0.5)×10-11 cm3 molecule-1s-1). The measured rate constants were (in units of cm3 molecule-1 s-1) 2,4-dimethyl-benzaldehyde, (4.32±0.67)×10-11; 2,5-dimethylbenzaldehyde, (4.37±0.68)×10-11; 3,4-dimethylbenzaldehyde, (2.14±0.34)×10-11; and 2,3,5- trimethylphenol, (12.5±1.9)×10-11, 2,3,6-trimethylphenol, (11.8±1.8)×10-11. Using an average OH concentration of 8.7×105 molecule cm-3, the estimated atmospheric lifetimes are ca. 7.5 h for 2,4- and 2,5-dimethylbenzaldehydes, ca. 15 h for 3,4-dimethylbenzaldehyde, ca. 2.5 h for 2,3,5- and 2,3,6-trimethylphenols. The reactivities of the trimethylphenols exceed those of the dimethyl-benzaldehydes by more than a factor of 3. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 523-525, 1997.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 147
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 545-560 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cracking reaction pathways and mechanisms of ethylcyclohexane and 1-cyclohexyloctane with a rare earth Y (REY) catalyst were studied. Experiments at 500°C indicated that the dominant reactions were ring opening with subsequent secondary cracking, cracking in the alkyl side chain, isomerization, and hydrogen transfer. A kinetic model of the catalytic cracking of 1-cyclohexyloctane was developed using a novel mechanism-based lumping scheme that exploits the chemical similarities within reaction families. The formal application of 17 reaction family matrices, which correspond to 13 reaction family classes, to the matrix representations of the reactants and derived products generated the model. The reaction family concept was further exploited to constrain the kinetics within each reaction family to follow a quantitative structure/reactivity Polanyi relationship. Ultimately, nine Polanyi relationship parameters and three coking/deactivation parameters were determined by optimizing the model fit to the experimental data. The resulting model correlations were excellent, as the overall parity between experimental and model values was yModel=-0.000470+0.986yExp with a correlation coefficient of 0.971. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 545-560, 1997.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 148
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 579-587 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: CF3O2CF3 was photolyzed at 254 nm in the presence of CO in 760 torr N2 or air at 296 K in a static reactor. In N2, the products CF3OC(O)C(O)OCF3 and CF3OC(O)O2C(O)OCF3 were detected by FTIR spectroscopy. In air, the only observed products were CF2O and CO2 and a chain process, initiated by CF3O, was invoked for the conversion of CO to CO2. From both product studies, a mechanism for the CF3O initiated oxidation of CO was derived, involving the addition reaction CF3O2 + CO → CF3OC(O). The rate constant for the reaction CF3O + CO at 296 K at a total pressure of 760 torr air was determined to be k(CF3O + CO) = (5.0 ± 0.9) × 10-14 cm3 molecule-1 s-1. © 1997 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 149
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 619-625 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using relative rate techniques the reactions of chlorine and fluorine atoms with HC(O)F have been determined to proceed with rate constants of k1 = (1.9 ± 0.2) × 10-15 and k2 = (8.3 ± 1.7) × 10-13 cm3 molecule-1 s-1, respectively. Stated errors reflect statistical uncertainty; possible systematic uncertainties could add additional 10% and 20% ranges to the values of k1 and k2, respectively. Experiments were performed at 295 ± 2 K and 700 torr total pressure of air. The results are discussed with respect to the design and interpretation of laboratory studies of the atmospheric chemistry of CFC replacements. © 1997 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 150
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 645-645 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 151
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 637-644 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The relative rate technique has been used to measure the hydroxyl radical (OH) reaction rate constant of ethyl 3-ethoxypropionate (EEP, CH3CH2(SINGLE BOND)O(SINGLE BOND)CH2CH2C(O)O(SINGLE BOND)CH2CH3). EEP reacts with OH with a bimolecular rate constant of (22.9±7.4)×10-12 cm3 molecule-1s-1 at 297±3 K and 1 atmosphere total pressure. In order to more clearly define EEP's atmospheric reaction mechanism, an investigation into the OH+EEP reaction products was also conducted. The OH+EEP reaction products and yields observed were: ethyl glyoxate (EG, 25±1% HC((DOUBLE BOND)O)C((DOUBLE BOND)O)(SINGLE BOND)O(SINGLE BOND)CH2CH3), ethyl (2-formyl) acetate (EFA, 4.86±0.2%, HC((DOUBLE BOND)O)(SINGLE BOND)CH2(SINGLE BOND)C((DOUBLE BOND)O)(SINGLE BOND)O(SINGLE BOND)CH2CH3), ethyl (3-formyloxy) propionate (EFP, 30±1%, HC((DOUBLE BOND)O)(SINGLE BOND)O(SINGLE BOND)CH2CH2(SINGLE BOND)C((DOUBLE BOND)O)(SINGLE BOND)O(SINGLE BOND)CH2CH3), ethyl formate (EF, 37±1%, HC((DOUBLE BOND)O)O(SINGLE BOND)CH2CH3), and acetaldehyde (4.9±0.2%, HC((DOUBLE BOND)O)CH3). Neither the EEP's OH rate constant nor the OH/EEP reaction products have been previously reported. The products' formation pathways are discussed in light of current understanding of oxygenated hydrocarbon atmospheric chemistry. © 1997 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 152
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the self-reactions of HO2, CF3CFHO2, and CF3O2 radicals and the cross reactions of HO2 with FO2, HO2 with CF3CFHO2, and HO2 with CF3O2 radicals, were studied by pulse radiolysis combined with time resolved UV absorption spectroscopy at 295 K. The rate constants for these reactions were obtained by computer simulation of absorption transients monitored at 220, 230, and 240 nm. The following rate constants were obtained at 295 K and 1000 mbar total pressure of SF6 (unit: 10-12 cm3 molecule-1 s-1): k(HO2+HO2)=3.5±1.0, k(CF3CFHO2+CF3CFHO2)=3.5±0.8, k(CF3O2+CF3O2)=2.25±0.30, k(HO2+FO2)=9±4, k(CF3CFHO2+HO2)=5.0±1.5, and k(CF3O2+HO2)=4.0±2.0. In addition, the decomposition rate of CF3CFHO radicals was estimated to be (0.2-2)×103 s-1 in 1000 mbar of SF6. Results are discussed in the context of the atmospheric chemistry of hydrofluorocarbons. © 1997 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 153
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 495-504 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The relative importance of three different routes for the N- nitrosation of amino acids (nitrosation by N2O3, by NO+/NO2H2+ and by intramolecular migration of the nitroso group from the initially nitrosated carboxylate group) was investigated for methylaminobutyric acid, methylaminoisobutyric acid, azetidine-2-carboxylic acid, azetidine-3-carboxylic acid, indoline carboxylic acid, and phenylaminoacetic acid. Reaction kinetics were determined by the initial rate and Guggenheim methods, by spectrophotometric monitoring of the formation of nitroso amino acid. Kinetic parameters were calculated using a nonlinear optimization algorithm based on Marquardt's method. In the experimental rate equation the dominant term corresponds to nitrosation by dinitrogen trioxide, which experiments at various temperatures show to take place via an ordered transition state. Nitrosation by intramolecular migration is significant for substrates facilitating the formation of a transition state structure with a 5- or 6-membered ring. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 495-504, 1997.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 154
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 515-521 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction rates of 2-chloro-3,5-dinitropyridine 1 with a series of arylthiolates 2a-h in methanol have been measured at 25°C. The products are the corresponding 2-thioaryl-3,5-dinitropyridine 3a-h. Good Hammett correlation with ρ value-1.19 was obtained suggesting an elimination-addition mechanism SNAr and the formation of Meisenheimer-like intermediates. Plot of log k2 vs. pKa values of arylthiols gave straight line with β=0.38 indicating that the π-bond breaking in the pyridine ring is so much advanced over bond making between the nucleophile and the carbon that bears the chlorine atom. Excellent correlation between log k2 and log K(carbon basicity of arylthiolates) was obtained. © 1997 John Wiley & Sons. Inc. Int J Chem Kinet 29: 515-521, 1997.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 155
