Library

Your email was sent successfully. Check your inbox.

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

Proceed reservation?

Export
Filter
  • ZIB Catalog
  • Articles: DFG German National Licenses  (218)
  • 2020-2024
  • 1990-1994  (218)
  • 1960-1964
  • 1830-1839
  • 1993  (218)
  • Physical Chemistry  (218)
Source
  • ZIB Catalog
  • Articles: DFG German National Licenses  (218)
Material
Years
  • 2020-2024
  • 1990-1994  (218)
  • 1960-1964
  • 1830-1839
Year
  • 101
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993), S. 435-444 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular structures of 1-phenyl- (5) and 1-(2-naphthyl)-8-tropylionaphthalene (6) hexafluoroantimonates were determined by x-ray crystallography and compared with those of 1,8-diphenylnaphthalene and related compounds. In these compounds, the two aromatic substituents face each other in a nearly parallel conformation with a splayed-out arrangement. In the cations 5 and 6, the distance between the facing rings is appreciably shorter than that of other 1,8-diarylnaphthalenes, suggesting the presence of some attractive force. This attraction is ascribed to an intramolecular charge-transfer interaction, and seems to bring about a slight inward bending of the 2-naphthyl substituent in the cation 6. AM1 calculations were carried out for these cations and the results are discussed in comparison with the results of x-ray crystallography.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 102
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993), S. 637-641 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The spectral changes of organic solutions of N,N,N′,N′-tetramethylenediaminoacetylacetonatocopper(II) perchlorate and a merocyanine dye in the presence of NaI or LiClO4 provide examples of anionic and cationic halochromism, respectively. The observed changes are interpreted as arising from all possible interactions in the three-component system of the dye, the salt and the solvent.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 103
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993), S. 59-63 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanism of substitution of the bromine atom in (Z)-α-bromo-β-arylthiovinyl phenyl sulphones, PhSO2CBr = CHSAr, with arylthiolates, Ar′S- was studied. The same mixture of the four possible products, PhSO2C(SAr′) = CHSAr (Ar, Ar′ = p-Tol, p-CIC6H4), was formed in both cross-experiments (Ar ≠ Ar′). A mechanism involving 1,2-intramolecular migration of the arylthio group is suggested.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 104
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993), S. 316-318 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is shown that a theoretical computation of the Dewar resonance energy of decamethyl [5] pericyclyne should give the same value for the homoaromaticity of this compound as that calculated earlier from heat of hydrogenation measurements. Both methods show this quantity to be small, but the accuracy of the methods appears insufficient for more exact agreement.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 105
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 106
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993), S. 7-14 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of hexadecyltrimethylammonium bromide (CTAB) micelles on the acid dissociation constant of para-substituted benzenethiols, α-toluenethiol and n-heptanethiol was determined. The effect of CTAB on the rate of thiolysis by the thiols was measured using para-substituted p-nitrophenyl benzoates. The effects of micelles were analysed using a pseudophase ion-exchange (PIE) model. The Brønsted plot for ester thiolysis showed discontinuity at the pKa of the leaving group in water and was linear in micelles. Micelles increased the Hammett ρ value for thiolysis of esters by α-toluenethiol from 2·08 to 2·68. The Hammett plot for the rection of benzenethiol with esters in water is linear with σ- and displays a ρ value of 0·87, whereas in micelles the plot is linear with σ and presents a ρ of 2·83. Taken together, these data indicate that micelles produce a change in the rate-limiting step of thiolysis of substituted benzoate esters, leading exclusively to rate-limiting thiolate attack. In micelles thiolysis may be concerted and the effect of the aggregate on the reaction mechanism can be ascribed to the interaction of the thiolate ions, and the transition states, with the head groups as well as a medium effect.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 107
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993), S. 29-43 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 2,4,6-Tris(aminocyclohexyl)triazine (1) and 2,4-bis(aminocyclohexyl)-6-methoxytriazine (2) are present in solution in two and three equilibrating conformations, respectively. The activation barrier for interconversion of the conformers 1a ⇌ 1b is 14·55 ± 0·2 kcal mol-1 (1 kcal = 4·184 kJ) and the activation barrier for interconversion of the conformers 2a ⇌ 2b ⇌ 2c is 14·2 ± 0·2 kcal mol-1. The conformational analyses of 1 and 2 were also followed by molecular mechanics calculations. Compounds 1 and 2 form H-bonded intermolecular complexes with bemegride (3). Association of 3 proceeds by selection of a specific conformation of 1 and 2, i.e. 1b and 2a, respectively. The association constants of 3-1b and 3-2a are to Ka = 915 and 450 l mol-1, respectively. Molecular mechanics calculations for the H-bonded intermolecular assemblies support the experimental observations of the selective conformational association.
    Additional Material: 17 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 108
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993), S. 153-159 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 1H, 13C, and 15N NMR studies, including the use of the 13C NMR deuterium perturbation method, showed that the interaction between naphthalene or its methylated derivatives and the nitrosonium cation result in the formation of π-complexes. The chemical behaviour of these complexes was investigated; in particular, their ability to be converted into binaphthyl derivatives was established.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 109
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 110
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The whole process for the syn addition of molecular fluorine to ethylene was analysed at the MP2/6-31 + G level with IRC calculation. The analysis indicates that fluorine approaches the C—C double bond vertically to form a perpendicular complex as the intermediate, which then reorientates to a rhombic-type complex as the transition state to give the final syn addition product. This shows that the square-type complex previously proposed is not involved in any stage of the reaction.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 111
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The methyl ester of 1H-indazole-3-carboxylic acid (2-Me) is formed in the diazotization of o-aminophenylacetic acid to o-diazoniumphenylacetic acid (1) in an intramolecular aliphatic diazonium coupling. 2-Me was identified and characterized by single-crystal x-ray diffraction and found to crystallize as hydrogen-bonded trimers of crystallographically independent molecules. The methylcarboxy groups are rotated slightly out of the best plane of the trimer resulting in only a pseudo-threefold axis. The crystal structure of 2-Me is compared with other indazoles and pyrazole. Regioselective electrophilic diazonium ion addition to the enol tautomer of 1 and subsequent hyrazone-azo tautomerization are proposed as a possible mechanism for indazole formation under acidic conditions. The tautomerization equilibrium between acetic acid and its enol 1,2-dihydroxyethene was studied and the effects of phenyl and o-diazoniumphenyl substitution on this equilibrium were explored with semi-empirical quantum mechanical methods. The performance of the semi-empirical method was assessed by comparison with ab initio and/or experimental data. It was found that the enol of o-diazoniumphenylacetic acid is stabilized greatly owing to extended conjugation and push-pull interactions in the enol form. These results suggest that the enol tautomer might be a viable reactive intermediate that warrants considerations in discussions of reaction mechanisms.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 112
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993), S. 233-242 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structure of 2-mesityl-2-phenylethenol (7) obtained by reduction of mesityl phenyl ketene with LiAlH4 and by acid-catalysed rearrangement of 1-mesityl-2-phenylethylene glycol was determined by x-ray crystallography to be Z [(Z)-7]. In contrast with a literature report, the reduction of 2-acetoxy-2-mesityl-2-phenylacetaldehyde did not provide the E isomer [(E)-7], but a mixture of (Z)-7 and 2-mesityl-2-phenylethenol. An (E)-7-(Z)-7 mixture of 1:5 was obtained starting from pure (Z)-7 at 80°C in dimethyl sulphoxide. The lower stability of (E)-7 was ascribed to higher steric effects due to a smaller Ph-C=C compared with Mes-C=C torsional angle and a preferred intramolecular π(Mes)-OH in (Z)-7 over π(Ph)-OH hydrogen bonding. In order to dissect the effects, the corresponding 2-mesityl-2-phenylvinyl methyl ethers (E)-15 and (Z)-15, where hydrogen bonding is absent, were prepared and equilibrated in chlorobenzene. The (Z)-15: (E)-15 ratio of ca 3:1 between 58° and 132° (ΔG=0·8 kcal mol-1) gives ΔH ≈ 0·6 kcal mol-1 and ΔS ≈ 0·5 e.u. It was concluded that steric effects contribute ca 1 kcal mol-1 and hydrogen bonding ca 1·5 kcal mol-1 to the higher stability of (Z)-7 over (E)-7. The unknown mesitylphenylacetaldehyde 16 was obtained from (Z)-7 at 135°C in 31% yield.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 113
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 114
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993), S. 293-301 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The deuterium isotope effect in the solvolysis of (Z)- and (E)-[methyl-d3]-2-ethylidene-1-adamantyl mesylates [(Z)- and (E)-1d-OMs] and iodides [(Z)- and (E)-1d-I] was studied in 2,2,2-trifluoroethanol at 25·0°C for mesylates and at 50·0°C for iodides. For the mesylates, which show a relatively small F-strain effect, the (Z/E)H rate ratio (117 ± 1) is essentially identical with the (Z/E)D rate ratio (116 ± 1) at 25·0°C. On the other hand, for the iodides, which show a larger F-strain effect, the (Z/E)H rate ratio (5413 ± 57) is greater than the (Z/E)D rate ratio (5040 ± 58) at 50·0°C. This indicates that (Z)-1h-I has greater F-strain than (Z)-1d-I in the ground state. These results again confirm that the F-strain effect in the (Z)-2-ethylidene-1-adamantyl derivatives exists between the (Z)-methyl group and the leaving group atom directly attached to the reaction centre.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 115
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993), S. 347-356 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of several metal ions and metal ion complexes on the hydrolysis and interconversion of uridylyl(2′,5′)uridine and its 3′,5′-isomer were studied as a function of pH and metal ion concentration. The hydrolysis was shown to be markedly accelerated by Zn2+, Cd2+ and trivalent lanthanide ions and by tri- and tetraaza complexes of Zn2+. In contrast, none of these species appreciably promotes the interconversion of the 2′,5′- and 3′,5′-isomers, in spite of the fact that this reaction proceeds through the same pentacoordinated intermediate as the hydrolysis. Lanthanide ions also promote the hydrolytic dephosphorylation of uridine 2′- and 3′-monophosphates, but have a barely noticeable effect on their interconversion. The mechanisms of the metal ion-promoted reactions are discussed.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 116
