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  • 1985-1989
  • 1980-1984  (151)
  • 1980  (151)
  • Physical Chemistry  (92)
  • Biochemistry
  • 1
    Electronic Resource
    Electronic Resource
    Hypoglycemic brain injury (1980)
    Springer
    Acta neuropathologica 50 (1980), S. 31-41 
    Details
    ISSN: 1432-0533
    Keywords: Hypoglycemia ; Nerve cell injury ; Biochemistry ; Light microscopy ; Rat cerebral cortex
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Profound hypoglycemia causing the disappearance of spontaneous EEG activity was induced by insulin in rats. For analysis of cerebral cortical concentrations of labile phosphates, glycolytic metabolites and amino acids, the brain was frozen in situ. For microscopic analysis of the corresponding cerebral cortical areas the brain was fixed by perfusion. Hypoglycemia with an isoelectric EEG for 30 and 60 min caused severe perturbation of the cerebral energy metabolites. After both 30 and 60 min of isoelectric EEG, two microscopically different types of nerve cell injury were seen. Type I injury was characterized by angulated, darkly stained neurons with perineuronal vacuolation, mainly affecting small neurons in cortical layer 3. Type II injured neurons, mainly larger ones in layers 5–6, were slightly swollen with vacuolation or clearing (depending on the histotechnique used) of the peripheral cytoplasm, but had no nuclear changes. Recovery was induced by glucose injection. Improvement in the cerebral energy state occurred during the 30 min recovery period even after 60 min of hypoglycemia. However, the persisting reduction in the size of adenine nucleotide and amino acid pools after 30 or 180 min recovery suggested that some cells remained damaged. In confirmation many type I injured neurons persisted during the recovery suggesting an irreversible injury. The disappearance of virtually all type II injuries indicated reversibility of these histopathological changes. The microscopic changes in hypoglycemia were different from those in anoxia-ischemia suggesting a dissimilar pathogenesis in these states despite the common final pathway of energy failure.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00688532
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  • 2
    Electronic Resource
    Electronic Resource
    The effect of mild microembolic injury on the energy metabolism of the cat brain (1980)
    Springer
    Journal of neurology 223 (1980), S. 285-292 
    Details
    ISSN: 1432-1459
    Keywords: Microembolism ; Cat brain ; Electrophysiology ; Biochemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung An ausgewachsenen Katzen wurde eine Mikroembolisierung der linken Hemisphäre durch Injektion von 2 Millionen Mikrosphären mit einem Durchmesser von 15±5 micron in die linke Arteria carotis communis hervorgerufen. Die pathophysiologischen und biochemischen Auswirkungen wurden elektroenzephalographisch und durch Bestimmung des Energie-Status des Hirnes beurteilt. Die Mikroembolisierung bewirkte eine augenblickliche Amplituden-Reduktion und Verlangsamung des linksseitigen EEGs mit anschließender Erholung innerhalb von 30 bis 60 min. Bei einigen Tieren trat auch über der gegenseitigen Hemisphäre eine vorübergehende Abflachung des EEGs auf. Im Gegensatz zu den deutlichen elektrophysiologischen Veränderungen änderten sich die Substrate des Energie produzierenden Stoffwechsels nur geringfügig. In der embolisierten Hemisphäre stieg das Pyruvat von 0,06 auf 0,10μmol/g und Laktat von 1,9 auf 4,6 μmol/g innerhalb von 5 min an. In den darauffolgenden 4h änderten sich diese Konzentrationen nicht wesentlich. Phosphokreatin, Adenosintriphosphat und das Energie-Potential der Adenin-Nukleotide veränderte sich während dieser Zeit nicht. Lediglich in der gegenüberliegenden Hemisphäre wurde vorübergehend eine Zunahme des ATP beobachtet. Bei 2 Tieren trat nach einigen Stunden eine sekundäre Abflachung und später vollständige Suppression des EEGs beider Hemisphären auf, die von einem völligen Zusammenbruch des Energiestoffwechsels begleitet war. Die Ursache hierfür war die Ausbildung eines massiven Hirnödems mit Steigerung des intrakraniellen Druckes und Kleinhirn-Herniation. Die Versuche legen den Schluß nahe, daß die einseitige Embolisierung des Hirnes mit 2 Millionen Mikrosphären trotz deutlicher elektrophysiologischer Symptome zu keinen wesentlichen Störungen des Energiestoffwechsels führt, solange kein Hirnödem und damit eine intrakranielle Hirndrucksteigerung auftritt. Dies steht in Übereinstimmung mit früheren Ergebnissen, die darauf hindeuten, daß das Ödem und nicht die Ischämie der wesentliche pathogenetische Faktor in der Ausbildung von Hirnschädigungen nach Mikroembolisierung ist.
    Notes: Summary Moderate unilateral cerebral ischemia was produced by microembolism in 24 adult cats. Two million plastic microspheres with a diameter of 15±5 microns were injected into the left common carotid artery via the lingual artery. The physiological and metabolic responses to embolism were assessed by electrocorticography and by determining the cerebral energy state. Embolism caused an immediate slowing and voltage reduction of the ipsilateral electrocorticogram with a gradual recovery after 30 to 60 min. Some animals also had an immediate and short depression of the contralateral electrocorticogram. In spite of the marked functional suppression, metabolites of the cerebral energy-producing metabolism in most of the animals changed only slightly. In the embolized hemisphere pyruvate increased from 0.06 to 0.10 μmol/g and lactate from 1.9 to 4.6 μmol/g within 5 min after embolization and remained at this level during the 4 h observation period. Phosphocreatine, adenosine triphosphate and the energy charge of the adenylate pool remained unchanged during this period. However, there was a slight increase of ATP in the non-embolized hemisphere during the early postembolic period. In two animals, the initial slowing of the electrocorticogram recurred and spread to the contralateral hemisphere, followed by bilateral flattening after a few hours. This delayed functional deterioration was accompanied by complete loss of energy-rich phosphates. These animals also had a progressive increase of cerebrospinal fluid (CSF) pressure and considerable brain swelling with cerebellar herniation after 4 h. It is concluded that unilateral cerebral embolism in the above concentration leads only to a slight increase of anerobic glycolysis without significant perturbation of the cerebral energy state, unless progressive brain swelling with cerebellar herniation supervenes. This supports previous findings, that brain edema and not initial ischemia is the main pathogenetic factor for tissue damage in cerebral microembolism.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00313342
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  • 3
    Electronic Resource
    Electronic Resource
    Biochemical composition of microfilarial and adult stages ofSetaria cervi (1980)
    Springer
    Parasitology research 62 (1980), S. 85-93 
    Details
    ISSN: 1432-1955
    Keywords: Biochemistry ; Nematodes ; Filariae ; Setaria cervi
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract The microfilariae and adults ofSetaria cervi, a filarial parasite of Indian water-buffalo (Bubalus bubalis Linn.) and of other ruminants were analysed for various biochemical constituents. Both stages of the parasite were rich in protein, carbohydrate, and lipids while nucleic acids were detectable in only small amounts. Microfilariae and adults contained 10 and 25% dry matter, 57.4 and 63.0% protein, 8.9 and 14.8% carbohydrate, and 12.8 and 9.2% lipid, respectively. Reducing sugars accounted for 52 and 67% respectively of the total carbohydrate in these two stages. Glycogen accounted for 95% of total carbohydrate in the cold PCA soluble fraction of adult worms while its concentration in microfilariae was very low. Glucose was the main constitutent of reducing sugars while concentrations of fructose were very low. Microfilariae contained more lipids, nucleic acids, mucopolysaccharides, and total phosphorus than adults. The phospholipid percentage was higher in microfilariae than in adults. The amino acid pattern of both stages was very similar.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00925369
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  • 4
    Electronic Resource
    Electronic Resource
    The vacuum UV photolysis of various C4 and C5 olefins: The energy content of the α- and β-methallyl fragments (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 17-28 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In recent publications from this laboratory, we have shown that the fragmentation of photoexcited olefinic molecules in the vacuum UV region leads mainly to the cleavage of a C - C bond located in the ß position relative to the double bond. The allyl fragment bears away part of the excess energy of the photon. At low pressure, this excited radical is capable of undergoing further decomposition. From the pressure effect, we were able to measure the first order rate constant for this secondary fragmentation. In this paper we shall use RRKM calculations in order to get a better idea on how the energy is distributed among the primary fragments. In cases where α- and β;-methallyl radicals were involved, the results show that an important part of the excess energy is located in the methallyl fragment in the 7.1 and 7.6 eV photolysis of 3-methyl-1-butene, 2-methyl-1-butene, and cis-2-pentene.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550120103
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  • 5
    Electronic Resource
    Electronic Resource
    The kinetics of the interaction of peroxy radicals. II. Primary and secondary alkyl peroxyThis work has been sponsored by Grants from the National Science Foundation (CHE-76-16787A02) U.S. Army Research Office (No. DAAG29-76-G0195) (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 43-53 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A chain mechanism is proposed to account for the very rapid termination reactions observed between alkyl peroxy radicals containing α-C - H bonds which are from 104 to 106 faster than the termination of tertiary alkyl peroxy radicals. The new mechanism is with termination by. \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm R}\overline {{\rm CHOO}} $\end{document} is the zwitterion originally postulated by Criegee to account for the chemistry of O3-olefin addition. Heats of formation are estimated for \documentclass{article}\pagestyle{empty}\begin{document}$ \overline {{\rm CH}_2 {\rm OO,}} {\rm }\overline {{\rm RCHOO}} $\end{document}, and \documentclass{article}\pagestyle{empty}\begin{document}$ ({\rm C}\overline {{\rm H}_3 )_2 {\rm COO}} $\end{document} and it is shown that all steps in the mechanism are exothermic. The second step can account for (1Δ)O2 which has been observed. k1 is estimated to be 109-2/θ liter/M sec where θ = 2.303RT in kcal/mole. The second and third steps constitute a chain termination process where chain length is estimated at from 2 to 10. This mechanism for the first time accounts for minor products such as acid and ROOH found in termination reactions. Trioxide (step 3) is shown to be important below 30°C or in very short time observations (〈10 s at 30°C). Solvent effects are also shown to be compatible with the new mechanism.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550120105
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  • 6
    Electronic Resource
    Electronic Resource
    The use of isotopic hydrogen exchange in the study of the acid-catalyzed hydrolysis of purine nucleosides (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 141-143 
    Details
    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
    URL: http://dx.doi.org/10.1002/kin.550120207
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  • 7
    Electronic Resource
    Electronic Resource
