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  • Physical Chemistry  (31)
  • Wiley-Blackwell  (31)
  • American Meteorological Society (AMS)
  • PANGAEA
  • 1990-1994  (17)
  • 1980-1984  (14)
  • 1993  (17)
  • 1984  (14)
Collection
Keywords
Publisher
  • Wiley-Blackwell  (31)
  • American Meteorological Society (AMS)
  • PANGAEA
Years
  • 1990-1994  (17)
  • 1980-1984  (14)
Year
  • 1
    Electronic Resource
    Electronic Resource
    Stereochemistry of aminolysis of N-pentafluorophenylcarbonimidoyl dichloride. Crystal and molecular structures of N2-pentafluorophenyl-N1,N1-dibenzylchloroformamidine (1993)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993), S. 319-325 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It has been established that the product of the reaction of N-pentafluorophenylcarbonimidoyl dichloride (1) with dibenzylamine, viz. N2-pentafluorophenyl-N1,N1-dibenzylchloroformamidine (4a) is a Z-isomer, whereas according to the concept of stereoelectronic control one might have expected a product with E-configuration. The heat of formation and the geometry of Z- and E isomer of N2-pentafluorophenyl-N1,N1-diethylchloroformamidine (4b) (the latter is a product of the reaction of 1 with diethylamine) were calculated with the semi-empirical MNDO method. The calculated geometry of (Z)-4b was found to be in a good agreement with the experimentally determined structure of 4a. The formation of (Z)-4b is more preferable energetically than that of (E)-4b; the calculated difference in the heats of formation is 2·8 kcal mol-1. Thermodynamic control of the reaction stereochemistry is proposed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610060602
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  • 2
    Electronic Resource
    Electronic Resource
    Basic hydrolysis of glyceryl nitrate esters. III. Trinitroglycerin (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1027-1051 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetics of the basic hydrolysis of glyceryl trinitrate (TNG) were investigated in CO2-free aqueous calcium hydroxide solutions. The hydrolysis reactions were carried out in a temperature controlled reactor vessel with provision for continuous N2 sparging of the reaction mixture. TNG hydrolyzed via second-order reaction at 25°C, 18°C, and 10°C. The activation energy of the hydrolysis reaction of TNG was calculated from the kinetic data and found to be equal to 27.53 kcal/mol. The major products of the hydrolysis of TNG in solution of calcium hydroxide were calcium nitrate and calcium nitrite, accounting for approximately 50% of the degradation products. The minor identified products such as calcium oxalate and nitrate esters amounted to approximatey 6% of the products. The remaining 30% of the isolated products was a mixture of calcium formate, a nitrate ester, and unidentified volatiles, polymerlike substances, and other organic residue.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160808
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  • 3
    Electronic Resource
    Electronic Resource
    Thermal decomposition of methyl nitrite in shock waves studied by laser probing (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1139-1150 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The unimolecular decomposition of methyl nitrite in the temperature range 680-955 K and pressure range 0.64 to 2.0 atm has been studied in shock-tube experiments employing real-time absorption of CW CO laser radiation by the NO product. Computer kinetic modeling using a set of 23 reactions shows that NO product is relatively unreactive. Its initial rate of production can be used to yield directly the unimolecular rate constant, which in the fall-off region, can be represented by the second-order rate coefficient in the Arrhenius form: \documentclass{article}\pagestyle{empty}\begin{document}$$k_1 = 10^{17.90 \pm 0.21} \exp (- 17200 \pm 400/T){\rm cm}^{\rm 3} {\rm mol}^{ - 1} {\rm s}^{ - 1}$$\end{document} A RRKM model calculation, assuming a loose CH3ONO≠ complex with two degrees of free internal rotation, gives good agreement with the experimental rate constants.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160909
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  • 4
    Electronic Resource
    Electronic Resource
    Basic hydrolysis of glyceryl nitrate esters. II. 1,2-glyceryl and 1, 3-glyceryl dinitrate esters (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1009-1026 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetics of the basic hydrolysis of 1,2-glyceryl dinitrate (1,2-DNG) and 1,3-glyceryl dinitrate (1,3-DNG) esters were investigated in CO2-free aqueous calcium hydroxide solutions. The hydrolysis reactions were carried out in a temperature controlled reactor vessel with provision for continuous N2 sparging of the reaction mixture. Both glyceryl dinitrate esters hydrolyzed via second-order reaction at 25°C. 1,2-DNG in basic solutions isomerized to 1,3-DNG which subsequently hydrolyzed to yield products. The main hydrolysis product of 1,3-DNG was identified as glycidyl nitrate. Other products formed during the basic hydrolysis of DNGs were nitrites and nitrates.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160807
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  • 5
    Electronic Resource
    Electronic Resource