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993), S. 367-373 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: NMR determination of site-specific hydrogen isotope ratios at natural deuterium abundance (SNIF-NMR) provides the basis for simultaneous access to primary and secondary thermodynamic fractionation factors in exchange reactions and avoids the need for selective isotope labelling of the reagents. The method was applied to the measurement of fractionation parameters involving OH, CH2, CH3 and =CH groups in keto-enol tautomeric equilibria. The fractionation factors relating the =CH and OH sites of the enol species are simply derived from 2H NMR spectra whereas the determination of isotope parameters which relate keto and enol positions exploits a combination of 2H and 1H NMR experiments. Since only monolabelled isotopomers have to be considered at natural abundance, the method also offers the advantage of avoiding the occurrence of complex equilibria associated with multi-labelled species possibly introduced by deuterium enrichment. The primary equilibrium isotope effects illustrate a preference of deuterium for the methylene fragment of the keto form with respect to the ethylenic position of the enol tautomer. Since the enol species is itself engaged in a fast tautomeric equilibrium associated with a symmetric or unsymmetric double minimum potential, the thermodynamic parameters are averaged over the exchanging partners. It is shown that the average thermodynamic fractionation factor relating the OH and =CH hydrogens of the enol are significantly influenced by the nature of the substituents at both carbonyl positions of the β-diketones. Moreover, methyl and chlorine substitution increases by a factor of about 1·1 the thermodynamic isotopic fractionation factor relating the -COCHCO- position of the keto form to the hydroxyl position of the enol.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 117
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 9-23 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Atmospheric pressure absolute rate coefficients have been determined for the gas phase reaction of OH radicals with methyl chloride (k1), methylene chloride (k2), and chloroform (k3) over an extended temperature range using a laser photolysis/laser-induced fluorescence technique. The rate coefficients are best described by the following modified Arrhenius equations: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 (295 - 995) = (4.64 \pm 0.58) \times 10^{ - 12} ({\rm T/300)}^{{\rm 0}{\rm .89}} \exp \{ (- 1447 \pm 75)/T\} cm^3 molec^{ - 1} s^{ - 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 (295 - 995) = (2.01 \pm 0.17) \times 10^{ - 12} ({\rm T/300)}^{{\rm 1}{\rm .09}} \exp \{ (- 771 \pm 48)/T\} cm^3 molec^{ - 1} s^{ - 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 (295 - 774) = (2.71 \pm 0.23) \times 10^{ - 13} ({\rm T/300)}^{{\rm 1}{\rm .52}} \exp \{ (- 261 \pm 42)/T\} cm^3 molec^{ - 1} s^{ - 1} $$\end{document} Measurements were obtained as a function of excimer photolysis intensity and are compared with previous results and extended to higher temperatures. Photolysis intensities in excess of 12 mJ-cm-2 were found to measurably increase (up to a factor of 2) the rate coefficients for k3 between 400-775 K, with the effect increasing with increasing temperature. A similar, yet much smaller (ca. 20-35%) increase was observed for k2 between 675-955 K. No effect was observed for k1 at any temperature. Relative absorption coefficient measurements at 193.3 nm indicated that chlorinated methane photolysis increases with both increasing temperature and increasing chlorine substitution. These measurements suggest that reactant photolysis may be responsible for the observed dependence of k2 and k3 on photolysis intensity at elevated temperatures. The puzzling and disconcerting discrepancy between previously published high temperature measurements of k3 and transition state model predictions is reconciled with these latest measurements. © 1993 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 118
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 119
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 63-66 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 120
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 53-62 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The stoichiometry and kinetics of the oxidation of thiourea (SC(NH2)2) by chlorine dioxide (ClO2) have been studied by uv-vis spectrophotometry using conventional and stopped-flow mixing techniques at 25.0 ± 0.1°C, pH 0.3-4.8. In high acid and initial 10:1 molar ratio of thiourea to chlorine dioxide, thiourea is oxidized relatively rapidly to dithiobisformamidine ion ((NH2)2CSSC(NH2)22+), which slowly decomposes to thiourea, sulfur, and cyanamide (NCNH2). In high acid and excess ClO2, thiourea is oxidized to relatively stable formamidine sulfinic acid ((NH) (NH2)CSO2H). In high acid and molar ratios of ClO2 to thiourea of 5:1 and higher, some oxidation to formamidine sulfonic acid ((NH) (NH2)CSO3H) occurs. At lower acidity, along with Cl-, the major ClO2 reduction product, byproduct sulfate is detected and, at pH 〈 3, ClO2-, also, appears. Kinetics data were collected for high excess thiourea with varying pH. The [ClO2]-time curves are straight lines with negative slopes that increase in magnitude with increasing [thiourea]. The dependence on [thiourea] is first-order; the dependence on [ClO2] is zero-order for 90% of reaction. With decreasing pH, the rate increases and the disappearance of ClO2 becomes autocatalytic. Studies of the effects of reaction products on the rate of reaction lead to the conclusion that autocatalysis at low pH is due to the greater reactivity of HClO2 compared with ClO2-. A 10-step mechanism incorporating a slow one-electron transfer from thiourea to ClO2 to generate the (NH) (NH2)CS · radical and subsequent more rapid reactions has been constructed and implemented in a computer simulation which provides a reasonably accurate fit to the observed kinetics curves. © 1993 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 121
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 1-8 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This article deals with the kinetics of decomposition of four isomers: N—Cl-(L)-2-Aminohexanoic acid, N—Cl-(L)-Leucine, N—Cl-(L)-Isoleucine, and N—Cl-(L)-tert-Leucine, in mild acid and basic aqueous solution. An alternative mechanism for this process which takes place through a nitrenium-like ion transition state is proposed. This mechanism is in consonance with the experimental data and with those available from the literature. © 1993 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 122
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 25-39 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Absolute rate constants for the gas-phase reactions of NO3 with HO2 and OH have been determined using the discharge flow laser magnetic resonance method (DF-LMR). Since OH was found to be produced in the reaction of HO2 with NO3, C2F3Cl was used to scavenge it. The overall rate constant, k1, for the reaction, HO2 + NO3 → products, was measured to be k1=(3.0 ± 0.7)×10-12 cm3 molecule-1 s-1 at (297 ± 2) K and P=(1.4 - 1.9) torr. This result is in reasonable agreement with the previous studies. Direct detection of HO2 and OH radicals and the use of three sources of NO3 enabled us to confirm the existence of the channel producing OH:HO2+NO3→OH+NO2+O2 (1a); the other possible channel is HO2+NO3→HNO3+O2 (1b). From our measurements and the computer simulations, the branching ratio, k1a/(k1a + k1b), was estimated to be (1.0-0.3+0.0). The rate coefficient for the reaction of OH with NO3 was determined to be (2.1 ± 1.0) × 10-11 cm3 molecule-1 s-1. © 1993 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 123
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 41-51 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: One of the important applications of chemical kinetics is the attempt to understand complex processes through kinetic modeling. This process frequently requires that rate constants be obtained by extrapolation of data either to higher or lower temperatures than the experimental, or by estimation or correlation with such data. Thermochemical kinetics combined with conventional transition state theory forms a framework from which this may be done. However, rate data for H transfer reactions may have a significant contribution from tunneling. In this work, a one dimensional approach to tunneling, consistent with conventional transition state theory, is taken to show how tunneling affects the extrapolation and correlation of rate constants in thermochemical kinetics. It is concluded that extrapolation and correlation are both quite good even when tunneling comprises 80% of the reaction. However, this is not without limitations, which are discussed. © 1993 John Wiley & Sons, Inc.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 124
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 67-78 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method is suggested for the determination of the character (homogeneous or heterogeneous) of the material transformation in the investigation of gas-phase reactions under tubular flow conditions. The method provides the estimation of the error in the rate constant of a gas-phase reaction due to the possible parallel occurrence of a heterogeneous process. © 1993 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 125
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 79-90 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Arrhenius parameters of the bimolecular rate constants for the decay of several phenoxyl radicals in aqueous solution were measured. The p-halophenoxyl radicals (F, Cl, and Br) decay in a diffusion controlled reaction as the activation energies are the same as that of diffusion of water (16 ± 1.5 kJ · mol-1). The A factors are 1012.2 ± 0.2. For alkyl and alkoxy substituted phenoxyl, slightly higher activation energies were found (19.5 - 21.9 kJ · mol-1). © 1993 John Wiley & Sons, Inc.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 126
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 91-96 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of dimerization of arylmercurials XC6H4HgCl (X = H, p-CH3, m-CH3, p-Cl, m-OCH3, m-CO2C2H5, and o-OCH3) in the presence of [ClRh(CO)2]2 was studied in hexamethylphosphoramide (HMPA). The experimental rate law obtained is -d[ArHgCl]/dt=k[ArHgCl]2. The kinetic parameters of these reactions have been reported, and the variation, therein, has been explained on the basis of steric effect of substituents. The apparent activation energy E is linearly proportional to pre-exponential factor lnA. A most plausible mechanism has been proposed on the basis of experimental results. © 1993 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 127
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 128
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 97-105 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of oxidation of methyl, ethyl, n-propyl, isopropyl, and n-butyl acetates to acetic acid and the corresponding aldehyde by the title oxidant in aqueous HCl medium at 40°C has been studied. The reaction shows first-order with respect to [oxidant] and fractional orders in [H+] and [ester]. An isokinetic relationship was observed with β = 374 K indicating enthalpy as the rate controlling factor. Attempts have been made to arrive at a linear free energy relationship through the Taft treatment. Electron releasing groups in the ester moiety increase the rate with ρ* = -9.88. A two-pathway mechanism, consistent with the observed kinetic data, has been proposed. © 1993 John Wiley & Sons, Inc.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 129