    Effect of solvent viscosity on the kinetics of reversible dimerization of phenoxy radicals (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 147-158 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Flash photolysis technique has been used to obtain the rate and thermodynamic parameters of the reversible dimerization reactions of a range of ten phenoxy radicals (I-X) in a toluene-dibutylphthalate mixture (0.6 cP ≤η≤18.4 cP): \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm R}^{.} + {\rm R}^{.} {\mathop{{\buildrel{-\!\!\longrightarrow}\over{\longleftarrow}}}\limits_{k_{-1}}^{k_1}}{\rm D} $$\end{document} The main reason for the difference in the k1 values are the different steric hindrances in radicals. It has been found that the values of k1 for 2,6-diphenyl-4-methoxy- (I), 2-phenyl-(III), and 2-methoxyphenoxy (IV) radicals are 3-5 times smaller than the respective diffusion constants calculated according to the Debye formula with regard to the spin-statistical factor: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{diff} = \sigma \frac{{8{\rm RT}}}{{3000{\rm \eta }}} $$\end{document} The resultant ΔH1≠values for these radicals in toluene and dibutylphthalate are close to the activation energies of the viscous flow of the solvents B. Linear relationships with a slope equal to unity are observed between log k1 and log(T/η). The recombination of radicals I, III, and IV is limited by translational diffusion. The k1 values for 2,6-diphenyl- (VII), 2,6-di-tert-butyl- (IX), and 2,6-di-tert-butyl-4-methylphenoxy (X) radicals are 10-60 times smaller than kdiff and Δ H≠ B. In the case of radical X in toluene ΔH1≠ 0. The recombination of these three radicals includes an intermediate step of complex formation: \documentclass{article}\pagestyle{empty}\begin{document}$${{\rm R}^\cdot+{\rm R}^\cdot}{\mathop {{\scriptstyle\longleftarrow}^{\hskip-13pt\longrightarrow}}}{\rm R^\cdot}\ldots {\rm R}^\cdot \rightarrow {\rm D}$$ \end{document} For 4-phenyl- (II), 2,6- dimethoxy- (V), 2,4-diphenyl- (VI), and radicals VII, IX, and X the linear relationships between log k1 and log (T/η) have a slope of from 0.5 ± 0.05 to 0.8 ± 0.05. The k1-1 versus η relationships for these radicals are not straight lines. The recombination of these six radicals is limited by translational and rotational diffusion. With the aid of theoretical models, the k1 versus η relationships have been used to derive the steric factor f in radical recombination and the angle θ between the axis and the solid angle generatrix. The solid angle defines the reaction spot on the radical-sphere surface. The recombination of the 2,6-diphenyl-4-diphenylmethylphenoxy radical (VIII) takes place in the region intermediate between the diffusion and the kinetic ones, and the relationship between log k1 and log (T/η) for this radical has a plateau portion. The log k-1 versus log (T/η) relationships have precisely the same form as the corresponding k1 relationships, which is quite in line with the theory of diffusion-controlled reversible recombination reactions.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550120302
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  • 8
    Electronic Resource
    Electronic Resource
    Reaction of di-tert-butylnitroxide radicals (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 871-881 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Di-tert-butylnitroxide (DTBN) is the simplest of the stable nitroxide radicals and is only consumed at temperatures higher than 90°C or in the presence of very reactive substrates. The pyrolysis of DTBN in solution gives, at least at low conversion, 2-methyl-2-nitrosopropane and di-tert-butylnitroxide-tert-butyl ether. The reaction involves, as the rate-limiting step, the cleavage of the C—N bond. This reaction takes place with an activation energy of 33 kcal/mol. DTBN is stable in the presence of styrene, aldehydes, hydrogen peroxide, α-methyl-N-ethyl nitrone, phenol, and triphenylmethane. On the other hand, it reacts readily with diethylhydroxylamine, ascorbid acid, ethanethiol, and hexanethiol. For the two former compounds the reaction involves a hydrogen transfer as the rate-determining step, and the reaction proceeds, a low conversion, with simple second-order kinetics. The reaction with the thiols is complex and shows a clear inductiontime.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550121106
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  • 9
    Electronic Resource
    Electronic Resource
    Masthead (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550120401
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  • 10
    Electronic Resource
    Electronic Resource
    The kinetics and the mechanism of the oxidation of carbon monoxide in the presence of hydrogen (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 55-75 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the slow oxidation of CO in the presence of H2 have been studied above the second explosion limit for the mixture 2CO + O2 + X% H2 at the temperature range of 530-570°C, pressures from 300 to 530 torr, and hydrogen contents of 1.1, 2.8, and 5.7%. The second explosion limit has been experimentally determined for the mixture of 2CO + O2 containing 1.0, 3.0, and 5.7% H2. On the basis of the oxidation scheme of CO in the presence of H2, which includes the accepted mechanism of oxidation of hydrogen supplemented by the reactions in which CO takes part, the second explosion limit and the profiles of the slow reaction are calculated by computer methods. The agreement found between experimental and calculated values allows one to conclude that the scheme under consideration rather completely described the slow reaction above the second limit and the occurrence of the second explosion limit in the mixture CO-O2-H2. The rate constant for the reaction HO2 + CO → OH + CO2 was calculated from the experimental data and was found to agree with previous determinations.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550120106
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  • 11
    Electronic Resource
    Electronic Resource
    A dual-path sequence of first-order reactions the protiodeacylation of acetylpropionylmesitylene (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 107-112 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An example of a sequence of competing first-order reactions, leading to a common product, has been found for the sulfodeacylation of acetylpropionylmesitylene. The basic reaction scheme is Scheme l and a kinetic analysis of the component rate constants allows an estimate to be made of the concentrations of the reactant and products as a function of time. In the present system the total concentration of the intermediates B, C, and D never exceeds 0.26% at 25°C, and therefore the kinetics, which were followed spectrophotometrically, were essentially of the conversion of substrate A to the final product E.The kinetics of protiodeacylation have been measured, over a range of temperatures, of propionyl-, dipropionyl-, and acetylpropionylmesitylenes in 89.8% (w/w) sulfuric acid.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550120204
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  • 12
    Electronic Resource
    Electronic Resource
    Thermal decomposition of 2,2-propane-d2. CH3CDCH3 radical isomerization (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 113-122 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decomposition of CH3CD2CH3 was studied from 713 to 853 K at pressures of 98-466 torr. The values of k1/k2 = 2.08 ± 0.05 and k3/k4 = 2.04 ± 0.66 were found independent of temperature by measuring the ratios of CH4/CH3D and CH3CHD2/CH3CD3, respectively, for the following reactions:. Isomerization of CH3CDCH3 was detected by measuring CHDCH2 formed from the isomerized radical. The expression of k21/k22 was found to be where k21 and k22 are the rate constants of. The results and conclusions are discussed and compared with previous works.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550120205
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  • 13
    Electronic Resource
    Electronic Resource
    Oxidation of cyanogen. II. The mechanism of the oxidationFor part I see[1] (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 159-168 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A detailed investigation of the mechanism of cyanogen oxidation is presented. Recent induction time measurements of ignition in cyanogen-oxygen-argon mixtures behind reflected shocks are computer modeled to obtain an agreement between the experimental and calculated values. A 15-step reaction scheme is suggested to reproduce the parameters E and βi in the experimental parametric relation: τ = 10αexp(E/RT)IICiβi. An explanation is offered to the very strong dependence of the induction time on the cyanogen concentration and the very weak dependence on the oxygen concentration. The sensitivity spectrum shows that the induction time is highly dependent on the O + C2N2 → NCO + CN and NCO + M → N + CO + M reactions (shortened) and the O + NCO → CO + NO and N + NCO → N2 + CO reactions (increased).
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550120303
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  • 14
    Electronic Resource
    Electronic Resource
    Atmospheric photodissociation lifetimes for nitromethane, methyl nitrite, and methyl nitrate (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 231-240 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Atmospheric photodissociation rate coefficients and photodissociation lifetimes for nitromethane, methyl nitrite, and methyl nitrate were calculated as a function of altitude from their measured visible and near ultraviolet photoabsorption cross sections at 298 K. The lifetime of methyl nitrite is nearly independent of altitude and is approximately 2 min. From 0 to 50 km the lifetime of nitromethane varies from 10 to 0.5 hr, while that of methyl nitrate changes from 5.3 to 0.09 days, respectively.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550120404
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  • 15
    Electronic Resource
    Electronic Resource
    The thermal decompositions of carbamates. IV. The ethyl N—methyl—carbamate system (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 241-252 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ethyl N—methylcarbamate decomposes thermally over the temperature range of 600-650 K by competing first-order reactions, one forming methylamine, carbon dioxide, and ethylene, the other forming methyl isocyanate and ethanol. The first-order rate constants are described in S—1 units by the equations where R = 1.986 cal/deg mol. The appareance of sym—dimethylurea among the products raised the possibility of gas-phase transesterifications. These were ruled out by the study of the reactions of sym-dimethylurea at 604 K which showed its behavior to be well explained by the rapid decomposition in the gas phase which is reversed in the condensation stage in the analysis.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550120405
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  • 16
    Electronic Resource
    Electronic Resource
    Thermal decomposition of ammonia in shock waves (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 439-450 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of ammonia was studied by means of the shock-tube and vacuum ultraviolet absorption spectroscopy monitoring the concentration of atomic hydrogen. The rate constants of both the initiation reaction and the consecutive reaction were determined directly as \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 = 10^{16.14} \exp (- 90.6{\rm kcal}/RT){\rm cm}^{\rm 3} /{\rm molsec} $$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{II} = 10^{14.30} \exp (- 23.29{\rm kcal}/RT){\rm cm}^{\rm 3} /{\rm molsec} $$\end{document} respectively.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550120702
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  • 17
    Electronic Resource
    Electronic Resource
    Deactivation of O2(A3Σu+) by O2, O, and Ar (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 501-508 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: O2 in the A3Σu+ state has been prepared in a discharge flow system by recombining oxygen atoms on a nickel surface. The decay of this excited state was followed by observing the emission between 280 and 400 nm. The wall deactivation was observed to approach unit efficiency. Rate constants were determined to be 0.9 × 10-11, 2.9 × 10-13, and 8.6 × 10-16 cm3/molecule sec for the quenching of O2(A3Σu+) by O, O2, and Ar, respectively.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550120706
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  • 18
    Electronic Resource
    Electronic Resource
    Reaction of carbon monoxide with ozone: Kinetics and chemiluminescence (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 535-546 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of carbon monoxide with ozone was studied in the range of 75-160°C in the presence of varying amounts of CO2 and, for a few experiments, of O2. At room temperature the reaction was immeasurably slow, but in a flow system it showed chemiluminescence with undamped oscillations. In a static system above 75°C the emission showed damped oscillations when O2 was present. In the absence ofadded O2 the emission showed a slow decay with a half-life of 1 hr. The luminescence consisted of partially resolved bands in the range of 325-600 nm, and the source was identified as CO2(1B2) → CO2(1Σg+) + hv. The kinetics were complex, and the observed rate law could be accounted for bya mechanism involving the chain sequence \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm O(}^{\rm 3} P{\rm ) + CO( + M)}\mathop {{\rm rightarrow}}\limits^{\rm 3} {\rm CO}_{\rm 2} {\rm (}^{\rm 3} B_{\rm 2} {\rm ) ( + M), CO}_{\rm 2} {\rm (}^{\rm 3} B_{\rm 2} {\rm ) + O}_{\rm 3} {\rm }\mathop {{\rm rightarrow}}\limits^{\rm 7} {\rm CO}_{\rm 2} {\rm (}^{\rm 1} \sum\nolimits_{\rm g}^{\rm + } {} {\rm ) + O}_{\rm 2} {\rm + O} $\end{document}. From measurements of -d[O3]/dtand relative emission, rate constant ratios were obtained and estimates of k3were made.