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 535-543 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The recently developed I-atom atomic resonance absorption spectrometric(ARAS) technique has been used to study the thermal decomposition kinetics of CH3I over the temperature range, 1052-1820 K. Measured rate constants for CH3I(+Kr)→CH3+I(+Kr) between 1052 and 1616 K are best expressed by k(±36%)=4.36×10-9 exp(-19858 K/T) cm3 molecule-1 s-1. Two unimolecular theoretical approaches were used to rationalize the data. The more extensive method, RRKM analysis, indicates that the dissociation rates are effectively second-order, i.e., the magnitude is 61-82% of the low-pressure-limit rate constants over 1052-1616 K and 102-828 torr. With the known E0=ΔH00=55.5 kcal mole -1, the optimized RRKM fit to the ARAS data requires (ΔE)down=590 cm-1. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 535-543, 1997.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 156
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 575-578 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The use of hydrogen peroxide in addition to ferrous and ferric salts has been shown an effective method in the decoloration of indigocarmine (IDS), Indigo-5,5′-disulfonic acid disodium salt.The kinetic experiments control have been carried out by means of a conventional spectrophotometric technique. In acid medium and the initial absence of Fe+2, the decoloration process obeys the following rate law:\documentclass{article}\pagestyle{empty}\begin{document}$$ -{{d[\rm{IDS}]} \over {dt}} = k_{\exp}[\rm{IDS}] $$\end{document}Effects of reagents concentrations, temperature, and acidity on the rate experimental constant have been discussed. A feasible reaction mechanism is finally proposed. The rate equation deducted from the mechanism is according to the achieved experimental results. © 1997 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 157
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 599-605 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reactions of 2-chloro-3-nitropyridine (ortho-like) and 5-nitro (para-like) isomer with morpholine and piperidine were studied in methanol and benzene at several amine concentrations and temperatures in the range 25-45°C. The data show that k3-NO2/k5-NO2 ratios are less than unity in methanol. The steric hindrance in the transition state of the 3-nitro (ortho-like) isomer retards o-substitution while the stability of p-quinonoid structure of the 5-nitro (para-like) isomer favors p-substitution. In benzene, the k3-NO2/k5-NO2 ratios are greater than unity. The hydrogen bonding formation between the ammonium hydrogen and the ortho-nitro group in the transition state of 3-nitro isomer favors the o-substitution. © 1997 John Wiley & Sons, Inc.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 158
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constant for the reaction of CH3OCH2 radicals with O2 (reaction (1)) and the self reaction of CH3OCH2 radicals (reaction (5)) were measured using pulse radiolysis coupled with time resolved UV absorption spectroscopy. k1 was studied at 296K over the pressure range 0.025-1 bar and in the temperature range 296-473K at 18 bar total pressure. Reaction (1) is known to proceed through the following mechanism:CH3OCH2 + O2 ↔ CH3OCH2O2# → CH2OCH2O2H# → 2HCHO + OH (kprod)CH3OCH2 + O2 ↔ CH3OCH2O2# + M → CH3OCH2O2 + M (kRO2)k = kRO2 + kprod, where kRO2 is the rate constant for peroxy radical production and kprod is the rate constant for formaldehyde production. The k1 values obtained at 296K together with the available literature values for k1 determined at low pressures were fitted using a modified Lindemann mechanism and the following parameters were obtained: kRO2,0 = (9.4 ± 4.2) × 10-30 cm6 molecule-2 s-1, kRO2,∞ = (1.14 ± 0.04) × 10-11 cm3 molecule-1 s-1, and kprod,0 = (6.0 ± 0.5) × 10-12 cm3 molecule-1 s-1, where kRO2,0 and kRO2,∞ are the overall termolecular and bimolecular rate constants for formation of CH3OCH2O2 radicals and kprod,0 represents the bimolecular rate constant for the reaction of CH3OCH2 radicals with O2 to yield formaldehyde in the limit of low pressure. kRO2,∞ = (1.07 ± 0.08) × 10-11 exp(-(46 ± 27)/T) cm3 molecule-1 s-1 was determined at 18 bar total pressure over the temperature range 296-473K. At 1 bar total pressure and 296K, k5 = (4.1 ± 0.5) × 10-11 cm3 molecule-1 s-1 and at 18 bar total pressure over the temperature range 296-523K, k5 = (4.7 ± 0.6) × 10-11 cm3 molecule-1 s-1. As a part of this study the decay rate of CH3OCH2 radicals was used to study the thermal decomposition of CH3OCH2 radicals in the temperature range 573-666K at 18 bar total pressure. The observed decay rates of CH3OCH2 radicals were consistent with the literature value of k2 = 1.6 × 1013exp(-12800/T)s-1. The results are discussed in the context of dimethyl ether as an alternative diesel fuel. © 1997 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 159
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 647-654 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pseudo-first-order rate constants (k1 obs) for the reaction of MeNHOH with NCPH obey the relationship: k1 obs=k′b[MeNHOH]T2 where [MeNHOH]T represents total concentration of N-methylhydroxylamine buffer. The rate constants, k1 obs obtained at different total concentration of acetate buffer ([Buf]T) in the presence of 0.004 mol dm-3 MeNHOH follow the relationship: k1 obs=kb[Buf]T. The values of acetate buffer-catalyzed rate constant (kb) at different pH reveal the occurrence of both general base- and general acid- or general base-specific acid-catalysis in the reaction of MeNHOH with NCPH. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 647-654, 1997.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 160
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 791-801 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two analytical models are presented to approximate the temperature dependent, rotationally-averaged vibrational-state-specific dissociation rate coefficient for collisions between diatomic molecules and rare gas atoms at combustion temperatures. The new models are derived by making simplifying approximations to a more detailed theoretical model recently reported in the literature. For accuracy, the first model requires, for a given collision pair, knowledge of the maximum vibrational quantum number, a single vibrational-rotational energy and an interaction parameter for dissociation, all of which are tabulated in this article for collisions of Ar with p-H2, O2, N2, and CO. This is in contrast to the recently reported theoretical model, which requires knowledge of all vibrational-rotational energies below the dissociation threshold, in addition to the interaction parameter for dissociation. The second model is simpler and more general than the first, but less accurate. To completely specify this model, knowledge of only the hard sphere cross section, and the characteristic temperatures for vibration and dissociation is required. The two analytical models are shown to agree well with the published theoretical values, with the accuracy of each model increasing with increasing temperature. The present models provide an accurate and efficient means of computing thousands or millions of rate coefficients for use in numerical simulations of combustion processes that couple kinetic equations with the governing equations of fluid dynamics. © 1997 John Wiley & Sons, Inc.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 161
