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  • 1
    Electronic Resource
    Electronic Resource
    The radiation crosslinking of poly(vinyl chloride) with trimethylolpropane trimethacrylate. I. Dose dependence and the effects of thermal treatment (1981)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 26 (1981), S. 3669-3688 
    Details
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The radiation crosslinking of poly(vinyl chloride), PVC, with trimethylolpropane trimethacrylate, TMPTMA, has been examined. The polyfunctional TMPTMA undergoes rapid polymerization incorporating the PVC into a three-dimensional network. The kinetics and mechanism of these crosslinking reactions were studied with particular reference to dose dependence and thermal treatment. The gel was rapidly formed with a TMPTMA polymerization rate greater than that of the PVC grafting reaction. Only 30-40% of the available bonds were used in the initial polymerization. The remaining 60-70% of the double bonds predominantly react in the final stages of crosslinking (80-100% gelation). The macroscopic properties (e.g., solubility, glass transition temperatures, mechanical characteristics, etc.) of the PVC-TMPTMA blend are discussed in terms of the molecular crosslinking mechanism. The effect of thermal treatment, during and after irradiation, on the reaction rates and mechanism is examined.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1981.070261114
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  • 2
    Electronic Resource
    Electronic Resource
    Compatibility in a blend of poly(2,3-dichloro-1-propyl acrylate) and poly(glycidyl methacrylate-co-ethyl acrylate) (1981)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 26 (1981), S. 2001-2013 
    Details
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The compatibility of mixtures of poly(2,3-dichloro-1-propyl acrylate) and poly(glycidyl methacrylate-co-ethyl acrylate) has been investigated by measurement of the following properties: density, light transmission, glass transition temperature, vapor absorption, and NMR relaxation times. To varying degrees, all results provided evidence supporting the contention that these mixtures are compatible.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1981.070260623
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  • 3
    Electronic Resource
    Electronic Resource
    A kinetics study of the reaction of Cl with NO2This work was supported by a NASA contract. The results were presented at the 13th Informal Conference on Photochemistry, Clear Water Beach, Florida, January 4-7, 1978. (1988)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 20 (1988), S. 811-814 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The third order rate coefficients for the addition reaction of Cl with NO2, Cl + NO2 + M → ClNO2 (ClONO) + M; k1, were measured to be k1(He) = (7.5 ± 1.1) × 10-31 cm6 molecule-2 s-1 and k1(N2) = (16.6 ± 3.0) × 10-31 cm6 molecule-2 s-1 at 298 K using the flash photolysis-resonance fluorescence method. The pressure range of the study was 15 to 500 torr He and 19 to 200 torr N2. The temperature dependence of the third order rate coefficients were also measured between 240 and 350 K. The 298 K results are compared with those from previous low pressure studies.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550201005
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  • 4
    Electronic Resource
    Electronic Resource
    A flash photolysis-resonance fluorescence kinetics study of ground-state sulfur atoms. II. Rate parameters for reaction of S(3P) with C2H4 (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 383-394 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute rate constants for the reaction of S(3P) with ethylene were measured over an ethylene concentration range of 7, a total pressure of 50 to 400 torr, and a flash intensity range of 10. At 298°K, the bimolecular rate constant was found to be invariant over this range of variables and had a measured value of 4.96 × 10-13 cm3 molec-1 s-1. Over the temperature range of 218° to 442°K, the rate data could be fit to a simple Arrhenius equation of the form \documentclass{article}\pagestyle{empty}\begin{document}$$k_1 = (7.13 \pm 0.74) \times 10^{ - 12} {\rm exp}\left({\frac{{{\rm - 1}{\rm .58} \pm {\rm 0}{\rm .08 kcal/mole}}}{{RT}}} \right)$$\end{document} Units are cm3 molec-1 s-1. The dependence of the measured value of k1 on the concentration of the reaction product ethylene episulfide is discussed.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550040403
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  • 5
    Electronic Resource
    Electronic Resource
    A flash photolysis-resonance fluorescence kinetics study of the reactions of ground-state sulfur atoms. V. Rate parameters for the reaction of S(3P)with cis-2-butene and tetramethylethylene (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 841-857 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate parameters for the reaction of ground-state atomic sulfur, S(3P), with the olefins cis-2-butene and tetramethylethylene have been determined over a temperature range of ∽280°K. A major finding of this study was that the rate constants for both reactions showed negative temperature dependencies. When k is expressed in the form of an Arrhenius equation, this necessarily leads to negative activation energies: k1 = (4.68 ± 0.70) × 10-12 exp (+0.23 ± 0.09 kcal/mole)/RT (219°-500°K) k2 = (4.68 ± 1.70) × 10-12 exp (+1.29 ± 0.23 kcal/mole)/RT (252°-500°K) Units are cm3 molec-1s-1. When a threshold energy of 0.0 kcal/mole is assumed for reaction (2), the temperature dependence of the preexponential term has a value of T-2. Making the usual simplifying assumptions, neither collision theory nor transition state theory leads to a preexponential factor with a strong enough negative temperature dependence. A comparison of these results with those derived from studies of the reactions of atomic oxygen, O(3P), with the same olefins shows that in both studies simple bimolecular processes were being examined. Also discussed are the possible experimental and theoretical ramifications of these new results.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050511