    Additional Material: 5 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    The rate constant of NO + O3 → NO2 + O2 in the temperature range of 283-443 K (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 547-554 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction NO + O3 → NO2 + O2 has been studied in a 220-m3 spherical stainless steel reactor under stopped-flow conditions below 0.1 mtorr total pressure. Under the conditions used, the mixing time of the reactants was negligible compared with the chemical reaction time. The pseudo-first-order decay of the chemiluminescence owing to the reaction of ozone with a large excess of nitric oxide was measured with an infrared sensitive photomultiplier. One hundred twenty-nine decays at 18 different temperatures in the range of 283-443 K were evaluated. A weighted least-squares fit to the Arrhenius equation yielded k = (4.3 ± 0.6) × 10-12 exp[-(1598 ± 50)/T] cm3/molecule sec (two standard deviations in brackets). The Arrhenius plot showed no curvature within experimental accuracy. Comparison with recent results of Birks and co-workers, however, suggests that a nonlinear fit, as proposed by these authors, is more appropriate over an extended temperature range.
    Additional Material: 3 Ill.
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  • 20
    Electronic Resource
    Electronic Resource
    On the gas-phase free radical displacement reaction CH3 + CD3COCD3 → CD3 + CH3COCD3 (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 623-635 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase free radical displacement reaction has been studied in the temperature range of 240-290°C and at 140°C with the thermal decomposition of azomethane (AM) and di-tert-butylperoxide (DTBP), respectively, as methyl radical sources. The reaction products of the CD3 radicals were analyzed by mass spectrometry. Assuming negligible isotope effects, Arrhenius parameters for the elementary radical addition reaction were derived: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{{\rm 10}} k_1 (cm^3 /mol\sec) = (10.5 \pm 0.4) - (11,500 \pm 1100)/4.576T $$\end{document}The data are discussed with respect to the back reaction and general features of elementary addition reactions.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550120904
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  • 21
    Electronic Resource
    Electronic Resource
    Masthead (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550121001
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  • 22
    Electronic Resource
    Electronic Resource
    The hydrogen peroxide-iodic acid-manganese (ii)-acetone oscillating system: Further observations (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 683-698 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The redox potential and iodine concentration behavior of the title reaction and component reactions have been examined. The effect of hydrogen peroxide, potassium iodate, manganese (II) sulfate, sulfuric acid, and acetone concentration on the time period and redox potential behavior is reported. Iodine production and consumption rates for the component reactions are given, and some mechanistic suggestions, involving iodine dioxide as the one electron oxidant, are made.
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    URL: http://dx.doi.org/10.1002/kin.550121003
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  • 23
    Electronic Resource
    Electronic Resource
    Azide mechanisms for the production of NCl metastables (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 741-753 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The production of both the b1Σ+ and a1Δ states of NCl has been observed from the reaction of HN3 with flowing streams of Cl and F atoms. The results suggest that a two-step reaction sequence is responsible for the production of excited NCl, as follows: The rate contant (all products) for the first step is k(F + HN3) 〉 1 × 10-11 cm3/molecule sec. Comparison of this value to results obtained in a previous study of the F + HN3 system yields a value k(F + N3) = 2 × 10-12 cm3/molecule sec. The rate constant for the reaction of chlorine atoms with HN3 was determined to be k(Cl + HN3) 1 × 10-12 cm3/molecule sec. The difference between the Cl + HN3 and F + HN3 rates is interpreted in terms of an addition-elimination mechanism.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550121007
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  • 24
    Electronic Resource
    Electronic Resource
    A systematic nomenclature for the “peroxyacyl nitrates,” the functional and structural misnomers for anhydride derivatives of nitrogen oxo acids (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 771-775 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550121011
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  • 25
    Electronic Resource
    Electronic Resource
    Rate coefficients of decomposition of azoethane and azoisopropane (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 993-999 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decompositions of azoethane and azoisopropane were studied in a large excess of ethylene in the temperature interval of 523-623 K. It was demonstrated that under such conditions, the bulk of the alkyl radicals react with ethylene. Via measurements on the consumption of the azo compound and on the formation of gaseous nitrogen, it was possible to determine the rate coefficients of the initiation reactions:\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm R - N} = {\rm N - R} \to {\rm N}_{\rm 2} {\rm + 2R}^{\rm .} $$\end{document}. The resulting data were as follows: For azoethane, \documentclass{article}\pagestyle{empty}\begin{document}$$ \log _{10} k_1 (\sec ^{ - 1}) = (15.8 \pm 0.1) - (205.1 \pm 1.5){\rm kJ/mol/2}{\rm .3RT} $$\end{document}. For azoisopropane, \documentclass{article}\pagestyle{empty}\begin{document}$$ \log _{10} k_1 (\sec ^{ - 1}) = (16.2 \pm 0.3) - (196.8 \pm 2.6){\rm kJ/mol/2}{\rm .3RT} $$\end{document}
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    URL: http://dx.doi.org/10.1002/kin.550121208
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  • 26
    Electronic Resource
    Electronic Resource
    Masthead (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550120501
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  • 27
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    Kinetics of oxidation of organic compounds by silver(II) in aqueous perchloric acid solution. IV. Aliphatic alcoholsPart III, E. Mentasti, E. Pelizzetti, and C. Baiocchi, J.C.S. Perkin II, 77 (1978). (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 285-299 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics and mechanism of the silver(II) oxidation of methanol, ethanol, 1-propanol, 1-methyl- ethanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, D4-methanol, and D6-methanol have been investigated at 8.0 and 20.0°C in aqueous perchloric acid media (1.00 ≤ [HClO4] ≤ 4.00M; μ = 4.0M). The kinetics were monitored by following the disappearance of Ag(II) with a spectrophotometric stopped-flow technique. The reactions are first order in each reactant and involve both Ag2+ and AgOH+ species. No kinetic or spectroscopic evidence for complex formation between reactants was obtained. The results are discussed with reference to electron density on the —OH or αC-H substrate sites and to the isotopic hydrogen/deuterium rate quotients found for methanol and ethanol.
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    URL: http://dx.doi.org/10.1002/kin.550120502
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  • 28
    Electronic Resource
    Electronic Resource
    Carbon kinetic isotope effect in the oxidation of methane by hydroxyl (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 371-377 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The carbon kinetic isotope effect in the reaction of CH4 with OH has an experimentally measured value of 1.003. The measurement was performed using a static system in which the source of OH was the gas-phase photolysis of H2O2 with ultraviolet light produced by a high-pressure mercury arc lamp. Implications for the tropospheric cycle of CH4 are considered briefly.
    Additional Material: 2 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550120602
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  • 29
    Electronic Resource
    Electronic Resource
    Titration of oxygen chemisorbed on platinum: Experiment and simulation (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 417-429 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The titration of chemisorbed oxygen by carbon monoxide to form carbon dioxide has been studied from 373 to 673 K over polycrystalline platinum. The pressure transients for CO and CO2 have been measured and simulated numerically. A complex Langmuir-Hinshelwood mechanism is found which fits all the data, and it is not necessary to invoke Eley-Rideal kinetics. The results fall into two temperature regimes, above and below 473 K, which are characterized by different Arrhenius parameters. A change in activation energy with oxygen coverage is also found below 473 K.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550120607
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  • 30
    Electronic Resource
    Electronic Resource
    Masthead (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550120701
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  • 31
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    Oxidation studies with peroxomonophosphoric acid. II. A kinetic and mechanistic study of dimethyl sulfoxide oxidation in acid and alkaline mediaPart I appeared in Bulletin ofthe Chemical Society of Japan, 52, 3084 (1979); see [1]. (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 491-499 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of dimethyl sulfoxide (DMSO) oxidation by peroxomonophosphoric acid (PMPA) in aqueous medium at 308 K and I = 0.4 mol/dm3 follow the rate expressions In the pH range from 0 to 2, where k1 and k2 are 5.092 × 10-1 dm3/mol sec and ≃ 0, respectively; in the pH range from 4 to 7, where k2 = 8.127 × 10-3 and k3 = 2.90 × 10-3 dm3/mol sec; and in the pH range from 10 to 13.6, where k4 ≃ 0, and k5 = 3.08 × 10-2 dm3/mol sec.The reaction is interpreted in terms of mechanisms involving an electrophilic and a nucleophilic attack of the peroxomonophosphoric acid species, respectively, in acid and alkaline regions, on the sulfur atom of the sulfoxide molecule giving rise to SN2-type transition states followed by oxygen-oxygen bond fission to form the products.
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  • 32
    Electronic Resource
    Electronic Resource
    Micellar effects upon electron transfer from ferrocenes (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 519-533 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidations of ferrocene (FcH) and n-butylferrocene (FcBu) by ferric salts (nitrate or bromide) are strongly inhibited by aqueous cetyltrimethylammonium bromide and nitrate (CTABr and CTANO3, respectively). The kinetics of inhibition fit a model in which the substrates are distributed between water, and the micelles and binding constants Ks to the micelle can be estimated. The oxidations are strongly catalyzed by micelles of sodium lauryl sulfate (NaLS), and the kinetics can be fitted to a model in which the reaction rate depends upon the concentration of both reactants in the micellar pseudophase and the rate constants in that pseudophase, which for both substrates are very similar to those in water. Some added salts reduce the micellar catalysis by excluding ferric ions from the micelle. The oxidations of FcH and FcBu by ferricyanide ions are too fast to be followed in water, but they are inhibited by anionic micelles of NaLS. By analyzing the rate surfactant profiles using independently measured values of Ks the second-order rate constants in water have been estimated.
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    URL: http://dx.doi.org/10.1002/kin.550120803
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  • 33
    Electronic Resource
    Electronic Resource
    Masthead (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550120901
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  • 34
    Electronic Resource
    Electronic Resource
    Rate constants for self- and cross terminations of transient radicals in solution by effect modulated electron spin resonance spectroscopy (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 637-647 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is shown how electron spin resonance spectroscopy with modulated radical initiation can be used to analyze by purely spectroscopic means the second-order termination kinetics of systems containing two different kinds of radicals. The technique is applied to species generated by photoreduction of acetone in tetraethoxy silane. The bimolecular self- and cross reactions of \documentclass{article}\pagestyle{empty}\begin{document}${\rm (CH}_{\rm 3} {\rm CH}_{\rm 2} {\rm O)}_{\rm 3} {\rm SiO\dot CHCH}_{\rm 3} (\dot R_1 )\,and\,(CH_3 )_2 \dot COH(\dot R_2 )$\end{document} are found to be encounter-controlled processes. For the cross termination the often used relation k12 = (4 k1k2)1/2 is verified experimentally.