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 107-112 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the electrophilic substitution of several trialkyltin chlorides by iodine monochloride are presented. Rate constants have been determined at four different temperatures and the activation parameters A, Ea, and ΔS°= are calculated. A mechanism is proposed involving charge-transfer as the driving force for the substitution. © 1993 John Wiley & Sons, Inc.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 130
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 131
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 113-123 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for base hydrolysis of the tris-(1,10-phenanthroline)iron(II) cation and for solvolysis of the cis-dichlorobis(1,2-ethanediamine)cobalt(III) cation have been measured in binary aqueous mixtures containing 1,2-ethanediol, 1,2- or 1,4-butanediol, 1,2- or 1,6-hexanediol, 1-propanol, or t-butyl alcohol, at 298.2 K. Kinetics of base hydrolysis of the cobalt(III) complex have also been monitored in methanol-water and ethanol-water mixtures, again at 298.2 K. The observed reactivity trends are discussed in terms of the hydrophilic and hydrophobic properties of the respective diols. The dominant factor determining reactivity is hydration of the attacking hydroxide or leaving chloride, as is evidenced by the close correspondence between rate constants and transfer chemical potentials for these anions. The role of hydration has also been probed through the determination of activation volumes for these two reactions in 60% 1,4-butanediol. © 1993 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 132
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 125-135 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Although hydrogen abstraction from 1,1,1,2-tetrachloroethane should produce only one kind of radical, CCl3CHCl, the presence of small amounts of trichloroethene, as impurity as well as product of reaction, induces the formation of the a priori unexpected CHCl2CCl2 radicals. The importance of this radical in the reaction pathways of the chlorination and the chlorine induced dehydrochlorination of CCl3CH2Cl, under different experimental conditions, is computed and discussed. For example, at 380 K, and for small partial pressures of chlorine (2 torr), the CHCl2CCl2 radicals account for more than 70% of the formation of the reaction products after only 2% reaction. The major role of trace quantities in long chain radical reactions is emphasized. © 1993 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 133
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 151-159 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants have been measured in several aqueous/organic solvent mixtures for the addition reaction of Cl2·- radicals with 2-propen-1-o1 and 2-buten-1-o1 as a function of temperature and with 2, 3-dimethyl-2-butene at room temperature. The rate constants were in the range of 106-109 L mol-1 s-1, the activation energies were relatively low (1-10 kJ mol-1), and the pre-exponential factors varied over the range log A = 7.9 to 9.4. The rate constants (k) decreased (by up to a factor of 30) upon increasing the fraction of organic solvent and log k correlated linearly with the dielectric constant for a given water/organic solvent system, but the lines for the different solvent systems had different slopes. A better correlation of log k was found with a combination of the solvatochromic factor, ET(30), and the hydrogen-bond donor acidity factor, α. This suggests that the rate of reaction is influenced by the solvent polarity and also by specific solvation of the ionic reactant and product. Solvent effect on the reaction of SO4·- with 2-propen-1-o1 was studied for comparison. © 1993 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 134
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 137-149 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for the gas phase reactions of hydroxyl radicals and chlorine atoms with a number of ethers have been determined at 300 ± 3 K and at a total pressure of 1 atmosphere. Both OH radical and chlorine atom rate constants were determined using a relative rate technique. Values for the rate constants obtained are as follows. TextcompoundkOH×1012(cm3 molecule-1 s-1)kC1×1011(cm3 molecule-1 s-1)Hexane5.53 ± 1.55 - 2-Chloro ethyl methyl ether4.92 ± 1.0914.4 ± 5.02,2-Dichloro ethyl methyl ether2.37 ± 0.504.4 ± 1.62-Bromo ethyl methyl ether6.94 ± 1.3816.3 ± 5.42-Chloro,1,1,1-trifluoro ethyl ethyl ether〈0.30.30 ± 0.10Isoflurane〈0.3〈0.1Enflurane〈0.3〈0.1Di-i-propyl ether11.08 ± 2.2616.3 ± 5.4Diethyl ether - 25.8 ± 4.4The above relative rate constants are based on the values of k(OH + pentane)=[3.94 ± 0.98]×10-12 and k(OH + diethyl ether)=[13.6 ± 2.26] × 10-12 cm3 molecule-1 s-1 in the case of the hydroxyl reactions. In the case of the chlorine atom reactions, the above rate constants are based on values of k(Cl + ethane)=[5.84 ± 0.88] × 10-11 and k(Cl + diethyl ether)=[25.4 ± 8.05] × 10-11 cm3 molecule-1 s-1. The quoted errors include ±2σ from a least squares analysis of our slopes plus the uncertainty associated with the reference rate constants.Atmospheric lifetimes calculated with respect to reaction with OH radicals are based on a tropospheric OH radical concentration of (7.7 ± 1.4) × 105 radicals cm-3, and lifetimes with respect to reaction with Cl atoms are based on a tropospheric Cl atom concentration of 1 × 103 atoms cm-3. Observed trends in the relative rates of reaction of hydroxyl radicals and chlorine atoms with the ethers studied is discussed. The significance of the calculated tropospheric lifetimes is also reviewed. © 1993 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 135
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 161-168 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics for the exchange of Li+, K+, Rb+, and Cs+ for Na+ as the exchangeable cation on bentonite and montmorillonite K10 and KSF have been studied using conductimetric stoppedflow. Dilute aqueous suspensions of the clays, of particle sizes of a few micrometers, were used, so that diffusion was fast and the rate-determining step was the substitution of one cation by another on the lattice surface. The kinetics were treated in terms of relaxation from equilibrium. Relaxation times ranged from 100 to 250 ms, and forward rate constants from 30 to 500 M-1 s-1. The reactions had very low activation enthalpies (7-25 kJ mol-1) and were only slow enough to be studied by the stopped-flow technique because of the large negative entropies of activation (-120 to -170 J K-1 mol-1). © 1993 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 136
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 169-182 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The equilibria and the stopped-flow kinetics of the reaction between the acid bromophenol blue (BPB) and several aromatic amines in toluene to form ion pairs have been investigated. Contrary to expectations, the rate of the proton-transfer increases with increasing activation enthalpy. This is explained in terms of the entropy of the transition state.The role of the electronic structure of the amine and of the solvent are discussed. Solvent effects were further investigated by comparing the activation parameters for the reaction between BPB and pyridine in chlorobenzene, toluene, and benzene. The solvent clearly plays a vital role in determining the rate of proton-transfer via the entropy of activation. The mechanism of the reaction (that proton-transfer is almost complete in the transition state, and is followed by amine migration and ring opening) is confirmed. © 1993 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 137
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 183-191 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: DF-CL studies using NO2 chemiluminescence detection of O yielded a rate constant k1 for O + SiH4 of (2.6 ± 0.5)×10-13 cm3 s-1 at 295 K, where the 95% confidence interval reflects accuracy. FP-RF studies using flash photolysis of SO2 followed by time-resolved vuv fluorescence detection of O at 295 K yielded k1 = (3.0 ± 0.5) ×10-13 cm3 s-1. These results are in good accord with most previous measurements and lead to a combined best estimate of k1 = (3.2 ± 0.4) × 10-13 cm3 s-1. The DF-CL and FP-RF methods appear to have little unrecognized systematic error. © 1993 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 138
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 193-198 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants have been measured for the reactions of the sulfate radical, SO4·-, with alkanes, alkenes, alcohols, ethers, and amines in 95% acetonitrile solution. The rate constants were in the range of 106 L mol-1 s-1 for the abstraction reactions and 107-109 L mol-1 s-1 for the addition and electron transfer reactions. These values are 20 to 80 times lower than those measured in aqueous solutions. Furthermore, the rate constants for the reactions of SO4·- with the primary alcohols increase with the number of carbon atoms and then level off, in contrast to the behavior observed in aqueous solution, where the rate constant increases more sharply for the larger alcohols. © 1993 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 139
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 199-203 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants have been measured in aqueous solutions for the reactions of the carbonate radical, CO3·-, with several saturated alcohols and one cyclic ether as a function of temperature. Arrhenius pre-exponential factors ranged from 2×108 to 1×109 l mol-1 s-1 and activation energies ranged from 16 to 29 kJ mol-1. The results suggest that the reactions are not pure hydrogen abstraction, but involve an additional interaction of the radical with the —OH or —O— linkage. © 1993 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 140
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 205-214 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The complex [Fe(imox) (Nmim)2], where imox is a planar bis(iminooxime) macrocyclic ligand and Nmim=N-methyl imidazole, undergoes substitution reactions in the presence of 2,2′bipyridine (bipy), leading to a series of intermediate mixed complexes. The forward and reverse rate constants for the substitution of the Nmim ligand by water are k1 = 0.23 s-1 and k-1=62 M-1s-1, respectively. The binding of a bipy to the [Fe(imox) (Nmim) (H2O)]+ complex proceeds according to k2 = 4.7×10-2 M-1 s-1 and k-2 = 3.6 × 10-4 s-1, yielding [Fe(imox) (bipy) (Nmim)]+, which eliminates Nmim according to k3 = 1.6 × 10-4 s-1. Further substitution in the [Fe(imox) (bipy)]+ complex with bipy takes place very slowly leading to the [Fe(imox) (bipy)2]+ and [Fe(bipy)3]2+ complexes. © 1993 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 141
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 215-219 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 142
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 143