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  • 6
    Electronic Resource
    Electronic Resource
    A flash photolysis resonance fluorescence kinetics study of ground-state sulfur atoms. III. Rate parameters for reaction of S(3P) with ethylene episulfide (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 149-153 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute rate constants for the reaction of S(3P) with ethylene episulfide were measured over a C2H4S concentration range of 5, a total pressure of 20-200 tort, and a flash intensity range of ˜4. Over this range of variables, the bimolecular rate constant was found to be invariant. Because of limitations imposed by the physical properties of the reactant C2H4S, temperature variations were necessarily held to the range 298-355°K. The bimolecular rate constant was found to be invariant over this limited temperature range, having a value of (4.47 ± 0.26) × 10-11 cm3 molec.-1 sec-1. The possible influence of this reaction in studies of the S(3P)-ethylene system are discussed.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050113
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  • 7
    Electronic Resource
    Electronic Resource
    A flash photolysis-resonance fluorescence kinetics study of ground-state sulfur atoms. IV. Rate parameters for reaction of S(3P) with propene and 1-butene (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 375-384 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using the technique of flash photolysis-resonance fluorescence, absolute rate constants have been measured for the reaction of S(3P) with propene and 1-butene. Variations in experimental conditions included the following: temperature (215-500°K); total pressure a factor of 10; olefin concentration, a factor of 6; flash intensity (S atom concentration), a factor of 10. It was found that over these variations in the experimental conditions only the temperature had a measureable effect on the bimolecular rate constant. The derived Arrhenius rate expressions for the reactions (2) and (3) were as follows: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_2 = \left( {6.03 \pm 0.72} \right) \times 10^{ - 12} \exp \left( {\frac{{ - 0.38 \pm 0.09kcal/mol}}{{RT}}} \right) $$\end{document} temperature range 214-500°K \documentclass{article}\pagestyle{empty}\begin{document}$$ k_3 = \left( {7.41 \pm 1.15} \right) \times 10^{ - 12} \exp \left( {\frac{{ - 0.36 \pm 0.09kcal/mol}}{{RT}}} \right) $$\end{document} Units are cm3 molec-1 s-1.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050308
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  • 8
    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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  • 9
    Electronic Resource
    Electronic Resource
    A flash photolysis-resonance fluorescence kinetics study of ground-state sulfur atoms: I. Absolute rate parameters for reaction of S(3P) with O2(3Σ). (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 367-382 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The flash photolysis-resonance fluorescence technique has been used to measure the reaction of ground-state sulfur atoms with molecular oxygen as a function of both temperature and total pressure. The most suitable source of S(3P) for this study was found to be COS in the presence of CO2, as a diluent gas and with the photolysis flash filtered so as to remove all radiation of wavelengths below 1650 Å. Under these conditions, it was found that over the temperature range of 252-423°K the rate data could be fit to a simple Arrhenius-type equation of the form \documentclass{article}\pagestyle{empty}\begin{document}$$k_1 = (2.24 \pm 0.27) \times 10^{ - 12} {\rm exp}\left({\frac{{{\rm - 0}{\rm .00} \pm {\rm 0}{\rm .10 kcal/mole}}}{{RT}}} \right)$$\end{document} Units are cm3 molec-1 s-1. The small A-factor for this reaction, the lack of any pressure dependence, and the direct observation of the production of O(3P) with increasing reaction time suggest that the S(3P) atom attacks the O2(3Σ) molecule end-on forming SOO which rapidly falls apart to form SO (3Σ) and O(3P).
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550040402
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  • 10
    Electronic Resource
    Electronic Resource
    A flash photolysis-resonance fluorescence study of the reaction of atomic hydrogen with molecular oxygen H + O2 + M → HO2 + M (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 401-416 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using the technique of flash photolysis-resonance fluorescence, absolute rate constants have been measured for the reaction H + O2 + M → HO2+M over a temperature range of 220-360°K. Over this temperature range, the data could be fit to an Arrhenius expression of the following form: \documentclass{article}\pagestyle{empty}\begin{document}$$k_{{\rm Ar}} = (6.75{\rm } \pm {\rm }1.1){\rm } \times {\rm }10^{ - 33} \exp {\rm }[685{\rm } \pm {\rm }128{\rm cal/mole]/}RT$$\end{document} The units for kAr are cm6/mole-s. At 300°K the relative efficiencies for the third-body gases Ar:He:H2:N2:CH4 were found to be 1.0:0.93:3.0:2.8:22. Wide variations in the photoflash intensity at several temperatures demonstrated that the reported rate constants were measured in the absence of other complex chemical processes.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550060310
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