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  • 35
    Electronic Resource
    Electronic Resource
    Masthead (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550121201
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  • 36
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    Photolysis of azomethane-propane mixtures. Arrhenius parameters for the hydrogen abstraction reactions of methyl with azomethane and with propane (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 1031-1043 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mixtures of up to 14% azomethane in propane have been photolyzed using mainly 366 nm radiation in the ranges of 323-453 K and 25-200 torr. Detailed measurements were made of the yields of nitrogen, methane, and ethane. Other products observed were isobutane, n-butane, ethene, and propene. A detailed mechanism is proposed and shown to account for the observed variation of product yields with experimental conditions. The quantum yield of the molecular process \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_3 {\rm N}_2 {\rm CH}_3 + h\nu \to {\rm C}_2 {\rm H}_6 + {\rm N}_2 $$\end{document} is found to be given by the temperature-independent equation\documentclass{article}\pagestyle{empty}\begin{document}$$ \phi _2 = 0.0092 \pm 0.0005] $$\end{document} The values of rate constants obtained are \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log} k_3 ({\rm cm}^3 /{\rm mol}\,{\rm sec}) = 12.03 \pm 0.15 - 40.8 \pm 1.1{\rm kJ}/{\rm mol}/(2.3RT) $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}k_4 ({\rm cm}^3 /{\rm mol}\,{\rm sec}) = 11.42 \pm 0.15 - 40.7 \pm 1.1{\rm kJ}/{\rm mol}/(2.3RT) $$\end{document} where the reactions are and it is assumed that the rate constant for the reaction is given by \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}k_5 ({\rm cm}^3 /{\rm mol}\,{\rm sec}) = 13.4 $$\end{document}
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  • 37
    Electronic Resource
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    Masthead (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550120101
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  • 38
    Electronic Resource
    Electronic Resource
    Masthead (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550120201
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  • 39
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    Kinetic studies of free radical reactions by mass spectrometry. I. The reactions SO + NO2 and ClO + NO (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 79-96 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel technique is described for forming ground-state SO X3Σ— radicals free of reactive impurities in a discharge-flow system. Mass spectrometric detection of SO and ClO free radicals has been used to study the kinetics of the following reactions at 295 K:
    Additional Material: 5 Ill.
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  • 40
    Electronic Resource
    Electronic Resource
    Masthead (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550120301
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  • 41
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    Evaluation of the rate coefficients and arrhenius parameters of hydrogen atom transfer reactions. II. Application of the method (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 183-214 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The bond-strength-bond-length (BSBL) method was used to estimate Arrhenius parameters and rate coefficients for various hydrogen atom transfer reactions of the type A + BC → AB + C. In most cases predicted activation energies agreed within 1.2 kcal/mol with the experimental values (average error = 1.12 and standard deviation = 1.42), and the calculated log A agreed within 0.55 log units with the literature data (average error = 0.47 and standard deviation = 0.57). Predicted activated complex properties were shown to agree very well with potential energy surface properties obtained from ab initio quantum mechanical calculations. Detailed comparison of the BSBL results and the results of bond-energy-bond-order (BEBO)-type calculations are presented.
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    URL: http://dx.doi.org/10.1002/kin.550120305
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  • 42
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    The rate constant for combination of a CCl3 radical with cyclohexyl or n-hexyl radicals. An evidence for the value of the rate constant for a Cl atom transfer (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 217-223 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The variation of the radiolytic yield of hexachloroethane in the system alkane + carbon tetrachloride can be used to measure the rate constant for the combination of a CCl3 radical with an alkyl radical. The treatment of the data for hexane and cyclohexane shows that the rate for a Cl atom transfer must be lower than the high values of Katz et al. and Tuan et al.
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    URL: http://dx.doi.org/10.1002/kin.550120402
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  • 43
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    Electronic Resource
    A modified model of diffusion-controlled reactions (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 261-270 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The treatment used for diffusion-controlled reactions is extended to the case when the final jumplike step of the reagent approach differs essentially from the preceding diffusion. In terms of the model proposed it is possible to take into account, in a simple way, chemical inhomogeneity of the reagents when the in-cage reaction rate depends on the pair state (for example, on the molecular orientation). In this connection the reaction can be controlled either by the reagent intrusion into the solvation shell of the partner, or by the in-cage relaxation.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550120407
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  • 44
    Electronic Resource
    Electronic Resource
    A concerted hydrogen-transfer reaction in the gas phase (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 301-313 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the thermal reaction of mixtures of ethylene and cyclopentene has been examined for the occurrence of a concerted hydrogen-transfer reaction,\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm C}_2 {\rm H}_4 + c - {\rm C}_5 {\rm H}_8 \to {\rm C}_2 {\rm H}_6 + c - {\rm C}_5 {\rm H}_6 $$\end{document}. The main products of the reaction were ethane and cyclopentadiene, and the rate of formation of ethane was first order in each reactant over a 2500-fold change in the ratio of concentrations of the reactants. An increased surface-to-volume ratio of the reaction vessel or additions of oxygen and nitric oxide had little effect on the rate of formation of ethane, and it was concluded that the dominant reaction in the system was the concerted hydrogen-transfer process. The rate constant for the reaction, measured over the temperature range of 325-505°C, was represented as\documentclass{article}\pagestyle{empty}\begin{document}$$ \log k(1./{\rm mol}\,{\rm sec)}\, = \,12.0 - \frac{{49,700}}{{2.3RT}} $$\end{document}
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550120503
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  • 45
    Electronic Resource
    Electronic Resource
    Masthead (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550120601
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  • 46
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    Electronic Resource
    Aluminium monoacetate complex formation reaction studied by the pressure-jump method (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 387-392 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: One of two pressure-jump relaxation processes observed in Al(III) acetate aqueous solution, the slow one, was studied kinetically. The relaxation was ascribed to the Al(III) monoacetate complex formation reaction. The detailed reaction mechanism, including the hydrolysis process, was revealed, and the rate constants were obtained.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550120604
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  • 47
    Electronic Resource
    Electronic Resource
    Reaction of hydrogen atoms with dimethyldisulfide (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 431-438 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hydrogen atoms, generated by the mercury (3P1) sensitization of H2, were allowed to react with dimethyldisulfide in the temperature range of 25-155°C. The only retrievable product is methanethiol, formed in the primary metathetical reaction \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm H} + {\rm CH}_3 {\rm SSCH}_3 {\rm CH}_3 {\rm SH} + {\rm CH}_3 {\rm S} $\end{document}. The intermediacy of thiyl radicals was clearly demonstrated in experiments carried out in the presence of ethylene where one of the major products detected was ethyl methyl sulfide, formed via CH3S + C2H5 → CH3SC2H5. The major fate of the CH3S radical is recombination and disproportionation, and the yield of methanethiol formed via disproportionation contributes less than 5% to the total thiol yield. The rate coefficient of step 1, from competition with the reaction \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm H} + {\rm C}_{\rm 2} {\rm H}_{\rm 4} {\rm C}_{\rm 2} {\rm H}_5 $\end{document}, is k1 = (5.7 ± 1.2) × 1012 exp[—(100 ± 100)/RT] cm3/mol sec.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550120608
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  • 48
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    A reinvestigation of the temperature dependence of the rate constant for the reaction O + O2 + M → O3 + M (for M = O2, N2, and Ar) by the flash photolysis resonance fluorescence technique (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 469-490 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The flash photolysis resonance fluorescence technique has been used to reinvestigate the kinetics of the oxygen atom-oxygen molecule combination reaction. Third-order rate constants for O2, N2, and Ar as deactivant molecules were determined over the temperature range of 219-368 K. The results presented herein are the most extensive data sets available for atmospheric modeling and are used to formulate a recommendation for such purposes. The recommended rate expressions are \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1^{{\rm air}} = (1.07 \times 10^{ - 34})\exp (525/T){\rm cm}^{\rm 6} /{\rm molecule}^{\rm 2} {\rm sec} $$\end{document} or \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1^{{\rm air}} = (6.3 \times 10^{ - 34})\exp (T/300)^{\rm - 1.9}{\rm cm}^{\rm 6} /{\rm molecule}^{\rm 2} {\rm sec} $$\end{document} Comparisons of these results with existing literature data are presented.
    Additional Material: 8 Ill.
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  • 49
    Electronic Resource
    Electronic Resource
    Consistency of a set of chemical reactions (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 509-517 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is a useful feature of many general chemical kinetics programs that the user's reaction scheme is tested as far as possible before a calculation is started. Attempts are made to answer the question: How far can a reaction scheme be tested for consistency, with respect to mass conservation, without knowing the molecular weights of the species involved? It is found that this problem can be transformed so that it is solvable by the standard methods used in linear programming.
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    URL: http://dx.doi.org/10.1002/kin.550120802
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  • 50
    Electronic Resource
    Electronic Resource
    Kinetics of the thermal decomposition of pyridine in a flow system (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 555-568 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the pyrolysis of pyridine was studied in the temperature range of 875-1050°C, at 1 atm total pressure, in a Vycor stirred-flow reactor. Initial concentrations ranged from 0.25 to 2 mol % in helium and reaction times from 0.25 to 4 sec. It was found at the lower temperatures that the reaction was mixed first and second order. At the higher temperatures an autocatalytic term, zero order in the substrate and first order in the concentration of pyridine decomposed, was necessary in addition to the other two terms to describe the kinetic data. Most of the product was in the form of a primarily aromatic, nonvolatile tar; the major volatile products were HCN and C2H2. An increase in the surface-to-volume ratio of the reactor decreased the rate, indicating a radical chain or sequential reaction with radical consumption on the surface. Experiments with additives showed that C2H2 increased the rate. Using the kinetic and product data, some mechanistic considerations are discussed, and a mechanism is proposed to account for the first-order term.
