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  • Physical Chemistry  (455)
  • Wiley-Blackwell  (455)
  • Springer
  • 1
    Electronic Resource
    Electronic Resource
    A kinetics study of the reactions of OH with several aromatic and olefinic compounds (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 783-804 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of hydroxyl radicals with eight substituted aromatic hydrocarbons and four olefins were studied utilizing the flash photolysis-resonance fluorescence technique. The rate constants were measured at 298°K using either Ar or He as the diluent gas. The values of the rate constants (k × 1012) in the units of cm3/molec. sec are (a) OH + o-xylene → products: (12.9±3.8), 20 torr He; (13.0±0.3), 20 torr Ar; (12.4±0.1), 200 torr He;(b) OH + m-xylene → products: (15.6±1.4), 3 torr Ar; (19.4±0.8), 20 torr Ar; (21.4±0.2), 20 torr He; (20.3±1.9), 200 torr Ar; (20.6±1.3), 200 Torr He;(c) OH + p-xylene → products: (8.8±1.2), 3 torr Ar; (10.1±1.0), 20 torr He; (10.5±0.6), 200 torr He;(d) OH + ethyl benzene → products: (7.50±0.38), 3 torr He; (7.06±0.26), 20 torr He; (7.95±0.28), 200 torr He;(e) OH + n-propylbenzene → products: (6.40±0.36), 20 torr He; (5.86±0.16), 200 torr He;(f) OH + isopropylbenzene → products: (7.79±0.40), 200 torr He;(g) OH + hexafluorobenzene → products: (0.221±0.020), 20 torr He; (0.219±0.016) 200 torr He;(h) OH + n-propyl pentafluorobenzene → products: (2.52±0.54), 3 torr He; (3.01±0.76), 20 torr He; (3.06±0.24), 200 torr He;(i) OH + propylene → products: (25.6±1.2), 20 torr He; (26.3±1.2), 200 torr He;(j) OH + 1-butene → products: (29.6±1.9), 3 torr He; (29.4±1.4), 20 torr He;(k) OH + cis-2-butene → products: (43.2±4.1), 3 torr He; (42.6±2.5), 20 torr He;(l) OH + tetramethylethylene → products: (56.9±1.3), 20 torr He.
    Additional Material: 15 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550100802
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  • 2
    Electronic Resource
    Electronic Resource
    Determination of propagation and termination rate constants by using an extension to the rotating-sector method: Application to PLPC and DLPC bilayers (1998)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 30 (1998), S. 753-767 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An extension to the rotating-sector method, which is usually applied to determine propagation and termination rate constants, is presented. The analytical treatment developed accounts for the simultaneous presence of a thermal initiation and of a first-order termination process. The applicability of the rotating-sector method is thus extended to situations where the rate in dark is higher than 5% of the rate in the presence of light, and more accurate estimates of the rate constants are obtained than before for any values of the “dark” rate. A previously published experiment on the application of the rotating-sector method to the autoxidation of styrene was reanalyzed. The estimates obtained for the propagation and the termination rate constants were 11% and 19% higher than the previous estimates, respectively. Finally, the improved rotating-sector method was also applied to the experimental determination of propagation (kp) and termination rate constants (2×kt) for both 1-palmitoyl-2-linoleoyl-sn-glycero-3-phosphocholine (PLPC) and 1,2-dilinoleoyl-sn-glycero-3-phosphocholine (DLPC) liposomes. The following results were obtained at 37°C: for PLPC kp =16.6 M-1s-1, and 2×kt=1.27×105 M-1s-1; for DLPC kp(intermolecular)=(13.3-13.9) M-1s-1, kp(intramolecular)=(4.7-5.4) s-1, and 2×kt=(0.99-1.05)×105 M-1s-1. The separation of the intermolecular and intramolecular propagation rate constants for DLPC was made possible both by a special adaptation of the rotating-sector equations to substrates with two oxidizable moieties, and by the experimental determination of the ratio between partially oxidized DLPC molecules (only one acyl is oxidized) and fully oxidized DLPC molecules (both acyls are oxidized). © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 753-767, 1998
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Tables of rate constants extracted from chemical kinetics and photochemical data for use in stratospheric modeling. Evaluation number 7 (1985)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 17 (1985), S. 1135-1151 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: These tables of evaluated rate constants for use in stratospheric modeling have been taken from the most recent report of the NASA Panel that has been periodically producing such reviews. They are reproduced here to make a broader community aware of their existence. This article should NOT be cited, nor should these rate constants be used without consulting the full report. All citations should be to that original report (JPL Publ. 85-37), which contains extensive documentation and discussion of the rationale of the evaluation. Copies may be obtained by requesting JPL Publ. 85-37 from Documentation Services, 111-116B, Jet Propulsion Laboratory, 4800 Oak Grove Drive, Pasadena, CA 91109.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550171010
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  • 4
    Electronic Resource
    Electronic Resource
    Kinetic study of the reaction of OH with HCl from 240-1055 K (1985)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 17 (1985), S. 1281-1297 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute rate coefficients for the reaction of OH with HCl (k1) have been measured as a function of temperature over the range 240-1055 K. OH was produced by flash photolysis of H2O at λ 〉 165 nm, 266 nm laser photolysis of O3/H2O mixtures, or 266 nm laser photolysis of H2O2. OH was monitored by time-resolved resonance fluorescenceor pulsed laser-induced fluorescence. In many experiments the HCl concentration was measured in situ in the slow flow reactor by UV photometry. Over the temperature range 240-363 K the following Arrhenius expression is an adequate representation of the data: k1 = (2.4 ± 0.2) × 10-12 exp[-(327 ± 28)/T]cm3 molecule-1 s-1. Over the wider temperature range 240-1055 K, the temperature dependence of k1 deviates from the Arrhenius form, but is adequately described by the expression k1 = 4.5 × 10-17 T1.65 exp(112/T) cm3 molecule-1 s-1. The error in a calculated rate coefficient at any temperature is 20%.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550171206