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 221-227 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction between chromium(VI) and L-ascorbic acid has been studied by spectrophotometry in the presence of aqueous citrate buffers in the pH range 5.69-7.21. The reaction is slowed down by an increase of the ionic strength. At constant ionic strength, manganese(II) ion does not exert any appreciable inhibition effect on the reaction rate. The rate law found is \documentclass{article}\pagestyle{empty}\begin{document}$$ r = k_p k_r [Cr({\rm VI})][{\rm L - ascorbic\,acid][H}^{\rm + }]/(1 + k_p [H^ +]) $$\end{document} where Kp is the equilibrium constant for protonation of chromate ion and kr is the rate constant for the redox reaction between the active forms of the oxidant (hydrogenchromate ion) and the reductant (L-hydrogenascorbate ion). The activation parameters associated with rate constant kr are Ea = 20.4 ± 0.9 kJ mol-1, ΔH≠ = 17.9 ± 0.9 kJ mol-1, and ΔS≠=-152 ± 3 J K-1 mol-1. The reaction thermodynamic magnitudes associated with equilibrium constant Kp are ΔH0 = 16.5 ± 1.1 kJ mol-1 and ΔS0 = 167 ± 4 J K-1 mol-1. A mechanism in accordance with the experimental data is proposed for the reaction. © 1993 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 144
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 249-263 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute rate constants for the addition of the 2-cyano-2-propyl radical to 26 alkenes CH2=CXY at 315 K were determined in solution by time-resolved electron-spin-resonance spectroscopy. They vary with the alkene substituents from 30 M-1 s-1 to 7′010 M-1 s-1. For styrene the temperature dependence is given by log k/M-1 s-1 = 7.7 - 26.1/Θ where Θ = 2.303 RT in kJ/mol. An analysis of the substituent effects in terms of polar and enthalpic factors reveals a dominant influence of the overall reaction enthalpy. © 1993 John Wiley & Sons, Inc.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 145
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 229-237 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetic isotope effect for the abstraction of hydrogen/deuterium from dimethylnitramine and dimethylnitramine-d6 by chlorine atoms has been studied in the temperature range 273-353 K. The rate constant ratio kH0/kD is given by the Arrhenius expression, kH/kD=(0.92 ± 0.07)exp(286 ± 250/RT), where R is expressed in cal mol-1 K-1. The absolute rate constant for the deuterium abstraction reaction is extrapolated as kD=(1.50 ± 0.90) × 10-10 exp(-1,486 ± 370/RT) cm3 molecule-1 s-1. The temperature dependence of the kinetic isotope effect was calculated using the conventional transition-state theory, and the obtained values for kH/kD and ΔEH, D are in good agreement with the experimental value for a bent transition state geometry, with two new vibrational frequencies of 340 cm-1 (272 cm-1) corresponding to the in-plane and out-of-plane motions of hydrogen (deuterium) atoms in the Cl…H…C arrangement. © 1993 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 146
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reaction between 1,2,3-trihydroxybenzene (pyrogallol) and O2 (autoxidation) have been determined by monitoring the concentration of dissolved dioxygen with a polarographic oxygen electrode. The reaction is carried out in pseudo-first-order excess pyrogallol, 25°C, 0.08 M NaCl, and 0.04 M phosphate buffer in the pH range 6.9-10.5. Data collection precedes reaction initiation, but only the data recorded after the estimated 3.2 s dead time are used in kinetics calculations. Observed rate constants are corrected for incomplete mixing, which is treated as a first-order process that has an experimentally determined mixing rate constant of 4.0 s-1. The rate law for the reaction is -d[O2]/dt=kapp[PYR]tot[O2], in which [PYR]tot is the total stoichiometric pyrogallol concentration. A mechanism is presented which explains the increase in rate with increasing [OH-] by postulating that H2PYR- (k2) has greater reactivity with dissolved dioxygen than does H3PYR (k1). The data best fit the equation kapp=(k1 + k2KH[OH-])/(1 + KH[OH-]) when the value of the hydrolysis constant KH (the quotient of the pyrogallol acid dissociation and water autoprotolysis constants) for this medium equals 3.1×104 M-1. The resulting values of k1 and k2, respectively, equal (0.13 + 0.01) M-1 s-1 and (3.5 plusmn; 0.1) M-1 s-1. This reaction is recommended as a test reaction for calibrating the dynamic response of an O2-electrode. © 1993 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 147
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 265-272 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reaction of OH radicals with t-amyl methyl ether (TAME) have been reinvestigated using both absolute (flash photolysis resonance fluorescence) and relative rate techniques. Relative rate experiments were conducted at 295 K in 99 kPa (740 torr) of synthetic air using ethyl t-butyl ether, cyclohexane, and di-isopropyl ether as reference compounds. Absolute rate experiments were performed over the temperature range 240-400 K at a total pressure of 4.7 kPa (35 torr) of argon. Rate constant determinations from both techniques are in good agreement and can be represented by k1=(6.32 ± 0.72) × 10-12 exp[(-40 ± 70)/T] cm3 molecule-1 s-1. Quoted errors represent 2σ from the least squares analysis and do not include any estimate of systematic errors. We show that results from the previous kinetic study of reaction (1) are in error due to the presence of a reactive impurity. Results are discussed in terms of the atmospheric chemistry of TAME. © 1993 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 148
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 273-284 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for the reactions of Cl atoms and OH radicals with haloalkanes were measured using the relative rate technique. From these values the atmospheric lifetimes of the organics with respect to Cl atoms and OH radicals were calculated. Cl atoms were produced by the photolysis of chlorine gas, and photolysis of methyl nitrite was the source of OH radicals. The rate constants were measured for a series of brominated and chlorinated alkanes for which measurements have not yet been reported excepting: k(Cl + 1-chloropropane) and k(OH + 1-chloropropane, 2-chloropropane, and bromoethane). The organics studied were 1-chloropropane, 2-chloropropane, 1,3 dichloropropane, 2-chloro 2methylpropane, bromoethane, 1-bromopropane, 2-bromopropane, 1-bromobutane, 1-bromopentane, and 1-bromohexane. Cl atom reactions were measured at 298 K, the OH radical reactions were measured at temperatures between 298-308 K. © 1993 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 149
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 285-303 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A kinetic mechanism for the chain decomposition of formaldehyde consistent with recent theoretical and experimental results is presented. This includes new calculations and measurements of the rate constant for the abstraction reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_{\rm 2} {\rm O + H} \to {\rm HCO + H}_{\rm 2} $$\end{document} The calculation uses a multi-reference configuration interaction wavefunction to construct the potential energy surface which is used in a tunneling-corrected TST calculation of the rate constant. The rate constant for the bond fission \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_{\rm 2} {\rm O + M} \to {\rm HCO + H + M} $$\end{document} at high temperatures was determined by an RRKM extrapolation of direct low temperature measurements. This mechanism has been successfully tested against laser-schlieren measurements covering the temperature range 2200-3200 K. These measurements are insensitive to all but the above two reactions and they confirm the large, non-Arrhenius rate for the abstraction reaction derived here from theory. Modeling of previous experiments using IR emission, ARAS, and CO laser absorption with this mechanism is quite satisfactory. The branching ratio of the rate of the faster molecular dissociation (CH2O + (M) → CO + H2 + (M)), to that of the bond fission reaction, was estimated to be no more than 2 or 3 over 2000 to 3000 K. Such a ratio is consistent with one recent theoretical estimate and most of the experimental observations. © 1993 John Wiley & Sons, Inc.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 150
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 305-322 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermal decomposition of formaldehyde diluted with Ar was studied behind reflected shock waves in the temperature range of 1200-2000 K at total pressures between 1.3 and 3.0 atm. The study was carried out for compositions from the concentrated mixture, 4% CH2O, to the highly dilute mixture, 0.01% CH2O by using time-resolve IR-laser absorption and IR-emission, and a single-pulse technique. From a computer-simulation study, the mechanism and the rate-constant expressions that could explain all of our data and previously reported ARAS data were discussed. This data obtained over a wide concentration range from 50 ppm CH2O to 4% CH2O were satisfactorily modeled by a five-reaction mechanism. © 1993 John Wiley & Sons, Inc.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 151
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 152
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 323-330 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The multiple photon absorption and decomposition of ethanol irradiated by pulsed 9P18 infrared radiation (1048.7 cm-1) from a TEA CO2 laser has been studied in the fluence range 15 to 5 J cm-2. The absorption cross-section is pressure-dependent due to rapid collisional rotational hole-filling. At low pressures the only important decomposition channel following absorption is molecular dehydration of ethanol to yield ethene, but at higher pressures hydrogen, methane, carbon monoxide, ethane, and ethyne are also produced. In the irradiation of pure ethanol under ‘collision-free’ conditions, thermal decomposition following collisional redistribution of energy makes only a small contribution to the overall decomposition yield at fluences above 3.5 J cm-2 but may become more significant at lower fluences. Modelling using RRKM calculations has been employed to link measured absorbed energies to extents of decomposition of ethanol. Both these calculations and the absorption measurements indicate that at low pressures only a fraction of the irradiated ethanol molecules absorb the 9P18 radiation. © 1993 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 153
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 331-339 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It has been usually thought that the rate of N-Cl-α-amino acids decomposition changes and that their coefficient of molar absorptivity falls when pH 〈 5, which has been explained on the basis of a hypothetical process of protonation at the N-Cl-amino group.We have proved: (i) the absence of protonation at the N-Cl-amino group, at least when pH 〉 2-; (ii) the effect of the method of mixing on the reaction rate; (iii) the absolute necessity of a very careful choice of buffers and solvents; and (iv) the need to check the accuracy of the mathematical model to describe the chemical processes. © 1993 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 154
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 341-351 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis of N-nitrosamines in solutions of acetonitrile follows a first-order reaction with respect to the concentration of nitrosamine. Quantum yields are very low (≈ 0.1) and depend on the concentration of nitrosamine, with the observation of a linear correlation between the reciprocal of quantum yield and the reciprocal of nitrosamine concentration. For all the nitrosamines studied, the final product of the photolysis appears to be unique, alkylidenimine, which in the case of nitroso methyl benzyl amine undergoes a relatively rapid hydrolysis, giving rise to benzaldehyde, following second order kinetics. A provisional model consistent with the experimental results obtained in this work is proposed. © 1993 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 155