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 803-817 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Experimental kineticists are always faced with the problem of reducing kinetic data to extract physically meaningful information. A particularly vexing problem arises when different models reproduce the data but yield different values for the physical parameters. For over forty-five years Monte Carlo simulation techniques have been used to study the statistical behavior of parameters extracted from data. Not only do these simulations provide realistic uncertainties, correlation coefficients, and confidence envelopes, but they also provide insight into the nature of the model. These insights may be obtained by viewing two-dimensional scatter plots of the fractional changes of the parameters and one-dimensional histograms of the distributions of the changes in the parameters. Monte Carlo simulations are illustrated with examples from OH+CH4 → CH3+H2O and the high-pressure rate coefficient for methyl-methyl association. A more complex problem involves models for pressure-dependent rate coefficients in the falloff region. We have modeled methyl-methyl association with five of the most current analytic approximations for behavior in the falloff region. All of these reproduce the data to within their uncertainties. However, when Monte Carlo techniques are applied the correlations between the parameters and the nonlinear nature of their behavior become evident. We postulate that the statistical behavior of the parameters of a model may be used to distinguish one model from another and, thereby, identify those analytic approximations that hold promise for further investigation and utilization. Finally, the recent advent of high-speed workstations implies that Monte Carlo simulations should become a routine part of the analysis of kinetic data. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 803-817, 1997
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 162
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 861-867 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Fluorimetric titrations of 4-hydroxydiphenyl ether and its anion give stretched sigmoid curves with two inflection points. This reveals that the rates of excited state proton exchange are comparable to the rates of deactivation of the conjugate pair. These curves are analyzed using the lifetimes of the species. The excited state equilibrium constants determined from rate constants and by other methods are compared. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 861-867, 1997
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 163
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute rate coefficient for the gas-phase reaction of NO3 with 3-fluoropropene has been measured using the discharge-flow technique coupled to a LIF detection system for a range of temperatures from 296 K to 430 K. The measured room temperature rate constant is (0.39 ± 0.02) × 10-14 molecule-1 cm3 s-1. The Arrhenius expression k = (7.17 ± 3.34) × 10-12 exp[-(2248 ± 169)/T] is proposed for the reaction.The reactivity of alkenes containing halogen atoms is discussed and compared to that of simple alkenes, on the basis of the correlations between the reactivity against NO3 and the ionization potential of the alkenes.Tropospheric half life of 3-fluoropropene has been estimated at night and during daytime for typical NO3 and OH trophospheric concentrations. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet: 29: 927-932, 1997.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 164
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 9-16 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidation of substituted benzyl alcohols by bis(2,2′-bipyridyl) copper(II) permanganate (BBCP), leading to the corresponding benzaldehydes is first-order with respect to BBCP. Michaelis-Menten type kinetics were observed with respect to the alcohols. The oxidation of a,a-dideuteriobenzyl alcohol indicated the presence of a substantial kinetic isotope effect. The rates of oxidation of meta- and para-substituted benzyl alcohols were correlated in terms of Charton's triparametric LDR equation whereas ortho- substituted benzyl alcohols were correlated with a four parametric LDRS equation. The results of correlation analyses point to an electron-deficient reaction center in the transition state. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 9-16, 1997.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 165
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 43-55 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute (flash photolysis) and relative (FTIR-smog chamber and GC) rate techniques were used to study the gas-phase reactions of Cl atoms with C2H6 (k1), C3H8 (k3), and n-C4H10 (k2). At 297 ± 1 K the results from the two relative rate techniques can be combined to give k2/k1 = (3.76 ± 0.20) and k3/k1 = (2.42 ± 0.10). Experiments performed at 298-540 K give k2/k1 = (2.0 ± 0.1)exp((183 ± 20)/T). At 296 K the reaction of Cl atoms with C3H8 produces yields of 43 ± 3% 1-propyl and 57 ± 3% 2-propyl radicals, while the reaction of Cl atoms with n-C4H10 produces 29 ± 2% 1-butyl and 71 ± 2% 2-butyl radicals. At 298 K and 10-700 torr of N2 diluent, 1- and 2-butyl radicals were found to react with Cl2 with rate coefficients which are 3.1 ± 0.2 and 2.8 ± 0.1 times greater than the corresponding reactions with O2. A flash-photolysis technique was used to measure k1 = (5.75 ± 0.45) × 10-11 and k2 = (2.15 ± 0.15) × 10-10 cm3 molecule-1 s-1 at 298 K, giving a rate coefficient ratio k2/k1 = 3.74 ± 0.40, in excellent agreement with the relative rate studies. The present results are used to put other, relative rate measurements of the reactions of chlorine atoms with alkanes on an absolute basis. It is found that the rate of hydrogen abstraction from a methyl group is not influenced by neighboring groups. The results are used to refine empirical approaches to predicting the reactivity of Cl atoms towards hydrocarbons. Finally, relative rate methods were used to measure rate coefficients at 298 K for the reaction of Cl atoms with 1- and 2-chloropropane and 1- and 2-chlorobutane of (4.8 ± 0.3) × 10-11, (2.0 ± 0.1) × 10-10, (1.1 ± 0.2) &times 10-10, and (7.0 ± 0.8) × 10-11 cm3 molecule-1 s-1, respectively. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 43-55, 1997.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 166
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 99-111 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Alkoxy and β-hydroxyalkoxy radicals are key intermediates formed in the atmospheric degradations of alkanes and alkenes, respectively. In the troposphere, these alkoxy radicals can decompose, isomerize, and react with O2. The literature data concerning the rates of these reactions are evaluated, and predictive schemes allowing the calculation of rate constants for these alkoxy radical reactions for atmospheric purposes are proposed. Good agreement between calculated reaction rates and experimental data concerning the absolute and relative importance of these reaction pathways is obtained, and alkoxy and β-hydroxyalkoxy radical reaction rates for radicals for which experimental data are not presently available can now be calculated for use in atmospheric modeling. © 1997 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 167
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 35-41 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-atom concentration profiles were measured in highly diluted C2N2/NO/Ar reaction systems behind reflected shock waves at temperatures between 3050 K and 4430 K by applying atomic resonance absorption spectroscopy (ARAS). C2N2 served as a thermal source for CN radical which react with both, NO and the subsequently formed N atoms. Computer simulations based on a simplified reaction mechanism revealed strong sensitivity of the measured N atoms to the elementary reactions: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{cl} \rm{CN} + \rm{NO} {\buildrel{\it k}_5\over\rightleftharpoons} \rm{NCO} + \rm{N} & (\rm{R}5)\\ \rm {CN} + \rm{N} {\buildrel{\it k}_9\over\rightleftharpoons} \rm{C} + \rm{N}_2 & (\rm{R}9)\\ \end{array} $$\end{document} A fitting procedure of all experiments allowed determination of individual values of the rate coefficients: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{lr} \rm {\it k}_5\ =\ 9.6\times 10^{13}\ \exp(-21200K/T)\ cm^3\ mol^{-1}\ s^{-1} & (1)\\ \rm {\it k}_9\ =\ 1.9\ .\ .\ .\ 6.0\times 10^{13}\ cm^3\ mol^{-1}\ s^{-1} & (2)\\ \end{array} $$\end{document} The present results enlarge the temperature range of the recommended Arrhenius expression of k5 |1| and confirm recent measurements of the backward reaction of (R-9) |2,3|. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 35-41, 1997.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 168