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  • 51
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    Kinetics and mechanism of the autoxidation of pentaerythrityl tetraheptanoate at 180-220°CPresented in part at the 174th National Meeting of the American Chemical Society, Chicago, IL, August 1977, Abstracts, No. PHYS 10 (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 577-603 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A kinetic and mechanistic study of the autoxidation of liquid pentaerythrityl tetraheptanoate (PETH) at 180-220°C has been carried out utilizing a stirred-flow reactor. The results are consistent with the occurrence of a chain reaction scheme similar to that proposed for n-hexadecane autoxidation, namely, the formation of monohydroperoxides by the intermolecular abstraction reaction (3), the formation of α,γ- and α,δ-dihydroperoxides and α,γ- and α,δ-hydroperoxyketones by intramolecular peroxy radical abstraction reactions (4) and (4*), the bimolecular termination of peroxy radicals, reaction (6), and the rapid conversion of α,γ-hydroperoxyketones to the corresponding cleavage acids and methyl ketones, reaction (7). Comparisons of various rate parameters for the n-hexadecane and PETH systems reveal that the values of k7 and (k3/H atom)/(2 k6)1/2 are within experimental uncertainties identical for the two systems at 180°C. The proposed reaction scheme includes the concurrent formation of hydroxy radicals and hydroperoxyketone species. The results of kinetic analysis and the experimentally observed isomer distributions of primary and secondary monohydroperoxide products at high and low oxygen pressures suggest that ≈60% of the hydrogen abstractions from PETH at high oxygen pressures occur by hydroxy radicals.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550120902
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  • 52
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    Kinetics of the reaction Cl + HO2 = HCl + O2, using molecular modulation spectrometry (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 649-660 
    Details
    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 (1), Cl + HO2 → HCl + O2, was measured using molecular modulation spectrometry to investigate HO2 radical kinetics in the modulated photolysis of Cl2—;H2—O2 mixtures at 760 torr pressure. HO2 was monitored directly in absorption at 220 nm, and k1 was determined from computer simulations of the observed kinetic behavior of HO2, using a simple chemical model. The results gave \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 /k_4 = 3.0_{ - 1.8}^{ + 5.1} \exp [+ (2120 \pm 370)/T] $$\end{document} where k4 is the rate constant for the reaction of Cl with H2. A consensus value of k4 gave k1 = 6.9 × 10-11 cm3/molecule sec, independent of temperature in the range of 274-338 K with an overall uncertainty of ±50%. The relative importance of reaction (1) for the conversion of Cl to HCl in the stratosphere is discussed briefly.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550120906
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  • 53
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    Rate data for O + OCS → SO + CO and SO + O3 → SO2 + O2 by a new time-resolved technique (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 729-739 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pulsed laser photolysis of O3 in a large excess of N2 has been used to generate O(3P) atoms in the presence of OCS. By observing chemiluminescence from the small fraction of electronically excited SO2 formed in the reaction of SO with O3, rate constants of (1.7 ± 0.2) × 10-14 and (8.7 ± 1.6) × 10-14 cm3/molecule sec have been determined at 296 ± 4 K for the reactions and In addition, it has been shown that any reaction between SO and OCS has a rate constant 10-14 cm3/molecule sec.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550121006
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  • 54
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    Electronic Resource
    Comments on “predicting gas phase organic molecule reaction rates using linear free energy correlations. I. O(3P) and OH addition and abstraction reactions” (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 761-765 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550121009
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  • 55
    Electronic Resource
    Electronic Resource
    Masthead (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550121101
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  • 56
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    A smog chamber and modeling study of the gas phase NOx-air photooxidation of toluene and the cresols (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 779-836 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An experimental and modeling study of irradiated toluene-NOx-air, toluene-benzaldehyde-NOx-air, and cresol-NOx-air mixtures at part-per-million concentrations has been carried out. These mixtures were irradiated at 303 ± 1 K in a 5800-liter Teflon-lined, evacuable environmental chamber, with temperature, humidity, light intensity, spectral distribution, and the concentrations of O3, NO, NO2, toluene, PAN, formaldehyde, benzaldehyde, o-cresol, m-nitrotoluene, and methyl nitrate beingmonitored as a function of time. For the toluene and toluene-benzaldehyde-NOx-air runs a variety of initial reactant concentrations were investigated. Cresol-NOx-air runs were observed to be much less reactive in terms of O3 formation and NO to NO2 conversion rates than toluene-NOx-air runs, with the relative reactivity of the cresol isomers being in the order meta » ortho 〉 para. The addition of benzaldehyde to toluene-NOx-air mixtures decreased the reactivity, in agreement with previous studies. Alternative mechanistic pathways for the NOx photooxidations of aromaticsystems in general are discussed, and the effects of varying these mechanistic alternatives on the model predictions for the toluene and o-cresol-NOx-air systems are examined. Fits of the calculations to most of the experimental concentration-time profiles could be obtained to within the experimental uncertainty for two of the mechanistic options considered. In both cases it is assumed that (1) O2 adds to the OH-toluene adduct ∼75% of the time forming, after a further addition of O2, a C7 bicyclic peroxy radical, and (2) this C7 bicyclic peroxy radical reacts with NO ∼75% of the time to ultimately form α-dicarbonyls and conjugated γ-dicarbonyls (e.g., methylglyoxal + 2-butene-1,4-dial) and ∼25% of the time to form organic nitrates. The major uncertainties in the mechanisms concern (1) the structure of the bicyclicperoxy intermediate, and (2) the γ-dicarbonyl photooxidation mechanism. Good fits to the o-cresol concentration-time profiles in the toluene-NOx runs are obtained if it is assumed that o7-cresol reacts rapidly with NO3 radicals. However, it is observed that the model underpredicts nitrotoluene yields by a factor of ∼10, but this is in any case a minor product. It is concluded that further experimental work will be required toadequately validate the assumptions incorporated in the aromatic photooxidation mechanisms presented here.
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    URL: http://dx.doi.org/10.1002/kin.550121102
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  • 57
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    FTIR studies of the kinetics and mechanism for the reaction of Cl atom with formylchloride (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 915-920 
    Details
    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 Cl + CHClO → HCl + CClO was determined from relative decay rates of CHClO and CH3Cl inthe photolysis of mixtures containing Cl2 (∼1 torr), CH3Cl (∼1 torr), and O2 (∼0.1 torr) in 700 torr N2. In such mixtures CHClO was generated in situ as a principal product prior to complete consumption of O2. The value of k(Cl + CHClO)/k(Cl + CH3Cl) = 1.6 ± 0.2(3σ) combined with the literature value of k(Cl + CH3Cl) = 4.9 × 10-13 cm3/molecule sec gives k(Cl + CHClO) = 7.8 × 10-13 cm3/molecule sec at 298 ± 2 K, in excellent agreement with a previous value of (7.9 ± 1.5) × 10-13 cm3/molecule sec determined by Sanhueza and Heicklen [J. Phys. Chem., 79, 7 (1975)]. Thus this reaction is approximately 100 times slower than the corresponding reactions of aldehydes and alkanes with comparable C—H bond energies (≤95 kcal/mol).
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    URL: http://dx.doi.org/10.1002/kin.550121203
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  • 58
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    The kinetics of the chlorine isotopic exchange between chloride ion at O,O-diarylphosphorochloridates or O,O-diarylphosphorochloridothionates (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 979-991 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the chlorine isotopic exchange reaction between tetraethylammonium chloride-36Cl and O,O-diarylphosphorochloridates (p-RC6H4O)2POCl or O,O-diarylphosphorochloridothionates (p-RC6H4O)2PSCl has been studied in acetonitrile solution. Good Hammett's correlations of the rate constants with Taft's σ0 constants were obtained. The values of the reaction constants ρ were found identical for phosphoryl and thiophosphoryl compounds. In comparison with oxygen in the phosphoryl group, the sulfur atom exhibits an electron-donating effect (Δσ0 ∼ 0.80). No correlation has been found for the enthalpy and entropy of activation. The effect of the substituents aryloxy groups, oxygen, or sulfur atoms in the phosphoryl group on the kinetics of the SN2-P reaction is discussed. The reactivity of the investigated compounds is determined by the extent of the positive charge localized on the phosphorus atom. The positive charge is formed by the direct interactions of the substituents with the reaction center and the indirect-intramolecular interactions revealed in the structure of the compound.
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    URL: http://dx.doi.org/10.1002/kin.550121207
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  • 59
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    The kinetics and mechanism of the oxidation of formic acid by bromine in acid aqueous media (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 1013-1020 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction between formic acid and bromine in strongly acid aqueous media at 298 K \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm Br}_2 + {\rm HCOOH} \to {\rm 2Br}^{\rm - } + 2{\rm H}^ + {\rm CO} $$\end{document} was studied by absorption spectrophotometry (λ = 447 nm). Reaction rates, expressed as R = -d[Br2]/dt, depend on the concentrations of HCOOH (0.3-2.4M), Br2[(2.7-13.6) × 10-3M], H+ (0.03-2.0M), and Br- (up to 0.6M). The mechanism with k1 = 20.2 ± 1.2 M-1 sec-1, pK2 = 3.76, pK3 = -1.20, accounts for all experimental observations. Br3- and HCOOH can be considered unreactive within experimental error. Apparent deviations from the basic mechanism at higher acidities can be quantitatively ascribed to the nonideality of ionic species.
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    URL: http://dx.doi.org/10.1002/kin.550121210
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  • 60
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    The √t law in solid-phase reactions verification of the √t law stability in h-atom abstraction reactions (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 271-281 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The law c = c0 exp(—K √t) in the alkyl radical abstraction reaction is affected by neither the matrix annealing nor the way of the radical generation. If the reaction runs at varying temperature, a dimensionless time τ which does determine unambiguously the degree of conversion can be introduced.
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    URL: http://dx.doi.org/10.1002/kin.550120408
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  • 61
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    Kinetics of radiation-induced abstraction of hydrogen atoms by CCl3 radicals in the liquid phase: 2,3-dimethylbutane (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 379-386 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gamma-radiation induced free radical reactions in carbon tetrachloride solutions of 2,3-dimethylbutane (DMB) were studied in the temperature range 32-118 °C. The kinetics of the following reactions were measured:\documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} {\rm CCl}_3 + {\rm RH} \to {\rm CHCl}_3 + {\rm R} \\ {\rm CCl}_{\rm 3} + {\rm CCl}_{\rm 3} \to {\rm C}_2 {\rm Cl}_6 \\ \end{array} $$\end{document} and the following rate constants expression was obtained:\documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_2 /k_3^{1/2} (M^{ - 1/2} \sec ^{ - 1/2} )\, = \,(2.40 \pm 0.17) - (6.96 \pm 0.26)/{\rm \theta } $$\end{document}. The activation energy and the A factor obtained are in good agreement with the values obtained at the gaseous phase, considering the activation energy for self-diffusion of CCl4.
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    URL: http://dx.doi.org/10.1002/kin.550120603
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  • 62
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    Oxidation of formic acid by bromine in aqueous, strongly acid media (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 393-402 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Spectrophotometric methods were used to investigate the rate of the reaction of Br2 with HCOOH in aqueous, acidic media. The reaction products are Br- and CO2. The kinetics of this reaction are complicated by both the formation of Br3- as Br- is formed and the dissociation of HCOOH into HCOO- and H+. Previous work on this reaction was carried out at acidities lower than the highest used here and led to the conclusion that only HCOO- reacts with Br2. It is agreed that this is by far the principal reaction. However, at the highest acidity experiments, an added small component of reaction was found, and it is suggested that it results from the direct reaction of Br2 with HCOOH itself. On this assumption, values of the rate constants for both reactions are derived here. The rate constant for the reaction of HCOO- with Br2 agrees with values previously reported, within a factor of 2 on the low side. The reaction involving HCOOH is more than 2000 times slower than the reaction involving HCOO-, but it does contribute to the overall rate as [H+] approaches 1M. These derived rate constants are able to simulate quantitatively the authors' absorbance-versus-time data, demonstrating the validity of their data treatment methods, if not mechanistic assignments. Finally, activation parameters were determined for both rate constants. The values obtained are: ΔE
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  • 63
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    The reaction of CH3O2 radicals with NO2 (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 1-16 
    Details
    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 CH3O2 + NO2 → (products) has been measured directly by flash photolysis and kinetic spectroscopy. At room temperature and at total pressures between 53 and 580 Torr, k3 = (9.2 ± 0.4) × 108 liter/mole sec so that the rate of formation of the probable primary product peroxymethyl nitrate (CH3O2NO2) may be significant in urban atmospheres.