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 353-362 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The hydrogen and chlorine atom abstraction reactions from CH3Cl by CF3 radicals produced by the photolysis of hexafluoroacetone (HFA) and CF3I were studied relative to the recombination of CF3 radicals (I)The Arrhenius parameters obtained in the temperature range 416 to 578 K are: \documentclass{article}\pagestyle{empty}\begin{document}$$ Logk_3 /k_2^{1/2} [{\rm cm}^{3/2} {\rm mol}^{ - 1/2} s^{ - 1/2}] = (5.39 + 0.10) - (10490 + 150)/\theta $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ Logk_4 /k_2^{1/2} [{\rm cm}^{3/2} {\rm mol}^{ - 1/2} s^{ - 1/2}] = (4.52 + 0.11) - (13370 + 250)/\theta $$\end{document} where Θ = 2,303.RT cal mol-1 and k2 is the recombination rate constant for the CF3 radicals.The factors that influence the transfer processes of chlorine and hydrogen are analyzed in a series of reactions of halomethanes with CF3 and CH3 radicals. © 1993 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 156
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 363-374 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A model based on the two film approximation is proposed for the description of the kinetics of the hydrogen isotope exchange between CHCl3 and D2O. In this model, details of mass transfer in interfacial region between the two liquid phases are considered and the kinetics of the exchange reaction is quantitatively described without an adjusting parameter. This model is successful in explaining the experimental results obtained with high alkali concentrations, which has not been sufficiently explained in our previous article [M. Iwasaki et al., J. Phys. Chem., 93, 5139 (1989)]. © 1993 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 157
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 375-381 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of NO with O2 has been investigated in aqueous solution. As demonstrated by ion chromatography, the sole product is NO2-. Kinetic studies of the reaction by stopped-flow methods with absorbance and conductivity detection are in agreement that the rate law is -d[O2]/dt=k[NO]2[O2] with k = 2.1 × 106 M-2 s-1 at 25°C. This rate law is unaffected by pH over the range from pH 1 to 13, and it holds with either NO or O2 in excess. By studying the reaction over the temperature range from 10 to 40°C, the following activation parameters were obtained: ΔH≠ = 4.6 ± 2.1 kJ mol-1 and ΔS≠=-96 plusmn; 4 J K-1 mol-1. © 1993 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 158
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 415-422 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetics of Nb(V) hydrolysis in MgCl2, Mg(ClO4)2 mixtures has been investigated by electroanalytical methods and the rate constants determined. A hydrolysis model based on species postulated in the literature is proposed. Resolution of the corresponding differential equations led to results consistent with experimental data obtained from polarographic current vs. time curves. © 1993 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 159
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 160
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 383-397 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using the cyclic voltammetry (CV), the electron-transfer kinetics for the reductions of NO+ and NO2+ cations have been studied at the Pt electrode in nitromethane, sulfolane, and propylene carbonate. The heterogeneous rate constants have been determined by two independent procedures from the transfer coefficient α, the diffusion coefficient D, from a detailed examination of the CV-peak separations, and from an inspection of the values of the cathodic peak potentials at different scan rates. The results have been compared to those reported in the literature, and discussed. In the classical model, outer-sphere electron-transfer reactions are considered subject to an activation energy arising from solvent reorganization and bond reorganization processes. The solvent and molecular reorganizational barriers for these electroreductions have been assessed in aprotic media. The Marcus-Hush theory has been applied to the self-exchange reactions of the NO2+/NO2 and NO+/NO couples in an attempt to predict the rate of electron transfer. The findings indicate some improvement between theory and experiment. However, it should be noted that the experimental values of ks found for the NO2+ reduction in the solvents used are still too high in comparison with those determined theoretically. In view of the fairly strong coordination of the solvent molecule(s) as ligand(s) to NO2+ and NO+ cations, we believe that such discrepancies should stem, to some extent, from the involvement of an inner-sphere pathway by generation of an activated complex on the surface of the Pt electrode. © 1993 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 161
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reaction of the benzyl radical with molecular oxygen has been studied between 393 and 433 K. The Discharge Flow technique with detection of benzyl radicals by Laser Induced Fluorescence in their visible absorption band has been used. All experiments have been performed at ≈1 torr in helium as the buffer gas. The radical benzyl decay plots are characteristic of the approach to equilibrium between benzyl and benzylperoxy: benzyl + O2 \documentclass{article}\pagestyle{empty}\begin{document}$ \mathbin{\lower.3ex\hbox{$\buildrel\textstyle\longrightarrow\over {\smash{\longleftarrow}\vphantom{_{\vbox to.5ex{\vss}}}}$}} $\end{document} benzylperoxy (k3, k-3). Thanks to a reasonable assumption concerning the standard entropy of the reaction (3) (ΔS298°=-29 cal mol-1 K-1), based on the additivity rules of Benson, the following reaction enthalpy is derived for reaction (3): ΔH298°=(-20 ± 1 kcal mol-1). This latter value is compared with a few enthalpies of other related reactions available in the literature. © 1993 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 162
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 437-443 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ninhydrin has been found to react with Cu(glycine)+ and Cu(alanine)+ in the ratio of 1:1. The kinetic studies of the reaction were carried out at different concentrations of the reactants at 80°C (pH = 5.0). The reaction proceeds through the formation of a ternary labile complex of ninhydrin with Cu(II) complexes of glycine and alanine. The kinetics were found to follow pseudo-first-order reaction path with respect to Cu(II)-complex in presence of excess [Ninhydrin]. Formation of a ternary labile complex indicates a template reaction mechanism based on the reactions with coordinated ligands. The variation of pseudo-first-order rate constants with [ninhydrin] was found to be in good agreement with equation \documentclass{article}\pagestyle{empty}\begin{document}$$ 1/k_{obs} = \frac{{B1}}{{[{\rm Ninhydrin}]}} + B_2 $$\end{document} where B1 and B2 are the unknown empirical parameters. The [acetate ion] has no significant effect on the rate constants. On the basis of observed data a probable mechanism has been proposed. © 1993 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 163
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 457-468 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A large number of substrates have hitherto been employed in the Belousov-Zhabotinsky (B-Z) oscillatory system in pure aqueous medium. A systematic study of aromatic bromate oscillators is limited by solubility problem relating to the compounds and the brominated derivatives. The use of aqueous-organic mixed media for the oscillatory study is found to be highly useful for the study of water insoluble substances. A comparative study of the oscillatory behavior of gallic acid as substrate in pure aqueous as well as in a number of mixed media have been made in order to ascertain the suitability of mixed media in oscillatory systems. The alteration of oscillatory characteristics in the presence of organic solvent can be understood in terms of the Field-Koros-Noyes (FKN) mechanism. The oscillatory behavior of seventeen new substrates in the ferroin-catalyzed bromate system in 20% (v) acetonitrile is also presented and discussed in this communication. The reactivity of structurally related substrates has been correlated to the structure in terms of the relevant oscillatory parameters. The use of aqueous-organic mixed media in oscillatory systems would enable the investigation of new classes of substrates since getting them into the solution phase would no longer be a limitation. © 1993 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 164
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A kinetic investigation is described of the reaction of ground state atomic carbon, C(2p2(3PJ)), monitored by time-resolved atomic resonance absorption spectroscopy, with a wide range of halogenated olefins and aromatic compounds. Atomic carbon was generated by the repetitive pulsed irradiation (λ 〉 ca. 160 nm) of C3O2 in the presence of excess helium buffer gas and the added reactant gases in a slow flow system, kinetically equivalent to a static system. C(23PJ) was then monitored photoelectrically by time-resolved atomic resonance absorption in the vacuum ultra-violet (λ = 166 nm, 33PJ ← 23PJ) with direct computer interfacing for data capture and analysis. The following absolute second-order rate constants for the reactions of C(23PJ) with the following reactants are reported: TextReactantkR/cm3 molecule-1 s-1 (300 K)C2F4(1.9 ± 0.1) × 10-10C2Cl4(10.6 ± 0.5) × 10-10CH2CF2(4.3 ± 0.2) × 10-10CHClCCl2(7.9 ± 0.4) × 10-10C6H6(4.8 ± 0.3) × 10-10C6F6(4.9 ± 0.3) × 10-10C6HF5(5.0 ± 0.3) × 10-10C6H2F4(4.4 ± 0.2) × 10-10C6H5 - CH3(5.5 ± 0.3) × 10-10C6F5 - CF3(5.4 ± 0.3) × 10-10These results, constituting the first reported body of absolute rate data for reactions of ground state carbon with these reactants, are compared with the analogous body of absolute rate data for atomic silicon in its Si(3p2(3PJ)) ground state, also determined hitherto by time-resolved atomic resonance absorption spectroscopy and demonstrating similar kinetic behavior. © 1993 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 165
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 445-455 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for several reactions of inorganic radicals with inorganic anions in aqueous and aqueous/acetonitrile solutions have been measured as a function of temperature by laser flash photolysis. The reactions studied were (1) Cl2- + N3-, (2) Br2- + N3-, (3) Cl2- + SCN-, (4) Br2- + SCN-, (5) SO4- + Cl-, (6) SO4- + CO32-, and (7) N3- + I-. The rate constants were corrected for ionic strength and ranged from 106 to 109 L mol-1 s-1. The Arrhenius activation energies varied from 2 to 12 kJ mol-1 for the first 4 reactions, were higher for reaction 6, and negative for reaction 5. The pre-exponential factors also varied considerably with log A ranging from 5 to 14. The values of k298 decreased in most cases by more than an order of magnitude upon increasing the acetonitrile (ACN) fraction from 0 to 70%. For most reactions, this decrease in k298 was due to changes in log A with little regularity in the small changes observed in Ea. For reaction 7, k298 was practically unchanged due to compensating effects of the changes in Ea and log A with ACN mol fraction, giving an isokinetic relationship. An isokinetic relationship was also observed in the case of reaction 6; Ea and log A change in parallel while changing ACN mol fraction. Reaction 3 (Cl2- + SCN-) was also studied in water/t-butanol and water/acetic acid mixtures. Linear correlation was found between log k and the dielectric constant of the medium for water/ACN and water/t-BuOH but the lines for the two solvent mixtures had different slopes, suggesting specific solvation effects in addition to the primary solvent polarity effects. With water/acetic acid, k decreased and then increased upon addition of acetic acid. © 1993 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 166