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 67-71 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Published experimental studies concerning the determination of rate constants for the reaction F + H2 → HF + H are reviewed critically and conclusions are presented as to the most accurate results available. Based on these results, the recommended Arrhenius expression for the temperature range 190-376 K is kF+H2 = (1.1 ± 0.1) × 10-10 exp |-(450 ± 50)/T| cm3 molecule-1 s-1, and the recommended value for the rate constant at 298 K is kF+H2 = (2.43 ± 0.15) × 10-11 cm3 molecule-1 s-1. The recommended Arrhenius expression for the reaction F + D2 → DF + D, for the same temperature range, based on the recommended expression for kF+H2 and accurate results for the kinetic isotope effect kF+H2/kF+D2 is kF+D2 = (1.06 ± 0.12) × 10×10 exp |-(635 ± 55)/T|cm3 molecule-1 s-1, and the recommended value for 298 K is kF+D2 = (1.25 ± 0.10) × 10-11 cm3 molecule-1 s-1. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 67-71, 1997.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 169
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 81-87 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants have been measured for the reaction of OH radicals with four amides, R1N(CH3) - C(O)R2 (R1 = H or Methyl, R2 = Methyl or Ethyl), at 300 and 384 K using flash photolysis/resonance fluorescence. Reactants are introduced under slow flow conditions and are controlled by two independent methods, gas saturation and continuous injection. It turns out that the reactivities of the amides are considerably lower than those of the corresponding amines. The pattern of rate constants obtained at 300 K: 14, 21, 5.2, and 7.6 · 10-12 cm3/s for N,N-Dimethylacetamide (dmaa), N,N-Dimethylpropionamide (dmpa), N-Methylacetamide (maa), and N-Methylpropionamide (mpa), respectively, indicates a single, dominating reaction center and strong electronic effects of the substituents at both sides of the amide function. Correspondingly, the observed negative temperature dependence (E/R = - 400 to - 600 K) excludes a direct abstraction mechanism. © 1997 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 170
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 113-117 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of pyrrolidine with O-ethyl S-(X-phenyl) dithiocarbonates (X = 4-methyl, 4-methoxy, H, 4-chloro, 4-nitro, 2,4-dinitro, and 2,4,6-trinitro) are subjected to a kinetic study in 44 wt% aqueous ethanol, 25.0°C, and ionic strength 0.2 M (maintained with KCl). Pseudo-first-order kinetics are found under amine excess. Linear plots of the pseudo-first-order rate coefficient against concentration of free-base pyrrolidine are obtained for all the reactions, the nucleophilic rate coefficient (kN) being the slope of such plots. The Bronsted-type plot (log kN vs. pKa for the leaving group) is linear with slope βlg = - 0.2, which is consistent with a mechanism through a tetrahedral intermediate (T±) where its formation is rate determining. The βlg value is very similar to that found in the same reactions in water. There is a great difference in the mechanism of the reactions of O-ethyl S-phenyl dithiocarbonate with pyrrolidine (order one in amine) and piperidine (complex order in amine) in aqueous ethanol, and this is attributed to a greater nucleofugality from T± of piperidine rather than pyrrolidine. © 1997 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 171
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 155-160 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The deactivation of I(2P½) by R-OH compounds (R = H, CnH2n+1) was studied using time-resolved atomic absorption at 206.2 nm. The second-order quenching rate constants determined for H2O, CH3OH, C2H5OH, n-C3H7OH, i-C3H7OH, n-C4H9OH, i-C4H9OH, s-C4H9OH, t-C4H9OH, are respectively, 2.4 ± 0.3 × 10-12, 5.5 ± 0.8 × 10-12, 8 ± 1 × 10-12, 10 ± 1 × 10-12, 10 ± 1 × 10-12, 11.1 ± 0.9 × 10-12, 9.8 ± 0.9 × 10-12, 7.1 ± 0.7 × 10-12, and 4.1 ± 0.4× 10-12 cm3 molec-1 s-1 at room temperature. It is believed that a quasi-resonant electronic to vibrational energy transfer mechanism accounts for most of the features of the quenching process. The influence of the alkyl group and its role in the total quenching rate is also discussed. © 1997 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 172
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 149-154 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reactions of ground state oxygen atoms with 1-pentene, 1-hexene, cis-2-pentene, and trans-2-pentene was investigated in the temperature range 200 to 370 K. In this range the temperature dependences of the rate constants can be represented by k = A′ Tn exp(- E′a/RT) with A′ = (1.0 ± 0.6) · 10-14 cm3 s-1, n = 1.13 ± 0.02, E′a = 0.54 ± 0.05 kJ mol-1 for 1-pentene: A′ = (1.3 ± 1.2) · 10-14 cm3 s-1, n = 1.04 ± 0.08, E′a = 0.2 ± 0.4 kJ mol-1 for 1-hexene; A′ = (0.6 ± 0.6) · 10-14 cm3 s-1, n = 1.12 ± 0.05, E′a = - 3.8 ± 0.8 kJ mol-1 for cis-2-pentene; and A′ = (0.6 ± 0.8) · 10-14 cm3 s-1, n = 1.14 ± 0.06, E′a = - 4.3 ± 0.5 kJ mol-1 for trans-2-pentene. The atoms were generated by the H2-laser photolysis of NO and detected by time resolved chemiluminescence in the presence of NO. The concentrations of the O(3P) atoms were kept so low that secondary reactions with products are unimportant. © 1997 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 173
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 187-194 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: For a number of hydrofluorocarbons (HFCs), EHez has been found to have a linear correlation with each of the following: (i) log (k/n); (ii) A/n; and (iii) Ea/R, where EH = HOMO energy of the molecule, z = average fractional positive charge on the abstractable hydrogen atom in the molecule, k = rate constant of the gas-phase H abstraction reaction of the molecule with OH radical at 298 K, n = number of abstractable H atoms in the molecule, A = preexponential factor, and Ea/R = activation temperature of the said reaction. These correlations have been used to estimate the temperature dependent rate constants for the reactions of OH radical with CF3CF2CH2CH2CF2CF3, CF3CH2CF2CH2CF3, CF3CF2CH2CH2F, CF3CH2CH3, CF3CH2CHF2, CF3CHFCH2F, and CHF2CHFCHF2 as {6.97 × 10-13 exp(1481/T)}, {5.43 × 10-13 exp(1754/T)}, {7.95 × 10-13 exp(l308/T)}, {8.0 × 10-13 exp(1300/T)}, {7.03 × 10-13 exp(1470/T)}, {7.33 × 10-13 exp(1417/T)}, and {8.09 × 10-13 exp(1285/T)}, respectively. These have not yet been measured experimentally. Linear correlation between EHez and log (k/n) has also been observed for nine halogen substituted acetaldehydes. On the other hand, EH is found to have a better linear correlation with log (k/n) than EHez in the case of fluorinated ethers and alcohols where the available experimental data are at present limited. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 187-194, 1997.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 174
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 195-201 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate coefficients for reactions between Cl radicals and four ketones were determined at 294 ± 1 K with a relative rate method using a laser photolysis technique. The experiments were conducted in synthetic air in a flow system at atmospheric pressure. A mixture of Cl2/ClONO2 was photolyzed and the formation of NO3 through the reaction Cl + ClONO2 → Cl2 + NO3 was measured with and without ketones in the reaction mixture. The NO3 radical concentration was measured by optical absorption using a diode laser as the light source. The rate coefficients for the Cl-ketone reactions could then be evaluated. The following rate coefficients were obtained (in units of cm3 molecule-1 s-1): cyclohexanone (7.00 ± 1.15) × 10-11; cyclopentanone (4.76 ± 0.33) × 10-11; acetone (1.69 ± 0.32) × 10-12; and 2,3-butanedione (7.62 ± 1.66) × 10-13. The accuracy of the method employed was tested by using the well-studied reaction between Cl and methane and a rate coefficient of (9.37 ± 1.04) × 10-14 cm3 molecule-1 s-1 was obtained, which is in good agreement with previous work. The errors are at the 95% confidence level. The results in this work indicate that a carbonyl group in a ketone lowers the reactivity towards α-hydrogen abstraction by Cl radicals, compared to the corresponding Cl-alkane reactions. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 195-201, 1997.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 175