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    URL: http://dx.doi.org/10.1002/kin.550120102
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    The kinetics of the interaction of peroxy radicals. I. The Tertiary Peroxy RadicalsThis work has been sponsored by Grants from the National Science Foundation (CHE-76-16787A02) and U.S. Army Research Office (No. DAAG29-76-G0195) (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 29-42 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Existing data on the self-reactions of tertiary peroxy radicals RO2 has been reanalyzed and corrected to deduce Arrhenius parameters for both termination and nontermination paths. For R = t-Butyl, these are logkt(M-1sec-1) = 7.1 - (7.0/θ) and logknt(M-1sec-1) = 9.4 - (9.0/θ), respectively, different from those recommended by other authors. The higher magnitudes observed for termination processes of tertiary peroxy radicals like those of cumyl and 1,1-diphenylethyl have been discussed in terms of a much greater cage recombination of cumyloxy radicals as contrasted with t-butoxy radicals. It is shown that for benzyl peroxy radicals, the R - O·2 bond dissociation energy is sufficiently low (18-20 kcal) that reversible dissociation into R· + O2 opens a competing second-order path to fast recombination R· + RO·22 → ROOR. This path is probably not important for cumyl peroxy radicals under usual experimental conditions but can become important for 1,1-diphenyl ethyl peroxy radicals at (O2) 〈 10-3M. At very low RO·2 concentrations (〈10-5M), in the absence of added O2, an apparent first-order disappearance of RO·2 can occur reflecting the rate determining breaking of the cumyl - O·2 bond followed by the second step above. The thermochemistry of RO·n is used to show that the reaction of R2O4 → 2RO + O2 must be concerted and cannot proceed via RO·3 which is too unstable and cannot form even from RO· + O2.
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    Demetallation of α,β,γ,δ-tetrakis(p-sulfophenyl) porphiniron(III) in mineral acid-alcohol-water media (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 97-105 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Demetallation rates of α,β,γ,δ-tetrakis(p-sulfophenyl)porphiniron(III) in hydrochloric acid-ethanol-water, perchloric acid-ethanol-water, and sulfuric acid-alcohol-water media were determined. For a given acidity value H0 the order of the rates for the three acids was HCl 〉 H2SO4 〉 HClO4. This is also the order for complex formation between acid anion and iron(III). Consequently ligands as well as protons are involved in the breaking of bonds between the metal and the porphyrin leading to the formation of the activated complex. The log k values for HCl and HClO4 media were not linearly related to the Hammett acidity function as they were for sulfuric acid-ethanol-water media. The average ΔH
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    Evaluation of the rate coefficients and arrhenius parameters of hydrogen atom transfer reactions. I. The method (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 123-139 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method is presented for the prediction of rate coefficients and Arrhenius parameters for bimolecular hydrogen atom transfer reactions A + BC → AB + C. The treatment sets out from structural considerations of the complex A ⃛ B ⃛ C and calculates the energy of the complex along the reaction path from empirical functions for a bonding energy term and an endgroup contribution. The treatment proceeds by assuming ultrasimple transition state models and assigning the force constants and vibrational frequencies. Finally the rate coefficient and Arrhenius parameters are obtained on the basis of separable activated complex theory. Application of the method requires known properties of reactant and product molecules and does not demand the use of adjustable parameters. The relation and differences between this method and the BEBO treatment as well as Zavitsas' method are dealt with.
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    Liquid-phase oxidation of isobutane - a reanalysis of the data (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 169-181 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Data on the liquid-phase oxidation of isobutane at 50 and 100°C have been reexamined, using a modified mechanism to take into account the termination by isobutylperoxy radicals. Algebraic expressions are derived from steady-state methods. Using Arrhenius parameters fitted by transition-state A factors and activation energies derived from observed “best” rate constants, new sets of parameters are derived for the rate constants for propagation by t—BuO2 + t—BuH → t-BuO2H + t—Bu⋅: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_4 \, = \,1 \times 10^{8 - 14.5/{\rm \theta }} {\rm M}^{{\rm - 1}} \sec ^{ - 1} $$\end{document} where θ = 2.303RT in kcal/mol. This, together with new values for the termination parameters and rates of i-butyl production by k4B, is shown to give good agreement with the published data. An important reaction:\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm R}'{\rm O}_{2}^{.} + {\rm RO}_{2} {\rm H}\mathop{{\buildrel{-\!\!\longrightarrow}\over{\longleftarrow}}}\limits^{{\rm 12}}{\rm R'O}_{\rm 2} {\rm H} + {\rm RO}_{2}^{.} $$\end{document} is shown to quench the possible contributions to termination of adventitious radicals such as CH3O⋅2.
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    Kinetics of oxidation of butane 2,3-diol by osmium(VIII) (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 225-230 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidation of butane 2,3-, propane 1,2-, ethane diol and 2-methoxy ethanol in aqueous alkaline medium by Os(VIII) has been studied. The reaction is base catalyzed and shows first-order kinetics in Os(VIII), whereas the order is less than 1 in butane 2,3-diol [BD]. The rate of oxidation is BD 〉 propane 1,2 〉 ethane diol ≈ 2-methoxy ethanol. The change in ionic strength has no effect on the rate of reaction. Activation parameters ΔE, PZ, and ΔS* have been evaluated.
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  • 69
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    Ion pair catalysis of the autooxidative cleavage of benzoin in emulsion systems (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 1045-1054 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study was made of the autooxidation of benzoin in organic-aqueous sodium hydroxide emulsions in the presence of several quaternary ammonium salts. The rate of the reaction was found to be accelerated by these salts, probably by ion pair extraction. In pyridine and acetonitrile systems the reaction was almost exclusively the formation of benzoate. Neither benzil nor benzaldehyde were intermediates in the oxidation process. The rate law for the reaction was found to be \documentclass{article}\pagestyle{empty}\begin{document}$$ - \frac{{dPo_2 }}{{dt}} = k\left[{{\rm Po}_{\rm 2} } \right]\left[{{\rm benzion}} \right]\left[{{\rm OH}^ - } \right] + k_2 \left[{{\rm Po}_2 } \right]\left[{{\rm benzion}} \right]\left[{{\rm OH}^ - } \right][{\rm R}_4 {\rm N}^ +] $$\end{document}which led to the conclusion that the rate-determining step in the catalyzed pathway was the reaction of oxygen with the ion pair:
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    Kinetics and mechanism of the germane decomposition (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 661-670 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The homogeneous gas-phase thermal decomposition kinetics of germane have been measured in a single-pulse shock tube between 950 and 1060 K at pressures around 4000 torr. The initial decomposition is GeH4 → GeH2 + H2 in its pressure-dependent regime, with log kGeH4(4000) = 13.83 ± 0.78 - 50,750 ± 3570 cal/2.303RT. RRKM calculations suggest that the high-pressure Arrhenius parameters are log k GeH4(M → ∞) = 15.5 - 54,300 cal/2.303RT. Extrapolations to static system pyrolysis conditions (T ∼ 600 K, P ∼ 200 torr) give homogeneous reaction rates which are much slower than those observed, hence the static system pyrolysis of germane must be predominantly heterogeneous. Shock-initiated pyrolysis reaction stoichiometry is 2 mol H2 per mole GeH4, suggesting that the subsequent decomposition of germylene is essentially quantitative. Investigations of the hydrogen product yields for pyrolysis of GeD4 in øCH3 further indicate that the germylene decomposition reaction is mainly GeH2 → H2 + Ge, but that a small amount of reaction to H atoms may also occur.
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    Determination of the mechanism of the oxidation of the trichloromethyl radical by the photolysis of chloral in the presence of oxygen (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 717-727 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photooxidation of chloral was studied by infrared spectroscopy under steady-state conditions with irradiation of a blackblue fluorescent lamp (300 nm 〈 λ 〈 400 nm, λmax = 360 nm) at 296 ± 2 K. The products were hydrogen chloride, carbon monoxide, carbon dioxide, and phosgen. The kinetic results reveal that the reaction proceeds via chain reaction of the Cl atom:The results lead to the conclusion that mechanism (B) is confirmed to be more likely than mechanism (A), which was favored at one time by Heicklen for the mechanism of the oxidation of trichloromethyl radicals by oxygen molecules: The ratio of the initial rates of CO and CO2 formation gave k7/k6 = 4.23M-1, and the lower limit of reaction (5) was found to be 3.7 × 108M-1 sec-1.
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    Kinetics and mechanism of the bromination of aromatic compounds by N-bromosuccinimide in solution (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 837-850 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of bromination of several aromatic compounds (anilides, anisoles, and phenols) was investigated in 80% aqueous acetic acid (v/v) in the temperature range 20-50°C using N-bromosuccinimide (NBS) as the reagent. The reaction was found to be first order in the aromatic substrate (ArH), and zero order in NBS, the overall order being 1. Stoichiometry of the reaction was 1:1. An increase in solvent polarity increased the reaction rate, and chloride ions were found to be specific catalysts for the reaction. Arrhenius activation energy remained almost constant for all the substrates. A probable mechanism explaining all these observed facts was proposed. The mechanism involved an attack by Br+ or more probably by a solvated Br+ ion on the aromatic substrate.
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    The structure and energies of some unsaturated four-membered ring carbocycles (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980), S. 30-35 
    Details
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: A number of cyclobutane derivatives containing one or more double bonds in endo- or exocyclic positions have been studied by the molecular mechanics method within the context of the MM2 force field. Generally speaking, the structures and energies of these compounds are well calculated in cases in which they are known experimentally and are predicted in others. Examples are shown of the use of the moments of inertia of molecules, which are known from microwave studies, in conjunction with molecular mechanics calculations to yield better structures than could be obtained by either method alone. Compounds examined include cyclobutene, methylenecyclobutane, Dewar benzene, and related compounds.
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    A simplex optimized INDO calculation of 13C chemical shifts in hydrocarbons (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980), S. 36-45 
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    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: The variable-size simplex optimization method is used to reparametrize the I + A and β parameters of an INDO approximation to the perturbed Hartree-Fock calculation of 13C chemical shifts in hydrocarbons. The absolute shifts for 39 nuclei in a set of molecules containing up to four carbons are reproduced within a standard error of 9.9 ppm for an unconstrained optimization and to a standard error of 10.0 ppm for an optimization constrained to yield gross atomic charges in agreement with double-zeta ab initio calculations.