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 167
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 469-477 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The substitution reaction between aquopentacyanoferrate(II) and tetraamminepirazynecarboxylatocobalt(III) to form a binuclear species is studied in various binary aqueous mixtures at different temperatures. Values of activation parameters seem to indicate no change in the mechanism of the reaction in the different mixtures. Medium effects have been rationalized by using a multiparameter regression of solvent parameters. Results show that the reaction follows a dissociative mechanism. © 1993 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 168
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 479-487 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate coefficients for the removal of O(1D) by reaction with the following seven bromocarbons were measured using time-resolved vacuum UV atomic resonance fluorescence detection of O(3P): CH3Br, CH2Br2, CHBr3, CF3Br (Halon-1301), CF2Br2 (Halon-1202), CF2ClBr (Halon-1211), and CF2BrCF2Br (Halon-2402). The branching ratios for the quenching of O(1D) to O(3P) by the above molecules were also determined. From these measurements, the rate coefficients for reactive and nonreactive loss of O(1D) were calculated. These results are discussed in terms of their atmospheric relevance and trends in reactivity of O(1D) with hydrocarbons upon halogen substitution. © 1993 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 169
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 489-507 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: One unit of S(IV) (SO2 or SHO3-) is oxidized per 2 units of [NiIII(cyclam)] species to obtain sulfate. Kinetic analyses have been done by varying the acidities (0.013 ≤ [H+] ≤ 1.0 M) and halide concentrations (0.000 ≤ [X-] ≤ 0.012 M; X=Cl and Br) at constant ionic strength (μ = 1.0 M). The rate law that incorporates the [X-] and [H+] dependence is -d[NiIII]T/dt=2k[NiIII]T[S(IV)]T where 2k={ka[H+] + kbK + kcXK′X[H+] [X-] + kdXK′XK[X-]} {[H+] + K}-1 {1 + K′X[X-]}-1, here ka=87 ± 7 M-1 s-1, kb=(2.5 ± 0.5)×103 M-1 s-1 and pK = 1.8 ± 0.2. Rate constants ka and kb are attributed to the reactions of [NiIII(cyclam) (H2O)2]3+ with SO2 and SHO3-, respectively. Monohalo species apparent equilibrium constants K′Cl=(1600 ± 400) M-1 and K′Br=(190 ± 20) M-1 and rate constants kcCl=80 ± 8 M-1 s-1 and kcBr = 140 ± 15 M-1 s-1 are ascribed to the protonated pathway, involving the [NiIII(cyclam) (H2O)X]2+ and SO2(aq) reaction pairs. The other two rate constants of kdCl=(5 ± 1)×103 M-1 s-1 and kdBr=(3.1 ± 0.5)×104 M-1 s-1, refer to the deprotonated pathway and are assigned to the [NiIII(cyclam) (H2O)X]2+ /SHO3- redox couple. A deuterium H2O / D2O isotope effect of 2.1-2.8 can be attributed partially to an equilibrium isotope effect at low acidity though a small kinetic isotope (2.5 ± 0.5) effect is evident for the dihydrogen sulfito pathway, ka. The kinetic isotope effect and the absence of sulfite radical scavenging effects are explained by a mechanism entailing migration of a hydride from sulfur to the NiIII center to produce a NiIII - H species, which rapidly comproportionates, and S(VI). © 1993 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 170
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A model scheme incorporating reactant inhibition in the rate process has been analyzed with a view to study the instability of homogeneous solution due to diffusion. Conditions for the occurrence of Turing as well as phase instability are derived and show the existence of multiplicity in the parameter space. The Ginzburg-Landau equation for the system is developed and solved numerically in various regions of the parameter space. The simple model system shows the existence of very rich behavior including normal and inverted bifurcations in the super and subcritical regimes. The various results are analyzed and discussed. © 1993 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 171
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 521-537 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A laser flash photolysis-long path absorption technique has been employed to study the kinetics of the reaction products as a function of temperature (248-346 K), pressure (16-800 torr), and buffer gas identity (N2, CF4). The reaction is found to be in the falloff regime between third and second-order over the entire range of conditions investigated. This is the first study where temperature-dependent measurements of k1(P, T) have been reported at pressures greater than 12 torr; hence, our results help constrain choices of k1(P, T) for use in models of lower stratospheric BrOx chemistry. Approximate falloff parameters in a convenient form for atmospheric modeling are derived. © 1993 John Wiley & Sons, Inc.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 172
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 539-548 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The relative hydroxyl radical reaction rate constants from the simulated atmospheric oxidation of selected acetates and other esters have been measured. Reactions were carried out at 297 ± 2 K in 100-liter FEP Teflon®-film bags. The OH radicals were generated from the photolysis of methyl nitrite in pure air. Using a rate constant of 2.63 × 10-11 cm3 molecule-1 s-1 for the reaction of OH radicals with propene, the principal reference organic compound, the rate constants (×1012 cm3 molecule-1 s-1) obtained for the acetates and esters used in this study are: Textn-propyl acetate3.42 ± 0.87n-butyl acetate5.71 ± 0.94n-pentyl acetate7.53 ± 0.482-ethoxyethyl acetate10.56 ± 1.312-ethoxyethyl isobutyrate13.56 ± 2.322-ethoxyethyl methacrylate27.22 ± 2.064-pentene-1-yl acetate43.40 ± 3.853-Ethoxyacrylic acid ethyl ester33.30 ± 1.22Error limits represent 2σ from linear least-squares analysis of data.A linear correlation was observed for a plot of the measured relative rate constants vs. the number of CH2 groups per molecule of the following acetates: methyl acetate, ethyl acetate, n-propyl acetate, butyl acetate, and pentyl acetate. © 1993 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 173
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 174
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 549-570 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This qualitative study examines the response of the novel energetic material ammonium dinitramide (ADN), NH4N(NO2)2, to thermal stress under low heating rate conditions in a new experimental apparatus. It involved a combination of residual gas mass spectrometry and FTIR absorption spectroscopy of a thin cryogenic condensate film resulting from deposition of ADN pyrolysis products on a KCl window. The results of ADN pyrolysis were compared under similar conditions with the behavior of NH4NO3 and NH2NO2 (nitramide), which served as reference materials. NH4NO3 decomposes into HNO3 and NH3 at 182°C and is regenerated on the cold cryostat surface. HNO3 undergoes presumably heterogeneous loss to a minor extent such that the condensed film of NH4NO3 contains occluded NH3. Nitramide undergoes efficient heterogeneous decomposition to N2O and H2O even at ambient temperature so that pyrolysis experiments at higher temperatures were not possible. However, the presence of nitramide can be monitored by mass spectrometry at its molecular ion (m/e 62). ADN pyrolysis is dominated by decomposition into NH3 and HN(NO2)2 (HDN) in analogy to NH4NO3, with a maximum rate of decomposition under our conditions at approximately 155°C. The two vapor phase components regenerate ADN on the cold cryostat surface in addition to deposition of the pure acid HDN and H2O. Condensed phase HDN is found to be stable for indefinite periods of time at ambient temperature and vacuum conditions, whereas fast heterogeneous decomposition of HDN at higher temperature leads to N2O and HNO3. The HNO3 then undergoes fast (heterogeneous) decomposition in some experiments. Gas phase HDN also undergoes fast heterogeneous decomposition to NO and other products, probably on the internal surface (ca. 60°C) of the vacuum chamber before mass spectrometric detection. © 1993 John Wiley & Sons, Inc.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 175
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 571-594 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A fast-flow technique suitable for measuring elementary rate constants over a wide range of pressures has been developed. The method operates under turbulent flow conditions, in contrast to laminar flow which characterizes the conventional low pressure technique. Flow visualization, velocity profile measurements, and tracer pulse studies have been carried out in a flow tube reactor to investigate the dynamics of both laminar and turbulent flow for chemical kinetics purposes. Furthermore, the wall collision frequency for the reactants has been determined: at the higher pressures it is greatly reduced in comparison with the frequency characteristic of the conventional low pressure laminar flow technique. Also, to test and validate the technique the bimolecular rate constants for the reactions H+Cl2 and H+O3 have been measured at total pressures in the 3-300 torr range; at pressures below 5 torr, as well as above 50 torr in the turbulent flow regime the agreement with the recommended literature values is excellent. © 1993 John Wiley & Sons, Inc.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 176
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 595-607 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of electron transfer reactions between acetophenones with Ce(IV) have been studied in aqueous acetic acid medium in the presence of cationic micelle Cetylpyridinium chloride (CPyCl) at different temperatures. Kinetic data reveal first-order dependence with respect to each of Ce(IV) and acetophenones. The cationic micelle, Cetylpyridinium chloride enhances the oxidation reactions. The catalysis fits to a model developed by Menger and Portnoy as well as Berezin's phase separation model. The binding and partition constants and the transfer free energy from water to micelle have been estimated and discussed, suggesting that the solubilization of both the reactants in the micellar phase, facilitates the oxidation. © 1993 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 177
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 609-631 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the present study the determination of the mechanism of the thermal decomposition of magnesium hydroxide from thermogravimetric experiments is attempted. For this purpose nonisothermal kinetic analysis of the dynamic experimental data is applied, using different methods, which are based on the best linearization of a functional form of the Arrhenius equation. The experiments were carried out under nonisothermal conditions in a thermogravimetric analyzer with nitrogen atmosphere, at five different heating rates, i.e., 3, 8, 15, 20, and 35 deg/min. The nonisothermal methods used for the kinetic analysis of the experimental data were the Coats-Redfern method, the Romero et al., the improved Coats-Redfern method, the differential method, the differential by Jerez et al., and a method using the heating rate as a variable. Applying each of these methods, the kinetic parameters and, in most cases, the form of the conversion function (kinetic model) which governs the dehydroxylation process of Mg(OH)2 were determined. From the comparative study of the results of the above methods and using criteria about the credibility of each method, it was concluded that the kinetic model which represents the mechanism of the dehydroxylation of magnesium hydroxide, is that corresponding to the two dimensions nucleation with a reference value of activation energy 117.67 kJ/mol. © 1993 John Wiley & Sons, Inc.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 178