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 527-533 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for the reactions of OH, NO3, and O3 with pinonaldehyde and the structurally related compounds 3-methylbutanal, 3-methylbutan-2-one, cyclobutyl-methylketone, and 2,2,3-trimethyl-cyclobutyl-1-ethanone have been measured at 300±5 K using on-line Fourier transform infrared spectroscopy. The rate constants obtained for the reactions with pinonaldehyde were: kOH=(9.1±1.8)×10-11 cm3 molecule-1 s-1, kNO3=(5.4±1.8)×10-14 cm3 molecule-1 s-1, and kO3=(8.9±1.4)×10-20 cm3 molecule-1 s-1. The results obtained indicate a chemical lifetime of pinonaldehyde in the troposphere of about two hours under typical daytime conditions, [OH]=1.6×106 molecule cm-3. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 527-533, 1997.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 176
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 339-348 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To better understand the general interrelationships between chemical transformations and physical transformations in solid-state reactions, we have studied the kinetics of methyl transfer in polycrystalline samples of tetraglycine methyl ester [TGME] over the temperature range of 83°C-115°C. Changes in the concentrations of the reactant and various intermediates (sarcosyltriglycine methyl ester METGME, and tetraglycine TG) and products (sarcosyltriglycine METG and N N-dimethyl glycyl triglycine Me2TG) were measured over the entire time course of the reaction using HPLC. Corresponding measurements of physical transformations occurring during the course of the reactions were made using X-ray powder diffractometry and differential scanning calorimetry. Kinetic curves for the loss of TGME in the range of 83°C-115°C have a sigmoldal shape and collapse into one curve when plotted in terms of reduced time. t/t0.5, as do plots of intermediate and product concentration plotted in the same manner. The first 25% of the reaction proceeds homogeneously through what is believed to be the formation of a crystalline solid solution of the intermediates and products in the reactant. The acceleratory character of the kinetic curves in the single-phase portion of the reaction has been described by a kinetic scheme that contains a concentration-dependent rate constant. The apperance of a new crystalline phase beyond 35% of the reaction changes the reaction mechanism from a bulk reaction to an interface-controlled process that causes further acceleration of the methyl transfer. The apparent activation energies for both single-phase and heterophase stages of the reaction are about 100-130 kJ/mole © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 339-348, 1997
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 177
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 349-358 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Relative rate constant measurements have been carried out on the Cl-atom reactions with benzene, chlorobenzene, toluene, xylene, and styrene in 740 torr of air at room temperature (295 K), using the photochemical reactor-FTIR spectroscopy technique. The Cl atoms were generated by the UV photolysis of Cl2, and the reference compounds were CHF, Cl for benzene and chlorobenzene and isobutane for toluene xylene and styrene. Using the absolute rate constant for these two reference compounds reported in the literature, the following kinetic data were obtained for the study compounds (in units of cm3s-1). \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{ll} {\rm Benzene} & (1.3\pm 0.3)\times 10 ^{-15}\\ {\rm Chlorobenzen} & (9.8\pm 2.4)\times 10 ^{-16}\\ {\rm Toluene} & (5.9\pm 0.5)\times 10 ^{-11}\\ o-{\rm Xylene} & (1.5\pm 0.1)\times 10 ^{-10}\\ m-{\rm Xylene} & (1.4\pm 0.1)\times 10 ^{-10}\\ p-{\rm Xylene} & (1.5\pm 0.1)\times 10 ^{-10}\\ {\rm Styrene} & (3.6\pm 0.3)\times 10 ^{-10}\end{array} $$\end{document} The quoted error bars are for ± 2σ. The present kinetic results are compared with available literature data to update and expand the kinetics database for Cl-atom reactions of organic compounds. The results are also analyzed to provide insights into the reaction mechanism for the Cl-atom initiated oxidation of benzene under atmospheric conditions. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 349-358, 1997
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 178
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 377-384 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ligand substitution reaction Fe(CN)5H2O3- + pyrazine → Fe(CN)5 pyrazine3- + H2O has been studied in sodium dodecyl sulfate SDS, hexadecyltrimethylammonium bromide, CTAB, and salt aqueous solutions at 298.2 K. Kinetics were studied in dilute and concentrated salt solutions and in SDS and CTAB solutions at surfactant concentrations below and above the critical micelle concentration. Experimental results show that salt effects can be explained by considering the interaction between the cations present in the working media which come from the background electrolyte, and the Fe(CN)5H2O3- species in the vicinity of the cyanide ligands. This interaction makes the release of the aqua ligand from the inner-coordination shell of the iron(II) complex to the bulk more difficult resulting in a decrease of the reaction rate when the electrolyte concentration increases. Kinetic data in surfactant solutions show that not only micellized surfactants are operative kinetically, but also nonmicellized surfactants are influencing the reactivity. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 377-384, 1997
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 179
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 431-436 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Solvent effects on the kinetics of aquation of [Co(dien)(en)Cl]2+ have been investigated within the temperature range (40-60°C) in acetone-water and ethanol-water media of varying solvent compositions up to 60% by weight of the organic solvent component. The variation of the activation paremeters (ΔG#, Δh#, and ΔS#) with the mole fraction of the organic solvent component was analyzed and discussed. The isokinetic plots were linear in both solvent systems and revealed the existence of compensation effect due to a strong solute-solvent interactions. The correlation of log k with the ionizing power (Y) was found to be linear in both solvent mixtures. Morever, the correlation of log k with D-1 was linear in case of ethanol-water medium while in case of acetone-water it was nonlinear. © John Wiley & Sons, Inc. Int J Chem Kinet 29: 431-436, 1997.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 180
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 437-443 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidation of ortho-, meta-, and para-substituted phenols by Quinolinium Dichromate (QDC) to the corresponding Quinones in aqueous acetic acid medium is first-order with respect to [QDC] and [phenol]. There is no effect of added Quinoline on rate. The reaction is acid catalyzed. A medium of low dielectric constant favors the oxidation process, and the rate of the oxidation process changes with change in the ionic strength of the medium. Electron releasing groups on the benzene ring enhance the rate of oxidation, while electron withdrawing groups retard, compared to the unsubstituted phenol. A correlation exists between log k2 and σ, the Hammett's substituent constant, with a slope of -3.79 at 303 K. Analysis of the rate data using σI and σR values indicate that both inductive and resonance effects of the substituents equally influence the rate of the reaction. The free energy of activation, ΔG≠, is linearly correlated with σ. A probable mechanism is proposed. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 437-443, 1997.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 181
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 473-481 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of HCo(CO)4 (HT) or DCo(CO)4 (DT) with excess cinnamaldehyde (CA) in methylcyclohexane (RH) at 22.2° and under 1 atm of CO follows pseudo-first-order kinetics in HT or DT with an inverse isotopic effect of 0.54. Identified products of the reaction are hydrocinnamaldehyde (HCA) and styrene (STY). The STY is believed to be an artifact of the thermal decomposition of the true product PhCH2CH2C( (DOUBLE BOND) O)Co(CO)4 (X) or its isomer. Reduction of the carbon-carbon double bond in CA is effected by hydrogen from both the cobalt compound and RH. It is proposed that the reaction involves a free-radical chain mechanism in which the rate of the slow step is proportional to [CA]0n, the initial molar concentration of CA raised to a power of 1.5- 1.8. Additionally the rate of conversion of CA to HCA and X meets the criteria of a homocompetitive reaction with [CA], [HCA], and [STY] simple functions of t0.5 (where t is reaction time) for use of DT or (in a single case) a function of (t0.5 + t) for use of HT. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 473-481, 1997.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 182