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    URL: http://dx.doi.org/10.1002/jcc.540010105
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    Orbital topology. I. A basic topological model for chemical systems, an orbital mapping technique, and analyses of model, thermal electrocyclic reactionsThis article is based in part on D. R. Kelsey's Ph.D. Thesis, California Institute of Technology, Pasadena, California, October 31, 1972; a brief discussion of these concepts and results has been presented at the American Chemical Society's 172nd National Meeting, San Francisco, September 2, 1976, abstract ORGN 199. (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980), S. 3-20 
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    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: A topological model which provides a unifying framework for chemical reactions and molecular structure is proposed. Such basic concepts as overlap, orthogonality, reaction continuity, reaction reversibility, and orbital correspondence are incorporated into the model in a logical fashion. A chemical reaction pathway is regarded as a function that transforms a reactant topological space into its equivalent product space. The unique character usually ascribed to reactants, products, and their wavefunctions is superfluous. The model also allows considerable approximation of the wavefunctions and the reaction pathway without affecting the overall result. A simple orbital mapping technique consistent with the model which traces the transformation of orbitals using intermolecular overlaps of the orbitals is also proposed. The suitability of a given pathway (“allowed” or “forbidden”) can be deduced explicitly without invoking symmetry (or other) rules and without resorting to detailed calculation of reaction energy surfaces. The validity of the mapping procedure has been confirmed by several thermal electrocyclic reactions: the ring-opening isomerizations of substituted cyclopropyl cations, cyclopropyl anion, cyclopropanone, cyclobutene, benzocyclobutene, Dewar benzenes, and 1,3-cyclohexadiene. Orbital mapping with EHT and CNDO/2 MOs correctly predicts the reaction stereochemistry (conrotatory or disrotatory) in every case.
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    Conformational analysis of proteins: Algorithms and data structures for array processing (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980), S. 46-58 
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    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: Current efforts to determine the nature of the interactions that influence protein folding involve, among other things, minimization of an appropriate empirical conformational energy function (ECEPP, Emprical Conformational Energy Program for Peptides) to obtain the native structure. Because of the prohibitive cost of such a massive computational project, either on a conventional large-scale machine at a self-supporting installation or on a dedicated minicomputer, an alternative computer hardware system has been developed to aid in the conformational analysis of proteins. It consists of a Floating Point Systems AP-120B array processor and a Prime 350 minicomputer host. A version of ECEPP has been adapted to run on the AP-120B. The data structures and algorithms chosen for this version reflect the highly unusual parallel architecture of this machine. Benchmark comparisons with BPTI (Bovine Pancreatic Trypsin Inhibitor), a protein of 58 residues and a known structure, have been carried out on this system as well as on an IBM 370/168. They show a significant advantage in speed for the AP-120B/Prime 350 system as well as a substantially lower cost. An energy minimization of BPTI with 154 variable dihedral angles is reported, an effort heretofore prohibited by the computer costs involved.
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    Masthead (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980) 
    Details
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jcc.540010201
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    A systematic preparation of new contracted Gaussian-type orbital sets. III. Second-row atoms from Li through ne (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980), S. 205-228 
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    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: Four minimal Gaussian basis sets are generated for the second-row atoms Li through Ne. The first one, MINI-1, consists of a 3-term contraction of primitive Gaussian-type orbitals for 1s, 2s, and 2p atomic orbitals. The convenient shorthand notation would be (3,3) for Li—Be and (3,3/3) for B—Ne. The second one, MINI-2, can be represented by (3,3/4) for B—Ne. In the same way, MINI-3 is described as (4,3) for Li—Be, and MINI-3 and MINI-4 are represented by (4,3/3) and (4,3/4) for B—Ne, respectively. Although the four basis sets are the minimal type, they give the valence shell orbital energies which are close to those of DZ. These four and other sets derived from them are tested for the hetero- and homodiatomic molecules and some organic molecules. They are found to give the orbital energies that agree well with those given by extended calculations. Atomization energies and other spectroscopic constants are also calculated and compared with those of extended calculations. The results clearly indicate that the present basis sets can be used very effectively in the molecular calculations.
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    The electronic structure and optical activity of conjugated dienes: 1,3-Butadiene and α- and β-phellandrene (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980), S. 240-256 
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    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: The optical activity of conjugated dienes is investigated by means of ab initio SCF-CI calculations. The computed electronic spectrum of trans-1,3-butadiene is shown to be in good agreement with the results of more rigorous calculations of the valence transitions and in satisfactory agreement with experiment. The optical rotatory strengths of the lower electronic transitions of twisted 1,3-butadiene as a function of dihedral angle are presented and simulated CD spectra are produced. The N → V1 (π2 → π3*) transition is predicted to have a positive rotational strength for all dihedral angles that correspond to a right-handed twist of the chromophore, in accord with the empirically deduced “diene rule” although for a twist angle of 60°, the rotatory strength is calculated to be almost zero. The role of the orientation of allylic bonds is investigated in the model system 1-butene in which the rotational strength of the π → π* transition as a function of rotation about the 2,3 bond is determined. The effect of allylic bond disposition in dienes on the optical activity of the long-wavelength π2 → π3* transition is simulated by use of the exciton coupling model of Harada and Nakanishi in which two 1-butene molecules with suitable geometries are coupled via interactions of the electric dipole transition moments of their π → π* transitions. The model systems 1,3-butadiene and 1-butene are used to rationalize the apparently anomalous optical activity of (-)-α-phellandrene and (-)-β-phellandrene, both of which should have a diene chromophore with a right-handed twist in their most stable conformers and so should be dextrorotatory. The experimental CD spectrum of α-phellandrene is determined at several temperatures down to -180°C. The observed variation of the apparent rotational strength of the N → V1 transition is in good agreement with that predicted by use of the exciton coupling model.
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    A theoretical comparison of cationic and anionic homoaromaticity: Reinforcement of cationic homoaromaticity by σ-nonclassical effects (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980), S. 189-191 
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    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: A MINDO/3 study of homoaromaticity in the 3-cyclobutenyl cation and the Mobius 3-cyclobutenyl anion has been used to evaluate cationic and anionic homoaromaticity quantitatively. π Homodelocalization energies of the two are found equal in isostructural planar comparisons. In planar optimized structures, the homodelocalization energy of the cation is slightly (about 4 kcal) greater than that of the anion, a consequence of the greater 1,3 distance in the latter. Full optimization produces a highly puckered and further stabilized cation, but engenders no change in the Mobius anion. The total stabilization of the cation relative to the anion is 13 kcal, in accord with the generalization that cationic homoaromaticity is more potent than the anionic variety. The fully optimized cation is revealed to actually have a much smaller π homodelocalization energy than the optimized anion, in contrast to the order of overall stabilities. σ-Nonclassical effects, which are stabilizing in the cation but destabilizing in the Mobius anion, provide the rationale for the above.
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    Applications of molecular mechanics calculations in carbohydrate chemistry. I. Conformational and constitutional equilibria of tetraoxabicyclo[4.4.0]- and -[5.3.0] decanes, bicyclic diacetals of alditols (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980), S. 192-198 
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    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: The energies of various conformations have been calculated by molecular mechanics for cis and trans isomers of 2,4,7,9-tetraoxabicyclo[4.4.0] decane and 3,5,8,10-tetraoxabicyclo[5.3.0]decane and their methyl derivatives. These molecules are models for reaction products from formaldehyde and the tetrols, pentitols, and hexitols. The conformational equilibria were analyzed for the cis-bicyclo [4.4.0] and cis-bicyclo[5.3.0] systems and compared with available experimental data. The thermodynamic stability of bicyclo[4.4.0] products was found to be higher than that of bicyclo[5.3.0] derivatives in the gas phase in every case studied. Discrepancies with experimental data that exist in a few cases can be ascribed to solvent effects.
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    Masthead (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980) 
    Details
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jcc.540010401
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    A theoretical approach to substituent effects.For previous articles in this series, see ref. 1. Structural consequences of electrostatic and orbital interactions in model mono- and disubstituted methanes (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980), S. 295-300 
    Details
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: Ab initio molecular orbital theory is used to examine the effect of substituents on bond lengths in mono- and disubstituted methanes. The relative importance of electrostatic and orbital interaction terms are assessed. The results suggest that for substituents (X) which show powerful σ effects and weak π interactions (e.g., F), the changes in bond length are due primarily to the electrostatic component except in some disubstituted methanes in which case the change in the hyperconjugative ability of the C - X bond is also important. On the other hand, substituents X which show weak σ effects but powerful π interactions (e.g., NH2) affect bond lengths primarily through hyperconjugative interaction of a filled or vacant π-type orbital on X with the adjacent bonds.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jcc.540010313
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  • 84
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    A comparative study of the structure and bonding of HOO, HOS, HSO, and HSS radicals by CNDO/2 and INDO methods (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980), S. 334-340 
    Details
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: Equilibrium geometries, force constants, barriers to linearity, charge distributions, dipole moments, and electron spin density of HOO, HOS, HSO, and HSS radicals are calculated by CNDO/2 and INDO methods using respectively the original and some recently introduced scheme of parametrization. Three sets of calculations, namely, CNDO/2(sp), CNDO/2(spd), and INDO, are performed, and the results are compared with the ab initio and experimental values, wherever available. A good agreement is obtained for geometry in the case of CNDO/2 (sp) and INDO calculations. The performance of CNDO/2 (spd) calculations in this regard is quite unreliable. The stretching force constants are considerably overestimated by all the methods, while the bending force constants are in reasonable agreement with the ab initio values. With respect to dipole moments, the CNDO/2 values are in better agreement with the ab initio results than the INDO values. In all the cases, the dipole moment vector directions are in complete disagreement with the ab initio predictions.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jcc.540010404
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  • 85
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    Electronic Resource
    Localized molecular orbitals and chemical binding in five-membered heterocycles. II (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980), S. 358-367 
    Details
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: The localized molecular orbitals (LMOs) of thiophene, furan, and pyrrole are derived from ab initio 4-31G wavefunctions using Boys' criteria for localization. From the transferability point of view, these LMOs are classified as (i) completely different and nontransferable LMOs (these are the lone-pair orbitals on O and N on one hand and those on S on the other hand), (ii) chemically similar lone pairs and inner shells on O and N (of furan and pyrrole, respectively), and (iii) chemically equivalent C—C, C=C, and C—H LMOs in the three heterocycles. The sp3 hybridization of the L core of sulfur, its appreciable polarization, and considerable involvement in bonding in the C—S bond region have been discussed. The present investigation indicates the limitation of the application of semiempirical MO methods to molecules that contain second-row atoms due to both the appreciable core - valence and π-σ interactions involving such atoms. Qualitative investigation of aromaticity and reactivity of the studied heterocycles agrees satisfactorily with experimental observations and shows that conclusions drawn based solely on static factor considerations (charge distribution in the noninteracting molecules) might very well be misleading and such factors determine the ease rather than the final orientation of the substituent.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jcc.540010407
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  • 86
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    An ab initio study of the geometry and energy of six planar conformers of β-hydroxyacrolein (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980), S. 373-385 
    Details