    Yields of singlet nitrenes from halogen atom - azide molecule reactions (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 977-993 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chemiluminescence from the a1Δ and b1Σ+ excited electronic states of nitrogen halide diatomics is observed when HN3 is allowed to react with mixtures of halogen atoms in a discharge-flow apparatus. Excited NF (a1Δ) is produced by the F + HN3 reaction, and NCl (a1Δ, b1Σ+) and NBr (a1Δ, b1Σ+) are produced by the F, Cl, + HN3 and F, Br + HN3 reactions, respectively. In the low-density limit, the yield of NF(a1Δ) was found to be near unity. The yields of the b1Σ+ states of NCl and NBr were determined to have a lower limit of ca. 10%. A number of results from these experiments, including direct observation of N3 radicals in the flow, support a hypothetical mechanism in which N3 acts as an intermediate. A second possible mechanism proceeding via an HNF intermediate cannot be ruled out.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160805
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  • 6
    Electronic Resource
    Electronic Resource
    A study of ethane decomposition in a shock tube using laser absorption of CH3 (1993)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 969-982 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate coefficient for the unimolecular reaction, C2H6 → CH3 + CH3, was measured in reflected shock wave experiments using narrow-linewidth laser absorption of methyl radicals at 216.6 nm. The experiments were conducted in the falloff regime at the conditions 1350 to 2110 K, 0.58 to 4.4 atm, in 50 to 500 ppm C2H6/Ar and 190 ppm C2H6/N2 mixtures. At temperatures below 1500 K, the measured rate coefficients are in good agreement with the expression of Wagner and Wardlaw (1989). Above 1500 K, the measurements fall increasingly below their predictions. © 1993 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550251109
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  • 7
    Electronic Resource
    Electronic Resource
    Intramolecular photoinduced electron transfer (PET) bond cleavage in some sulfonium salt derivatives. Effect of distance and thermodynamics on PET rate (1993)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993), S. 333-340 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rate of intramolecular photoinduced electron transfer (PET) between a naphthacene electron donor (D) and a sulfonium electron acceptor (A) was found to be dependent on the thermodynamics for PET and distance between D and A. The slopes of In kET vs through-bond and through-space distance plots was found to be -0·60 and -0·91 Å-1, respectively. The product distribution obtained from the photolysis of regioisomeric naphthacenyl sulfonium salt derivatives was found to be independent of distance. Photolysis of three regioisomeric naphthacenyl phenylmethyl-p-cyanobenzylsulfonium salts produced unsubstituted thiomethylphenylnaphthacene and mono-, di- and tri-p-cyanobenzyl-substituted thiomethylphenylnaphthacene. The appearance of the out-of-cage di- and trisubstituted photoproducts suggests that secondary photochemistry and intermolecular electron transfer bond-cleavage reactions are occurring when the concentration of the sulfonium salt in acetonitrile is 10-2 and 10-3 M and the degree of conversion is high. The primary photoproduct is the mono-substituted naphthacene derivative.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610060604
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  • 8
    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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  • 9
    Electronic Resource
    Electronic Resource
    Catalytic activity of polypodands and glymes under solid-liquid phase-transfer catalysis conditions. Amolecular mechanics study (1993)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993), S. 113-121 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A molecular mechanics study of cyclophosphazenic polypodands and of glymes, of their complexes with ion pairs (IPs) M+ I- (M+ = Li+, Na+, K+, Rb+) and IP aggregates (M+ I-)n was carried out to investigate the catalytic activity of these ligands in solid-liquid phase-transfer reaction. This activity is explained by their ability to bind IP aggregates effectively and to activate the anion by increasing the interionic distance in the single IP.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610060208
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  • 10
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of electron transfer reactions of aquo-thallium(III) and coordinated thallium(III). Reduction of thallium(III) and chlorothallium(III) complexes by L-ascorbic acid in aqueous acid medium (1993)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 6 (1993), S. 179-186 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The stoichiometry of the reaction of TIIII with ascorbic acid (H2A) in the presence and absence of chloride ion conforms to TIIII + H2A 〉 TII + 2H+ + A. where A is dehydroascorbic acid. The reaction exhibits complex kinetics and the reactivity of various chlorothallium (III) species decreases in the order of [TIOH]2+ 〉 TI3+ 〉 [TICI]2+ 〉 [TICI2]+ 〉 TICI3 〉 [TICI4]-. The mass balance relationship was employed to calculate the equilibrium concentration of the chloride ion for evaluation of the rate constants.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610060309
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