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 633-638 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of photochemically generated energetic hydrogen atoms with 1-chloropropane, reaction (1), has been examined for translational energies of H* in the range 40 to 110 kJ mol-1. Integral probabilities for reaction (1) have been determined, and the phenomenological threshold energy is 47 ± 10 kJ mol-1. The moderating effect of CO2 on reaction (1) for hydrogen atoms of initial energy 108 kJ mol-1 has also been studied. © 1993 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 179
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 639-649 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The products formed by the hydroxyl radical initiated photo-oxidation of diethyl ether have been investigated by irradiating synthetic air mixtures containing diethyl ether and nitrous acid in amounts approaching ppbv levels in a smog chamber. The decay of reactants and formation of products were monitored by gas chromatography, HPLC, and by chemiluminescent analysis. The major products are ethyl formate and formaldehyde, minor products include ethyl acetate, acetaldehyde, peroxyacetyl nitrate, methyl nitrate, and ethyl nitrate. The products observed arise from the decomposition reactions of the 1-ethoxyethoxy radical and its reaction with oxygen. One molecule of nitric oxide appears to be oxidized per molecule of diethyl ether reacted. This is lower than would be expected on the basis of the proposed mechanism and possible reasons for the discrepancy are discussed. © 1993 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 180
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 181
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A variety of relative and absolute techniques have been used to measure the reactivity of fluorine atoms with a series of halogenated organic compounds and CO. The following rate constants were derived, in units of cm3 molecule-1 s-1: CH3F, (3.7 ± 0.8) × 10-11, CH3Cl, (3.3 ± 0.7) × 10-11; CH3Br, (3.0 ± 0.7) × 10-11; CF2H2, (4.3 ± 0.9) × 10-12; CO, (5.5 ± 1.0) × 10-13 (in 700 torr total pressure of N2 diluent); CF3H, (1.4 ± 0.4) × 10-13; CF3CCl2H (HCFC-123), (1.2 ± 0.4) × 10-12; CF3CFH2 (HFC-134a), (1.3 ± 0.3) × 10-12, CHF2CHF2 (HFC-134), (1.0 ± 0.3) × 10-12; CF2ClCH3 (HCFC-42b), (3.9 ± 0.9) × 10-12, CF2HCH3 (HFC-152a), (1.7 ± 0.4) × 10-11; and CF3CF2H (HFC-125), (3.5 ± 0.8) × 10-13. Quoted errors are statistical uncertainties (2σ). For rate constants derived using relative rate techniques, an additional uncertainty has been added to account for potential systematic errors in the reference rate constants used. Experiments were performed at 295 ± 2 K. Results are discussed with respect to the previous literature data and to the interpretation of laboratory studies of the atmospheric chemistry of HCFCs and HFCs. © 1993 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 182
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 667-680 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Relative rate experiments using UV photolysis of F2 or Cl2 have been used to determine rate constant ratios for several hydrofluorocarbon (HFC) reactions with Cl or F atoms and for HFC alkyl radicals with molecular halogens. For mixtures with F2 present, dark reactions are, also, observed which are attributed to thermal dissociation of the F2 to form F atoms. At 296 K, the rate of reaction (1a) [CF2HCH3 + F → CF2CH3 + HF] relative to (1b) [CF2HCH3 + F → CF2HCH2 + HF] is k1a/k1b = 0.73 (±0.13) and is independent of T (= 262-348 K). At 296 K, the ratio of reaction (2a) [CF2HCH2F + F → products] to that of (k1a + k1b) is (k1a + k1b)/k2a = 2.7 (±0.4), and for reaction (2b) [CF3CH3 + F → products] (k1a + k1b)/k2b = 22 ± 12. The temperature dependence (263-365 K) of the rate constant of reaction (3) [CF3CFH2 + Cl → products] relative to reaction (4) [CF3CFClH + Cl → products] is k3/k4(±10%) = 1.55 exp(-300 K/T). For the alkyl radicals formed from HFC 152a (CF2HCH2 and CF2CH3) and from HFC 134a (CF3CFH), rate constants for the reactions with F2 and Cl2 were measured relative to their reactions with O2. The rate constant of reaction (5cl) [CF2CH3 + Cl2 → CF2ClCH3 + Cl] relative to (5o) [CF2CH3 + O2 → CF2(O2)CH3] is k5cl/k5o(±15%) = 0.3 exp(200 K/T). For reaction (5f) [CF2CH3 + F2 → CF3CH3 + F], k5f/k5o(±35%) = 0.23. The ratio for reaction (6f) [CF2HCH2 + F2 → CF2HCH2F + F] relative to (6o) [CF2HCH2 + O2 → CF2HCH2O2] is k6f/k6o(±40%) = 1.23 exp(-730 K/T). The rate constant ratio for reaction (8cl) [CF3CFH + Cl2 → CF3CFClH + Cl] relative to reaction (8o) [CF3CFH + O2 → CF3CFHO2] is k8cl/k8o(±18%) = 0.16 exp(-940 K/T). For reaction (8f) [CF3CFH + F2 → CF3CF2H + F], k8f/k8o(±35%) = 0.6 exp(-860 K/T). © 1993 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 183
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 681-700 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new method for analyzing the problems of chemical kinetics is elaborated involving the technique of mathematical modeling. Namely, the matching method of the asymptotic expansion is applied to analyzing the inhibition mechanism of oxidation. The proposed approach is an extension of the well-known method of quasi-stationary concentrations and may be applied to study a series of problems in the field of chemical kinetics. Three different time scales were established for the mechanism of inhibited oxidation under restrictions k7[InH]0/(2k6Wi)1/2 ≤ 1 and k8 ≫ 2k6 ≫ k7. At the first time scale (that is very fast and is measured in second fractions) the concentration of radicals In only changes while [RO2] ≃ [RO2]0, [In H] ≃ [In H]0 are constants. At the second time scale (s), [RO2] changes while [In] ≃ [In]st, [In H] ≃ [In H]0 are constants. At the third time scale (min), [In H] changes. An asymptotic analysis of the differential equations allows us to find out both the time duration of each step and the variation of the component which changes at this step. After that the rate constants k8, 2k6, k7 are determined from comparison with the experimental measurements of [In], [RO2], and [In H]. Due to the simplicity and efficiency of the asymptotic method, one may be applied to treating the complex multicenter radical chain processes such as conjugated oxidation, radical copolymerization, sulfoxidation, etc. © 1993 John Wiley & Sons, Inc.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 184
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ultraviolet absorption spectrum, kinetics, and mechanism of the self reaction of CF3CF2O2 radicals have been studied in the gas phase at 295 K. Two techniques were used; pulse radiolysis UV absorption to measure the spectrum and kinetics, and long-path length FTIR spectroscopy to identify and quantify the reaction products. Absorption cross sections were quantified over the wavelength range 220-270 nm. At 230 nm, σCF3CF2O2 = (2.74 ± 0.46) ×10-18 cm2 molecule-1. This absorption cross section was used to derive the observed self reaction rate constant for reaction (1), defined as, -d[CF3CF2O2]/dt = 2k1obs[CF3CF2O2]2: k1obs = (2.10 ± 0.38) ×10-12 cm3 molecule-1 s-1 (2σ).The observed products following the self reaction of CF3CF2O2 radicals were COF2, CF3O3CF3, CF3O3C2F5, and CF3OH. CF3O2CF3 was tentatively identified as a product. The carbon balance was 90-100%. The self reaction of CF3CF2O2 radicals was found to proceed via one channel to produce CF3CF2O radicals which then decompose to give CF3 radicals and COF2. In the presence of O2, CF3 radicals are converted into CF3O radicals. CF3O radicals have several fates; self reaction to give CF3O2CF3; reaction with CF3O2 radicals to give CF3O3CF3; reaction with C2F5O2 radicals to give CF3O3C2F5; or reaction with CF3CF2H to give CF3OH. As part of this work a rate constant of (2.5 ± 0.6) ×10-16 cm3 molecule-s-1 was measured for the reaction of Cl atoms with CF3CHF2 using a relative rate technique. Results are discussed with respect to the atmospheric chemistry of CF3CF2H (HFC-125). © 1993 John Wiley & Sons, Inc.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 185
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 745-753 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A detailed kinetic study of the reaction between toluidine blue (tolonium chloride) (TB+Cl-) and stannous chloride is carried out in aqueous hydrochloric acid. The depletion kinetics of toluidine blue were spectrometrically monitored at 626 nm. The reaction had fractional order with respect to toluidine blue (one half), three halves with respect to Sn2+, and first-order dependence on H+ ion. Stoichiometric ratio between reductant and oxidant is 1:1. During the reaction Sn2+ is oxidized to Sn4+ and toluidine blue is reduced to colorless base in two univalent steps. © 1993 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 186
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 719-743 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A critical reappraisal and kinetic modeling is presented of a sodium/N2O system. The analysis provides a compelling argument that previously reported kinetic decay rates may refer not to the reaction of O with NaO but rather to that of O with Na2O. The system shows pronounced propensity for a significant portion of the NaO to be quantitatively converted to Na2O on a time scale commensurate with that of the Na/N2O titration reaction. The O atom in the system does appear to originate from the photolysis of a residual level of NaO. The observed Na(2P) chemiluminescence, used to track the O atom decay rates, can be consistent with the O + NaO reaction as previously surmised. It is unlikely that the alternate O + Na2 and O + Na2O chemiluminescent channels can generate the observed intensity levels. This reanalysis, which provides for the observed first order dependences on N2O(Na2O) and O atom concentrations has significant implications for the Chapman atmospheric mechanism of the sodium airglow. Its conclusions resurrect the viability of the original scheme which requires efficient branching of the O + NaO reaction to Na(2P). Recent suggestions invoking the participation of NaO(A2Σ+) require the latter to have a metastable nature with respect to its radiative and collisional quenching (N2, O2) channels, for which there is no current evidence.An additional evaluation of the rate constant measurements for the fast reactions of NaO with NO or CO indicates that these most probably are kinetically complex and involve longlived transition states. Their rate constants are predicted to have small negative activation energies and pressure dependences. In the case of NaO with CO this may explain its low Na(2P) chemiluminescent efficiency. For the NaO + O reaction, a rate constant of about 4 ×10-11 cm3 molecule-1s-1 is predicted at room temperature. This is similar to that used in earlier atmospheric models. Its magnitude circumvents the consequences of the reaction's large entropy decrease which otherwise implies too large a cross-section for the reverse reaction. A smaller value also is more likely to be consistent with a normal short-lived collisional transition state, which will allow for a more significant Na(2P) quantum efficiency. © 1993 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 187