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 483-493 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: NO2 concentration profiles in shock-heated NO2/Ar mixtures were measured in the temperature range of 1350-2100 K and pressures up to 380 atm using Ar+ laser absorption at 472.7 nm, IR emission at 6.25±0.25 μm, and visible emission at 300-600 nm. In the course of this study, the absorption coefficient of NO2 at 472.7 nm was measured at temperatures from 300 K to 2100 K and pressures up to 75 atm. Rate coefficients for the reactions NO2+M→NO+O+M (1), NO2+NO2→2NO+O2 (2a), and NO2+NO2→NO3+NO (2b) were derived by comparing the measured and calculated NO2 profiles. For reaction (1), the following low- and high-pressure limiting rate coefficients were inferred which describe the measured fall-off curves in Lindemann form within 15% [FORMULA] The inferred rate coefficient at the low- pressure limit, k1o, is in good agreement with previous work at higher temperatures, but the energy of activation is lower by 20 kJ/mol than reported previously. The pressure dependence of k1 observed in the earlier work of Troe[1] was confirmed. The rate coefficient inferred for the high pressure limit, k1∞, is higher by a factor of two than Troe's value, but in agreement with data obtained by measuring specific energy-dependent rate coefficients.For the reactions (2a) and (2b), least-squares fits of the present data lead to the following Arrhenius expressions: [FORMULA] For reaction (2), the new data agree with previously recommended values of k2a and k2b, although the present study suggests a slightly higher preexponential factor for k2a. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 483-493, 1997.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 183
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 6-(Triphenylphosphonio-3′-cyclopentadienyl)-2,3,5-trihalocyclohexa-2,5-diene-1,4-diones (2) are a new class of phosphorus containing dyes that behave as weak bases. Mono-protonation occurs at the cyclopentadiene ring leading to three isomers as assessed by NMR. The kinetics of the protonation were studied by the stopped-flow technique in aprotic media. The activation energies and deuterium isotope effects suggest that the rate-limiting step is the addition of trifluoroacetic acid to the quinone ring rather than direct protonation of the cyclopentadiene ring. © 1997 John Wiley & Sons, Inc.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 184
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 695-704 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Cl- and Br- initiated oxidations of CHCl(DOUBLEBOND)CCl2 in 700 torr of air at 296 K have been studied using a Fourier transform infrared spectrometer. Rate constants k(Cl+CHCl(DOUBLEBOND)CCl2)=(7.2±0.8)×10-11 and k(Br+CHCl(DOUBLEBOND)CCl2)=(1.1±0.4)×10-13 cm3 molecule-1 s-1 were determined using a relative rate technique with ethane and ethylene as references, respectively. The major products observed were CHXClC(O)Cl, (X=Cl or Br), CHClO, and CCl2O. Combining results obtained for the Cl-initiated oxidation of CHCl2(SINGLEBOND)CHCl2, we deduced that Cl-addition on trichloroethylene occurs via channel 1a, Cl+CHCl(DOUBLEBOND)CCl2→ CHCl2(SINGLEBOND)CCl2, (100±12)%. Self-reaction of the subsequently generated peroxy radicals CHCl2(SINGLEBOND)CCl2O2 leads to CHCl2CCl2O radicals which were found to decompose via channel 8a, CHCl2C(O)Cl+Cl, (91±11)% of the time, and channel 8b, CHCl2+CCl2O, (9±2)%. The reaction Br+CHCl(DOUBLEBOND)CCl2→CHBrCl(SINGLEBOND)CCl2 (17a) accounted for ≥(96±11)% of the total reaction. Decomposition of the CHBrCl(SINGLEBOND)CCl2O radicals proceeds (≥93±11)% via CHBrClC(O)Cl+Cl. As part of this work, k(Cl+CHCl2C(O)Cl)=(3.6±0.6)×10-14 and k(Cl+CHCl2(SINGLEBOND)CHCl2)=(1.9±0.2)×10-13 cm3 molecule-1 s-1 were measured. Errors reported above include statistical uncertainties (2σ) and estimated systematic uncertainties. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet: 29: 695-704, 1997.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 185
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 717-723 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The OH radical yields generated in the ozonolysis of ethene (ET), propene (PR), cis-2-butene (CB), trans-2-butene (TB), 2,3-dimethyl-2-butene (TME), and isoprene (ISP) in the presence of 20 Vol.% O2 have been determined in a darkened glass reactor at 1 bar total pressure. The hydroxyl radicals formed were scavenged by an excess of CO added to the systems. The O2 present converted H atoms formed in this reaction into HO2. From measurements of the increase in CO2 generation by FTIR the OH formation yields were determined to be 0.08 (ET), 0.18 (PR), 0.17 (CB), 0.24 (TB), 0.36 (TME), and 0.19 (ISP), respectively, per molecule of reacted ozone. The combined error in the OH determinations is estimated to be 〈10%. © 1997 John Wiley & Sons, Inc.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 186
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 819-824 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An investigation is presented on the kinetics of complexation of aqueous solution of octacyanomolybdate (IV) and -tungstate (IV) after photoinitiation with one of the mixed group ligands containing both N and O, diethanolamine (DEOA), [NH(CH2CH2OH)2]. Under the steady state conditions and with approximation k3 〉 k4 over a range of concentrations, the observed rate law is:\documentclass{article}\pagestyle{empty}\begin{document}$$ \cal{k}_{\rm obs.}={\cal{k}_{2}\cal{k}_{4}\rm {I}_{a}[\rm {OH}^{-}][\rm {NH}(\rm{CH}_{2}\rm{CH}_{2}\rm{OH})_{2}]\over \rm{I}+\it \cal{k}_{2}[\rm {OH}^{-}]} $$\end{document}The complexes show shift in electronic transition supporting the mechanism of association of the ligand followed by the abstraction of some small molecules and then substitution by the ligand. The presence of the specific isobestic point also contributes towards the stability of the complex. The rate constant and quantum yield values are dependent on both the concentration of the metal cyanide and the ligand predicting the mechanism to be an associative one. The complexes have strong absorption in the visible range and are assigned metal-to-ligand electron transfer transition. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 819-824, 1997
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 187
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 767-772 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is shown experimentally that pentafluoroethane undergoes rapid protium-deuterium exchange with water in the presence of hydroxide ion. Addition of dimethylsulfoxide enhances the rate at least by a factor of 100. The first measured fractionation factor data are presented for the temperature range of 50-120°C. These values are compared with the theoretical estimations calculated by using isotopic reduced partition function ratios based on molecular vibrational frequencies. Although catalytic exchange is slow at ambient temperature, the reaction rate becomes measureable above around 60°C because of large activation energy (92 kJ/mole). Comparisons are made with similar data available for various halomethane and haloethane systems. © 1997 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 188
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 835-838 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants are reported for substitution at vanadium(IV) in bis-cyclopentadienylvanadium dichloride by a range of anionic and uncharged nucleophiles in acetonitrile solution. Rate constants have been determined for replacement of the first and of the second chloride. The reactivity of V(cp)2Cl2 is compared with that of Ti(cp)2Cl2. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 835-838, 1997
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 189