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: Ab initio calculations with full geometry optimization have been carried out on the planar cCc, cTc, tTc, tCt, tTt, and cCt conformers of β-hydroxyacrolein using the 4-21G basis set, and on the cCc and cCt conformers using the 4-31G basis set. The hydrogen-bonded cCc conformer is the most stable and the cCt conformer the least stable, with the other conformers following the above sequence. β-Hydroxy substitution has scarcely any influence on the geometry of the trans-acrolein structure, whereas the geometry of the cis-acrolein structure shows significant changes which depend on whether the O—H group is cis or trans with respect to the CHO group about the C=C bond. The ΔET values for cis → trans isomerization about the C—C bond in cCt and cTc support the hypothesis that these changes in geometry are the result of a destabilizing interaction in cCt and a stabilizing interaction in cTc. The geometry of the hydrogen-bonded structure cCc sets it apart from all the other conformers: it has by far the longest C=C, the longest C=O, the longest O—H, the shortest C—C, and the shortest C—O. Its formation from cCt involves a lengthening of C=C, C=O, and O—H and a shortening of C—C and C—O, indicating a delocalization of charge within the ring. 4-21G calculations have also been made for a distorted cCt structure that has the same bond lengths and angles as the equilibrium cCc structure, and the distortion energy, cCt (equm. geom.) → cCt (distorted geom.), is found to be +13.1 kJ mole-1. Taking the energy of this distorted cCt structure as the baseline, the hydrogen-bonding energy in cCc is found to be  - 80.3 kJ mole-1.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jcc.540010409
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  • 87
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    Electronic Resource
    Masthead (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980) 
    Details
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jcc.540010101
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  • 88
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    Electronic Resource
    Orbital topology. II. Orbital mapping of unsymmetrical molecules. A survey of the thermal isomerizations of dewar isomers of isoelectronically substituted benzenes, cyclopentadienes, and cyclopentadienyl ions (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980), S. 21-29 
    Details
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: Orbital mapping analysis, based on EHT and CNDO/2 semiempirical molecular orbitals, has been used to survey the thermal, disrotatory, ring-opening isomerizations of bicyclo[2.2.0]hexa-2,5-dienes (Dewar benzenes), bicyclo[2.1.0]pent-2-enes, and bicyclo[2.1.0]pent-2-en-5-yl ions to their planar isomers. Results indicate that isoelectronic substitution (CH replaced by C-, O+, N, NH+, etc.) in the molecular framework may favor allowed thermal reactions in some cases, in contrast to the disallowed reaction predicted for the parent hydrocarbons.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jcc.540010103
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  • 89
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    Metal-metal bond energies in Mo2, Mo2Cl84-, and Mo2(O2CH)4 (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980), S. 59-63 
    Details
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: Previous attempts to determine the strengths of multiple metal-metal bonds are reviewed. Estimates of 73 and 97 kcal/mole for the Mo—Mo bond energies in Mo2Cl84- and Mo2(O2CH)4, respectively, are obtained by combining the known experimental bond energy in Mo2 (96.5 ± 5 kcal/mole) with the results of SCF-Xα-SW calculations on Mo2, Mo2Cl84-, and Mo2(O2CH)4. Possible errors in the estimates are discussed. It is noted that the quadruple bonds in the complexes are predicted stronger per component than the sextuple bond in the diatomic.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jcc.540010107
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  • 90
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    Electronic Resource
    A pseudopotential SCF-MO study of Te42+ (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980), S. 64-68 
    Details
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: A recently developed ab initio pseudopotential molecular orbital approach was applied to the Te42+ ion, a system outside the practical reach of conventional all-electron treatments. Computations were carried out with a minimal STO-4G basis set. Results account reasonably well for the observed optical absorption spectrum and suggest the origin of a hitherto unassigned weak band. Ground-state properties, which included the structure, force field, and vibrational frequencies, were also investigated. Treated as a free, gas-phase ion, tetratellurium (II) yielded a bond length 0.05 Å shorter than the experimental value for the ion in a crystal lattice. Placement of static, point-charge counterions in the Te42+ coordination sphere increased the bond length to a value 0.005 Å longer than derived by experiment. Calculations on neutral, cyclic Te4 provided a theoretical single-bond reference length 0.09 Å longer than that obtained for the ion in a counterion environment. Comparisons between observed and calculated frequencies suggest an assignment of the vibrational spectrum different from the provisional assignment in the literature.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jcc.540010108
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  • 91
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    Electronic Resource
    Integrated spatial electron populations in molecules: Application to simple molecules (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980), S. 81-87 
    Details
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: The electron projection function P(x, z) = ∫ ρ(x, y, z) dy is used to evaluate charge transfer and covalency in two series of molecules, LiX and CH3X (X = Li, BeH, BH2, CH3, NH2, OH, and F), with wavefunctions derived from STO-3G, 4-31G, and, in some cases, 6-31* ab initio calculations. The precision of the method and comparison with Mulliken populations analysis are described. Particular attention is given to CH3Li which by our criteria is wholly ionic.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jcc.540010111
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  • 92
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    Electronic Resource
    Isomeric structures of protonated ozone: A theoretical study (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980), S. 94-98 
    Details
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: Ab initio molecular orbital calculations have been used to determine the structure of protonated ozone. Four stable minima were found on the O3H+ singlet potential energy surface. Three forms correspond to ozone protonated at the central oxygen (C2v) or at the terminal oxygen (two Cs isomers, E and Z). The fourth isomer (Cs) is a derivative of trioxirane. The most stable structure is the planar E form I. The proton affinity of ozone (to give I) is given as 123.6 kcal/mole (MP2/6-31G*//4-31G). The energy difference between I and protonated trioxirane VI is greater than that between ozone and trioxirane.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jcc.540010113
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  • 93
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    Electronic Resource
    The application of molecular mechanics to the structures of carbohydrates (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980), S. 99-109 
    Details
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: A study is reported of the accuracy with which the geometries of pyranose and methyl pyranoside molecules are predicted by molecular mechanics. Calculations of the conformational energies of the model compounds dihydroxymethane, methoxymethanol, and dimethoxymethane, made with the program MMI, produced results that compare well with previous ab initio molecular orbital calculations. This indicates that MMI gives a satisfactory account of the energetic and conformational aspects of the anomeric effect, a conclusion further supported by calculations on 2-methoxytetrahydropyran. The prediction of the observed preferred conformations of the primary alcohol group in aldohexopyranoses appears to be less satisfactory. MMI-CARB, a version of MMI with changes in some of the equilibrium C—O bond lengths of the program, has been used to calculate the geometries of 13 pyranose and methyl pyranoside molecules, the crystal structures of which have been studied by neutron diffraction. When the C—C—O—H torsion angles are constrained to approximately the values observed in the crystal structures, good agreement is obtained between the theoretical and experimental molecular geometries. The rms deviation for C—C and C—O bonds, excluding those significantly affected by thermal motion in the crystal structure determinations, is 0.005 Å. Corresponding figures for the valence angles that do not involve hydrogen atoms and for the ring torsion angles are 1.2° and 2.0°, respectively. The Cremer and Pople puckering parameters for the pyranose rings are reproduced within 0.026 Å in Q and 5.4° in θ.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jcc.540010114
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  • 94
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    The C4H4CO potential surface. Reactions involving bicyclo[2.1.0]pentenone (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980), S. 129-133 
    Details
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: MNDO and MINDO/3 calculations were used to study the photochemical formation, thermal rearrangements, and dissociation of bicyclo[2.1.0]pentenone. The “forbidden” thermal conversion to cyclopentadienone requires little activation, which accounts for the low kinetic stability of bicyclo[2.1.0]pentenone. The theoretical results seem to be compatible with the available experimental evidence for the tri-tert-butyl-substituted systems and suggest an explanation for observed differences in reactivity.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jcc.540010204
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  • 95
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    Electronic Resource
    On the relative importance of core and valence shell representations in the calculation of conformational energies using small Gaussian basis sets (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980), S. 134-140 
    Details
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: Several “core-deficient” small Gaussian basis sets were constructed and analyzed in terms of the balance requirements of functions that contribute predominantly to the core. Variations in the conformational energy barriers and geometrical parameters for ammonia and ethane, calculated with these basis sets, were analyzed with a gradient technique. A scheme for the reduction of the size of molecular basis sets is proposed.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jcc.540010205
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  • 96
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    Graph theoretical characterization and computer generation of certain carcinogenic benzenoid hydrocarbons and identification of bay regions (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980), S. 149-157 
    Details
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: An algorithm is developed for generating and characterizing carcinogenic catacondensed benzenoid hydrocarbons. The bay regions in these structures are identified by a technique that we developed at Johns Hopkins. Using the three-digit code proposed by Balaban, and the concept of ring adjacency matrix expounded here, we generate catacondensed benzenoid hydrocarbons in the computer and identify the number of potentially carcinogenic bay regions in each of them. The results of computer generation agree with the combinatorial enumeration of Harary and Read. All structures containing up to five rings and some with six rings and the number of bay regions in these are presented. Computer results for the structures and bay regions of all seven-, eight-, and nine-membered unbranched catacondensed benzenoid hydrocarbons and the number of bays are available from the authors.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jcc.540010207
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  • 97
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    A note on density matrix extrapolation and multiple solutions of the unrestricted Hartree-Fock equations (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980), S. 178-180 
    Details
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: Unrestricted Hartree-Fock (UHF) SCF-MO calculations on the doublet reaction surface for the addition of methylidyne (CH) to ethylene (C2H4) using the standard extrapolation techniques of the GAUSSIAN 70 program show erratic behavior. On the other hand, the potential energy surface calculated without extrapolation of the density matrix and by using the final density matrix of a neighboring point as the initial guess for the density matrix for the new point gave a smooth potential curve without any kinks or erratic pattern. Therefore, the density extrapolation technique should be used with particular caution in UHF calculations.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jcc.540010210
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  • 98
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    The torsional potential function for n-butane (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980), S. 181-184 
    Details
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: The energies of four different conformations for n-butane were calculated by the ab initio method using an STO-3G basis set. Fully relaxed molecular geometries obtained from molecular mechanics (MM2) were used. The two energy minima [anti (C2h), gauche (C2)] and the two maxima (C2, C2v) had the following relative energies: 0.0, 0.88, 3.56, 5.99 kcal/mole. These are approximate Hartree-Fock numbers. It is estimated that inclusion of electron correlation in the calculation would lower the last number to about 5.1 kcal/mole while leaving the first three values essentially unchanged.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jcc.540010211
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  • 99
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    Electronic Resource
    Atomic Xα calculations based on EHFS(α) = Eexp (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980), S. 88-93 
    Details
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: The total energies and one-electron energies for first- and second-row atoms were calculated by using the Hartree-Fock and the Hartree-Fock-Slater Hamiltonian with Xα orbitals, ui(αexp); α was parametrized from EHFS(αexp) = Eexp. The EHF(αexp) total energies are always higher than the Hartree-Fock energies for the atoms. The relation of the calculated ionization potential to the experimental ionization potential depends on the α used to define ui(α), αexp, or αHF.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jcc.540010112
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  • 100
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    Electronic Resource
    An analysis of the molecular packing of maleic hydrazide (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 1 (1980), S. 261-265 
    Details
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: A molecular packing analysis of the hydrogen-bonded layer structure of maleic hydrazide shows that even in such a structure, the van der Waals energy is the dominant component of the lattice energy. The hydrogen-bond energy of the observed structure is greater than that for alternative structures based on a different mode of hydrogen bonding, and this makes the observed more stable.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jcc.540010307
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