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 771-776 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chemical kinetics of benzonitrile nitration with mixed acid is investigated in the temperature range 283-299 K. Pseudo-first-order rate constants are evaluated by means of rate experiments on homogeneous reacting mixtures having large stoichiometric excesses of nitric acid.The second-order kinetic constants for nitronium ion attack to the aromatic substrate are derived on the basis of the assessed nitration mechanism. An activation energy of 604 ± 37 kJ mol-1 is calculated for this reaction step. © 1993 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 188
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 755-770 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetics of uncatalyzed and Ru(III)-catalyzed oxidations of mono-, di-, and tri-chloroacetic acids by the title compound (bromamine-B or BAB) in HCl medium has been studied at 40°C. The uncatalyzed reaction shows a first-order dependence of the rate on [BAB], and fractional and zero orders in [acid] at low and high [HCl] ranges, respectively. The Ru(III)-catalyzed reaction, on the other hand, shows a first-order behavior on each of [BAB] and [substrate], second-order dependence on [Ru(III)], and inverse fractional and inverse first orders in [acid] at low and high [HCl] ranges. Addition of halide ions and the reduction product of BAB, benzenesulfonamide, has no effect on the reaction rate. Variation of ionic strength of the medium has no influence on the reaction. Solvent isotope effect was studied using D2O. Activation parameters have been evaluated from the Arrhenius plots. Mechanisms consistent with the above kinetic data have been proposed. The protonation constant of monobromamine-B evaluated from the uncatalyzed reaction is 12.4 while that evaluated from Ru(III) catalyzed reaction is 12.7. A Taft linear free-energy relationship is noted for the catalyzed reaction with ρ* = 1.2 and 0.07 indicating that electron withdrawing groups enhance the rate. An isokinetic relation is observed with β = 338 K indicating that enthalpy factors control the reaction rate. © 1993 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 189
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 777-782 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This article proposes a mechanism of CO2 hydrate formation taking into account both diffusion and reaction, and gives an analysis of its kinetics. The most important assumptions on the model are that water dissolves into liquid CO2 and reacts to form CO2 hydrate, and that the hydrate blocks the dissolution and diffusion of water. Computational simulations were conducted, and the model proposed explains well the many observations on the CO2 hydrate formation in previous articles. It is concluded that liquid CO2 disposed in a deep ocean will form a very thin film of CO2 hydrate, and this will greatly control the CO2 diffusion in the ocean. © 1993 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 190
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 191
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 783-794 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gas-phase reaction of ozone with unsaturated alcohols, carbonyls, and esters in air have been investigated at atmospheric pressure, ambient temperature (285-295 K), and in the presence of sufficient cyclohexane to scavenge the hydroxyl radical which forms as a product of the ozone-unsaturated compound reaction. The reaction rate constants, in units of 10-18 cm3 molecule-1 s-1, are 0.26 ± 0.05 for acrolein, 1.07 ± 0.05 for 2-ethyl acrolein, 6.0 ± 0.4 for ethyl vinyl ketone, 4.9 ± 0.4 for 3-buten-1-ol, 14.4 ± 2.0 for allyl alcohol, 105 ± 7 for cis-3-hexen-1-ol, 7.5 ± 0.9 for methyl methacrylate, 2.9 ± 0.3 for vinyl acetate, 4.4 ± 0.3 for methyl crotonate, and 8.1 ± 0.3 for the 1,1-disubstituted alkene 2-ethyl-1-butene. Substituent effects on reactivity are discussed by comparison with alkenes and indicate that the reactivity of unsaturated alcohols is the same as that of alkene structural homologues and that the  - C(O)OR,  - C(O)R, and  - CHO groups decrease the reactivity towards ozone as compared to alkyl groups. Estimates are made of the atmospheric persistence of these unsaturated compounds using the kinetic data obtained in this study as input to structure-reactivity and linear free-energy relationships. © 1993 John Wiley & Sons, Inc.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 192
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 795-803 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Flowing and static gas-phase samples of HNO3 in O2 and N2 were analyzed by long-path ultraviolet/visible (UV/VIS) spectroscopy to reveal the presence of both NO2 and NO3, the concentrations of which were calculated using differential absorption cross sections. NO2 is produced predominantly by the heterogeneous decomposition of HNO3, whereas NO3 is generated in the gas phase by the thermal decomposition of N2O5, a product of the self-disproportionation of liquid HNO3. © 1993 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 193
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 819-824 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using a relative rate technique the reactions of chlorine and fluorine atoms with CF3CHO have been determined to proceed with rate constants of (1.8 ± 0.4) × 10-12 and (2.7 ± 0.1)×10-11 cm3 molecule-1 s-1, respectively. Experiments were performed at 295 ± 2 K and 700 torr total pressure of nitrogen. The results are discussed with respect to the design and interpretation of laboratory studies of the atmospheric chemistry of CFC replacements. © 1993 John Wiley & Sons, Inc.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 194
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 805-817 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This article describes the first direct determination of the rate coefficient for the self-reaction between two NO3 radicals. A laser photolysis technique was used to generate NO3, and time-resolved decays of NO3 were followed after stopping the photolysis. The products of the reaction are inferred to be NO2 and O2. The derived rate coefficient at room temperature for the self-reaction of (2.3 ± 0.8) ×10-16 cm3 molecule-1s-1 is in excellent agreement with the only other data, which were obtained in an indirect study. Consideration is given to the magnitude and influence of secondary chemistry and to the participation of FO in the chemistry of the NO3 buildup phase. The studies were conducted over a pressure range of 8 to 100 torr in helium. No clear pressure dependence was observed, and some tentative inferences are drawn both from this result and from the absolute magnitude of the rate coefficient about the mechanism of the reaction. There is apparently no role for the reaction in the chemistry of the atmosphere. © 1993 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 195
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 825-831 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of methyl tert-butyl ether (abbreviated as MTBE) from methanol (MeOH) and tert-butyl alcohol (TBA) in the liquid phase was studied by using Amberlyst 15 in the H+ form as an acid catalyst. Experiments were carried out in a stirred batch reactor at different temperatures (313, 318, and 323 K) under atmospheric pressure.It was found that catalyst sizes and rotation speeds had no significant effects on reaction rates. Mechanism studies showed that three reactions took place simultaneously. It was also found that dehydration of TBA could not be neglected. The experimental concentration profiles with time could be simulated well by simple kinetics. Finally, rate constants could be expressed by Arrhenius equations. © 1993 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 196
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 833-844 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate coefficients for the removal of Cl atoms by reaction with three HCFCs, CF3CHCl2 (HCFC-123), CF3CHFCl (HCFC-124), and CH3CFCl2 (HCFC 141b), were measured as a function of temperature between 276 and 397 K. CH3CF2Cl (HCFC-142b) was studied only at 298 K. The Arrhenius expressions obtained are: k1 = (3.94 ± 0.84)× 10-12 exp[-(1740 ± 100)/T] cm3 molecule-1 s-1 for CF3CHCl2 (HCFC 123); k2 = (1.16 ± 0.41) × 10-12 exp[-(1800 ± 150)/T] cm3 molecule-1 s-1 for CF3CHFCl (HCFC 124); and k3 = (1.6 ± 1.1) × 10-12 exp[-(1800 ± 500)/T] cm3 molecule-1 s-1 for CH3CFCl2 (HCFC 141b). In case of HCFC 141b, non-Arrhenius behavior was observed at temperatures above ca. 350 K and is attributed to the thermal decomposition of CH2CFCl2 product into Cl + CH2CFCl. In case of HCFC-142b, only an upper limit for the 298 K value of the rate coefficient was obtained. The atmospheric significance of these results are discussed. © 1993 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 197
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 198
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 845-863 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal reaction of HNCO with NO2 has been studied in the temperature range of 623 to 773 K by FTIR spectrometry. Major products measured are CO2 and NO with a small amount of N2O. Kinetic modeling of the time resolved concentration profiles of the reactants and products, aided by the thermochemical data of various likely reactive intermediates computed by means of the BAC-MP4 method, allows us to conclude that the reaction is initiated exclusively by a new bimolecular process: with a rate constant, k1 = 2.5 × 1012e-13,100/T cm3/mols. The well-known bimolecular reaction is the only strong competitive process in this important reactive system throughout the temperature range studied. Kinetic modeling of NO formation and NO2 decay rates gave rise to values of k10 which were in close agreement with literature data. © 1993 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 199
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 865-874 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A kinetic study on the basic hydrolysis of cephaloridine at pD= 10.5 was carried out by using the 1H—NMR technique. Epimerization at H7, a nucleophilic attack of hydroxyl ion on the β-lactam carbonyl group followed by the release of the pyridine molecule, and isomerization of the double bond at position 3 in the dihydrothiazine ring were the major reactions observed.Based on the results obtained, it should be emphasized that the presence of a pyridine group at 3′ results in a slightly increased formation constant for the exo methylene compound relative to other cephalosporins with different substituents at that position.The activation energy for the epimerization constant and the cleavage of the β-lactam ring at pD 10.5 was 21.2 kcal/mol. © 1993 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 200
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 875-880 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constant for the reaction of phenyl radical with hydrogen bromide has been measured with the cavity-ring-down method at six temperatures between 297 and 523 K. The Arrhenius expression for the H abstraction reaction can be effectively given by: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_\phi = 10^{ - 10.39 \pm 0.10} {\rm exp[-(551} \pm {\rm 19 +)/T]cm}^{\rm 3} /{\rm s} $$\end{document}. The values of these parameters are similar to those for the H + HBr reaction, but are in sharp contrast to those for alkyl radical reactions. The gross difference between the alkyl radical reactions and the phenyl and H-atom reactions could be rationalized in terms of the inductive effects of these radicals as measured by Taft's σ* (polar) constants. © 1993 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
Close ⊗
This website uses cookies and the analysis tool Matomo. More information can be found here...