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 839-849 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ignition delay times of acetonitrile (CH3CN) in mixtures containing acetonitrile and oxygen diluted in argon were studied behind reflected shock waves. The temperature range covered was 1420-1750 K at overall concentrations behind the reflected shock wave ranging from 2 to 4×10-5 mol/cm3. Over this temperature and concentration range the ignition delay times varied by approximately one order of magnitude, ranging from ca. 100 μs to slightly above 1 ms. From a total of some 70 tests the following correlation for the ignition delay times was derived: tign=9.77×10-12 exp(41.7×103/RT)×{[CH3CN]0.12[O2]-0.76[Ar]0.34} s, where concentrations are expressed in units of mol/cm3 and R is expressed in units of cal/(K mol). The ignition delay times were modeled by a reaction scheme containing 36 species and 111 elementary reactions. Good agreement between measured and calculated ignition delay times was obtained. A least-squares analysis of 60 computed ignition delay times from six different groups of initial conditions gave the following temperature and concentration dependence: E=46.2×103 cal/mol, βCH3CN=0.43, βO2=-1.18, and βAr=0.18. The ignition process is initiated by H-atom ejection from acetonitrile. The addition of oxygen atoms to the system from the dissociation of molecular oxygen and from the reaction CH3CN+O2 → HO2·+CH2CN·is negligible. In view of the relatively high concentration of methyl radicals obtained in the reaction CH3CN+H → CH3+HCN, the branching step CH3+O2 → CH3O+O plays a more important role than the parallel step H+O2→ OH+O. A discussion of the mechanism in view of the sensitivity analysis is presented. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 839-849, 1997
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 190
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 855-860 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase reaction of ozone with vinylcyclohexane and methylene cyclohexane has been investigated at ambient T and p=1 atm of air in the presence of sufficient cyclo-hexane or 2-propanol added to scavenge OH. The reaction rate constants, in units of 10-18 cm3 molecule-1 s-1, are 7.52±0.97 for vinylcyclohexane (T=292±2 K) and 10.6±1.9 for methylene cyclohexane (T=293±2 K). Carbonyl reaction products were cyclohexyl meth-anal (0.62±0.03) and formaldehyde (0.47±0.04) from vinylcyclohexane and cyclohexanone (0.55±0.10) and formaldehyde (0.60±0.05) from methylene cyclohexane, where the yields given in parentheses are expressed as carbonyl formed, ppb/reacted ozone, ppb. The sum of the yields of the primary carbonyls is close to the value of 1.0 that is consistent with the simple mechanisms: O3+cyclo(C6H11)-CH(DOUBLEBOND)CH2→α(HCHO+cyclo(C6H11)CHOO)+(1-α)(HCHOO+cyclo(C6H11)CHO) for vinylcyclohexane and O3+(CH2)5C(DOUBLEBOND)CH2→α(HCHO +(CH2)5COO)+(1-α)(HCHOO+(CH2)5C(DOUBLEBOND)O) for methylene cyclohexane. The coefficients α are 0.43±0.10 for vinylcyclohexane and 0.52±0.05 for methylene cyclohexane, i.e., (formaldehyde+the substituted biradical) and (HCHOO+cyclohexyl methanal or cyclo-hexanone) are formed in ca. equal yields. Reaction rate constants, carbonyl yields, and reaction mechanisms are compared to those for alkene structural homologues. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 855-860, 1997
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 191
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 915-925 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction \documentclass{article}\pagestyle{empty}\begin{document}$\rm {H + HI}\mathop\rightarrow\limits ^{1}\rm {H}_{2}+\rm {I}$\end{document} was studied at 298 K and millitorr pressures employing the “Very Low Pressure Reactor” (VLPR) kinetic technique. H-atoms were generated by dissociating H2 molecules (of a H2/Ar mixture) in a microwave discharge cavity that preceded the very low pressure well-mixed reaction vessel. Quadrupole mass spectrometry was used to analyze molecules and atoms. The mass signal intensities of I and HI were measured at both 20 and 40 eV ionizing potentials while those of H and H2 were measured at 40 eV due to the very weak signal of these species at lower ionization potentials. Three different exit flow orifices were utilized in the reported VLPR experiments of about 2, 3, and 5 mm inner diameter to vary the species concentration under steady-state reaction conditions. A rate constant of k1=(2.1±0.2)×10-11 cm3/molecule.s was determined for the forward reaction at 298 K, which lies between the two previously reported values directly measured at 298 K. Satisfactory mass balance relations were obtained for the iodine atoms (from the HI and I species) which were better than 90% for most of the experiments. The value of the reported rate constant (k1) is 14.3% higher than the value measured by Umemoto et al. [6], and 33.3% lower than the value measured by Lorenz et al. [4]. Based on this comparison, the activation energy E1 of the forward reaction probably lies between those two previously reported values of 580 and 720 cal/mol. Transition State Calculations of A1 and A2 for the reaction of \documentclass{article}\pagestyle{empty}\begin{document}$\rm {H + I}_{2}\mathop\rightarrow\limits ^{2}\rm {HI + I}$\end{document} are in good agreement with the data on both reactions and suggest an activation energy of about 500±100 cal/mol for E2.© 1997 John Wiley & Sons, Inc. Int J Chem Kinet: 29: 915-925, 1997.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 192
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 127-129 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Time-resolved frequency-modulation spectroscopy is shown to be an effective method for measuring the rates of gas-phase reactions. As an example, the rate constant for the reaction of CN with C2H4 at 298 K is measured to be 2.5 ± 0.2 × 10-10 cm3s-1, in good agreement with other literature values. The efficiency and sensitivity of this technique will be of interest to the chemical kineticist. © 1997 John Wiley & Sons, Inc.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 193
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 139-147 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The laser photolysis-long path transient absorption technique was used to study the mechanism and products of the reaction O(3P) + OClO (→M) Products (3) at 260 K in 100 to 400 torr of He, N2, and Ar. ClO was not detected as a reaction product, 〈5% yield, from this reaction at 400 torr and 260 K. A broad UV absorption feature associated with a product of this reaction, with a peak located at 260 nm, was observed. The peak absorption cross section of this species was measured to be (1.72 ± 0.12) × 10-17 cm2 molecule-1. The rate coefficient for the appearance of this species was measured to be (1.69 ± 0.46) × 10-13 cm3 molecule-1 s-1 and was independent of pressure. The rate coefficient for the appearance of the species is ca. 10 times lower than that for the disappearance of O(3P), indicating that the observed species is not a direct product of the reaction of O(3P) with OClO. Mechanistic considerations and the possible identity of the absorber are discussed. © 1997 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 194
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 171-179 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Iron(III)-2,2′-bipyridyl complex obtained, in situ, by direct mixing of iron(III) and 2,2′-bipyridyl, oxidizes aniline, thiourea, and ascorbic acid. The reaction is markedly accelerated by sodium dodecyl sulphate. The rate-[surfactant] profile exhibits a maximum. The kinetic analysis of the micellar effect has been carried out using Berezin's approach. The binding constants of 2,2′-bipyridyl, aniline, thiourea, and ascorbic acid have been determined. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 171-179, 1997.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 195
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 25-33 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants k1, k2, and k3 have been measured at 298 K by means of a laser photolysis-laser magnetic resonance technique and (or) by a laser photolysis-infrared chemiluminescence detection technique (LMR and IRCL, respectively). \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{llclrr} {\rm Cl}+{\rm I}_2\longrightarrow {\rm ICl}+{\rm I}; & k_1 & = & (2.5\pm 0.7)\times 10^{-10} & ({\rm IRCL}) & (1)\\ & k_1 & = & (2.8\pm 0.8)\times 10^{-10} & ({\rm LMR}) & \\ {\rm SiCl}_3+{\rm I}_2\longrightarrow {\rm SiCl}_3{\rm I}+{\rm I}; & k_2 & = & (5.8\pm 1.8)\times 10^{-10} & ({\rm IRCL}) & (2)\\ {\rm SiH}_3+{\rm I}_2\longrightarrow {\rm SiIH}_3+{\rm I}; & k_3 & = & (1.8\pm 0.46)\times 10^{-10} & ({\rm LMR}) & (3)\\ \end{array} $$\end{document} As an average of the LMR and IRCL results we offer the value k1 = (2.7 ± 0.6) × 10-10. Units are cm3 molecule-1 s-1; uncertainties are 2σ including precision and estimated systematic errors. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 25-33, 1997.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 196