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  • 5
    Electronic Resource
    Electronic Resource
    Kinetics of the reaction of C2H5O2 with NO at 295 K (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 183-194 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of C2H5O2 with NO in helium carrier gas at 295 K with [He] = 1.6 × 1017 cm-3 has been studied using a gas flow reactor sampled by a mass spectrometer. Because no parent molecular ion or suitable fragment ion produced by C2H5O2 could be detected, the reaction was followed by measuring the formation of NO2. In so doing, account had to be taken of the small amount of HO2 known to be present in the reaction mixture, which also leads to NO2 on reaction with NO. The rate coefficient for the total reaction of C2H5O2 with NO was found to be (8.9 ± 3.0) × 10-12 cm3/s, and the path which produces NO2 was found to account for at least 80% of all C2H5O2.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140208
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  • 6
    Electronic Resource
    Electronic Resource
    Evaluated kinetic and photochemical data for atmospheric chemistry: Supplement III (1989)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 115-150 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550210205
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  • 7
    Electronic Resource
    Electronic Resource
    The nature of field effects and their fall-off with distance: The acidity of substituted quinuclidinium and bicyclooctylammonium ions (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 353-360 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Gas-phase acidities are reported for series of substituted quinuclidinium and bicyclo [2.2.2] octylammonium ions. Ab initio calculations are also reported for these equilibria at the STO-3G and 3-21G (for the quinuclidines) bases and can be used to extend the results. pKa values obtained for the bicyclooctylammonium ions are compared with previously reported results for the quinuclidinium ions. The results, as a whole, are considered together with similar values obtained for other saturated systems, to look at the varying transmission of field effects with distance. The falloff observed between the two series in the gas phase is considerably less than expected from simple electrostatics. In contradication with a recent claim, it is also shown that field effects, as measured by the parameter σF, give a good measure of the effect of the substituents in each series compared with a combination of resonance and electronegativity effects.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610040606
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  • 8
    Electronic Resource
    Electronic Resource
    Addition of hydroxylamine to cyclohexanone and bicyclic ketones. Steric, electronic and hydrogen bonding effects on the general mechanism of addition of amines to carbonyl compounds (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 107-112 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Three different types of pH-rate profiles were observed for the addition of amines to carbonyl compounds, depending on the relative predominance, at weakly acidic pH, of either a concerted or a stepwise mechanism. The predominant mechanism depends on the basicity of the amine and the mutual equilibrium affinity for adduct formation between the carbonyl compound and the amine. The reaction of hydroxylamine with cyclohexanone and bicyclic ketones was studied in order to examine the roles of steric and electronic effects in this mechanism. Cyclohexanone and 3-chlorobicyclo [2.2.1] heptan-2-one exhibit the profile expected for a single change in the rate-determining step with increasing pH from uncatalysed attack of the amine on the carbonyl group to hydronium ion-catalysed dehydration of the carbinolamine. In contrast, both bicyclo [2.2.1] heptan-2-one and bicyclo [2.2.2] octan-2-one show an unexpected profile with two negative breaks and five kinetically significant regions. This profile is explained by stabilization of the zwitterionic intermediate T± by intramolecular hydrogen bonding, leading to the formation of the carbinolamine by a stepwise mechanism at weakly acidic pH.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610040207
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  • 9
    Electronic Resource
    Electronic Resource
    Acidities of 4-substituted benzoic, bicyclo[2.2.2]oct-1-yl and bicyclo[2.2.2]oct-2-enyl carboxylic acids (1993)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993), S. 685-689 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experimental gas-phase acidities are reported for a series of 4-substituted bicyclo [2.2.2] oct-1-yl carboxylic acids and for a limited number of the corresponding bicyclo [2.2.2] oct-2-enyl carboxylic acids. Similar acidities are also reported for additional 4-substituted benzoic acids, allowing a comparison of field and resonance effects between the three series. Ab initio molecular orbital calculations for these series of acids confirm the conclusion that the aromatic acids display direct field and resonance effects, whereas the acidities in the aliphatic series acids are largely determined by direct field effects.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610061205
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  • 10
    Electronic Resource
    Electronic Resource
    Interaction of dichlorocarbene with imines (1993)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993), S. 83-84 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The interaction of dichlorocarbene with imines and ketene imines was studied by means of the MNDO method. The results indicate that the lack of ylide cyclization products in the reactions of dichlorocarbene with ketene imines is due to a high reactivity of ketene imine ylides in intermolecular reactions, rather than stereoelectronic factors preventing cyclization. It was shown that the dichlorocarbene reaction with N-benzylideneaniline resulting in gem-dichloraziridine proceeds through transient formation of ylide.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610060203
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