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 57-66 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By conducting an excimer laser photolysis (193 and 248 nm) behind shock waves, three elementary reactions important in the oxidation of H2S have been examined, where, H, O, and S atoms have been monitored by the atomic resonance absorption spectrometry. For HS + O2 → products (1), the rate constants evaluated by numerical simulations are summarized as: k1 = 3.1 × 10-11exp|-75 kJ mol-1/RT| cm3molecule-1s-1 (T = 1400-1850 K) with an uncertainty factor of about 2. Direct measurements of the rate constants for S + O2 → SO + O (2), and SO + O2 → SO2 + O (3) yield k2 = (2.5 ± 0.6) × 10-11 exp|-(15.3 ± 2.5) kJ mol-1/RT| cm3molecule-1s-1 (T = 980-1610 K) and, k3 = (1.7 ± 0.9) × 10-12 exp|-(34 ± 11) kJ mol-1/RT| cm3molecule-1s-1 (T = 1130-1640 K), respectively. By summarizing these data together with the recent experimental results on the H(SINGLE BOND)S(SINGLE BOND)O reaction systems, a new kinetic model for the H2S oxidation process is constructed. It is found that this simple reaction scheme is consistent with the experimental result on the induction time of SO2 formation obtained by Bradley and Dobson. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 57-66, 1997.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 197
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for the reaction of 1-chloro-2,3-epoxypropane with p-cresol in the presence of basic catalysts were studied at the temperature range of 71-100°C.It was found that in the presence of sodium p-cresolate, three consecutive reactions proceeded giving the following products: 1-chloro-3-(tolyloxy)-2-propanol (CTP), 1-(p-tolyloxy)-2,3-epoxypropane (TEP) as a main product, and 1,3-di(p-tolyloxy)-2-propanol (DTP). Their rate constants at 71°C were: k1 = 0.030 ± 0.009, k2 = 1.58 ± 0.02, and k3 = 0.033 ± 0.005 dm3/mol · min, respectively.In the presence of quaternary ammonium salts, this process consisted of 5 reactions which led to CTP as a main product as well as TEP and 1,3-dichloro-2-propanol (DCP). The rate constant of CTP formation at 71°C was established, k1 = 0.130 ± 0.030 dm3/mol · min, as were the ratios of the other rate constants k2/k-4 = 1.5 ± 0.2, k5/k-4 = 20.0 ± 5.0, and k4/k1 = 0.6 ± 0.7. Based on the changes in Cl- ion concentration during the reaction, the catalystic activity of quaternary ammonium salts was explained.The kinetic model of these reactions in the presence of basic catalysts has been proposed and appropriate kinetic equations have been presented. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 73-79, 1997.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 198
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chlorine transfer reaction between 3-azabicyclo[3,3,0]octane “AZA” and chloramine was studied over pH 8-13 in order to follow both the amination and halogenation properties of NH2Cl. The results show the existence of two competitive reactions which lead to the simultaneous formation of N-amino- and N-chloro- 3-azabicyclo[3,3,0]octane by bimolecular kinetics. The halogenation reaction is reversible and the chlorine derivative obtained, which is thermolabile and unstable in the pure state, was identified by electrospray mass spectrometry. These phenomena were quantified by a reaction between neutral species according to an apparent SN2-type mechanism for the amination process and a ionic mechanism involving a reaction between chloramine and protonated amine for the halogenation process. Amination occurs only in strongly basic solutions (pH ≥ 13) while chlorination occurs at lower pH's (pH ≤ 8). At intermediate pH's, a mixture of these two compounds is obtained. The relative proportions of the products are a function of intrinsic rate constants, pH and pKa of the reactants. The rate constants and thermodynamic activation parameters are the following: k1 = 45.5 × 10-3 M-1 s-1; ΔH10# = 59.8 kJ mol-1; ΔS10# = - 86.5 J mol-1 K-1 for amination; k2 = 114 × 10-3 M-1 s-1; ΔH20# = 63.9 kJ mol-1; and ΔS20# = - 48.3 J mol-1 K-1 for chlorination. The ability of an interaction corresponding to a specific(NH3Cl+/RR′NH) or general (NH2Cl/RR′NH) acid catalysis has been also discussed. © 1997 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 199
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 119-125 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reactions between sodium nitrite and phenol or m-, o-, or p-cresol in potassium hydrogen phthalate buffers of pH 2.5-5.7 were determined by integration of the monitored absorbance of the C-nitroso reaction products. At pH 〉 3, the dominant reaction was C-nitrosation through a mechanism that appears to consist of a diffusion-controlled attack on the nitrosatable substrate by NO+/NO2H2+ ions followed by a slow proton transfer step; the latter step is supported by the observation of basic catalysis by the buffer which does not form alternative nitrosating agents as nitrosyl compounds. The catalytic coefficients of both anionic forms of the buffer have been determined. The observed order of substrate reactivities (o-cresol ≈ m-cresol 〉 phenol ≫ p-cresol) is explained by the hyperconjugative effect of the methyl group in o- and m-cresol, and by its blocking the para position in p-cresol. Analysis of a plot of ΔH# against ΔS# shows that the reaction with p-cresol differs from those with o- and m-cresol as regards the formation and decomposition of the transition state. The genotoxicity of nitrosatable phenols is compared with their reactivity with NO+/NO2H2+. © 1997 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 200
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 323-331 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A laser-flash photolysis/UV absorption technique has been used to study the temperature dependence (from T = 300 - 470 K) of the self-reaction kinetics of representative primary secondary and tertiary β-hydroxyperoxy radicals \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{lclr} 2\,\rm{HOCH}_2\rm{CH}_2\rm{O}_2 & \longrightarrow & 2\,\rm{HOCH}_2\rm{CH}_2\rm{O}\,+\,\rm{O}_2 & (1\rm{a})\\ & \longrightarrow & \rm{HOCH}_2\rm{CH}_2\rm{OH}\,+\rm{HOCH}_2\rm{CH}_2\rm{O}\,+\,\rm{O}_2 & (1\rm{b})\\ 2\,\rm{HOCH}(\rm{CH}_3)\rm{CH}(\rm{CH}_3)\rm{O}_2 & \longrightarrow & 2\,\rm{HOCH}(\rm{CH}_3)\rm{CH}(\rm{CH}_3)\rm{O}\,+\,\rm{O}_2 & (2\rm{a})\\ & \longrightarrow & \rm{HOCH}(\rm{CH}_3)\rm{CH}(\rm{CH}_3)\rm{OH} & \\ & &+\rm{HOCH}(\rm{CH}_3)\rm{CH}(\rm{CH}_3)\rm{O}+\rm{O}_2 & (2\rm{b})\\ 2\,\rm{HOC}(\rm{CH}_3)_2\rm{C}(\rm{CH}_3)_2\rm{O}_2 & \longrightarrow & 2\,\rm{HOC}(\rm{CH}_3)_2 \rm{C}(\rm{CH}_3)_2\rm{O}\,+\,\rm{O}_2 & (3)\\ \end{array} $$\end{document} The following Arrhenius expressions were derived for the rate coefficients of reactions (1)-(3) (in cm3 molecule -1s-1) and for the product branching ratios of reactions (1) and (2) as a function of temperature (all errors 1σ) \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l}k_1=(6.9_{+2.1}^{-1.5})\times 10 ^{-14}\,\exp[(1040\pm 100)/\rm{T}]\\ \beta_1=(3100_{+3700}^{-1700})\,\exp[(-2400\pm 280)/\rm{T}] (\hbox{ where } \beta_1=k_{1a}/k{1\rm{b}})\\ k_2=(7.7_{+12.8}^{-4.8})\times 10 ^{-15}\,\exp[(1330\pm 350)/\rm{T}]\\ \beta_2=(4.0_{+0.2}^{-0.1})\times 10 ^{4}\,\exp[(-3600\pm 100)/\rm{T}]\\ k_3=(4.7_{+6.5}^{-2.7})\times 10 ^{-13}\,\exp[(-1420\pm 320)/\rm{T}]\\ \end{array} $$\end{document} The calculated rate coefficients for reactions (1)-(3) at 298 K are therefore (in 10-13 cm3molecule -1s -1 23 ± 2, 6.7 ± 1.3, and 0.040 ± 0.012, respectively which compare well with the values measured elsewhere at this temperature using a similar technique. The product branching ratios and the Arrhenius parameters are compared with those for other substituted and unsubstituted peroxy radical self reactions. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 323-331, 1997
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
Close ⊗
This website uses cookies and the analysis tool Matomo. More information can be found here...