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  • 1
    Electronic Resource
    Electronic Resource
    Kinetics of the solvolysis of the trans-dichlorobis(1,2-diaminoethane)-cobalt(III) Ion in water + urea mixtures (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 529-536 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Following the kinetic investigation of the solvolysis of a range of cobalt(III) complexes in mixtures of water + cosolvent wherethe cosolvent enhances the solvent structure and decreases the dielectric constant, kinetic data are now reported for such a solvolysis in water + urea where urea acts as a structure breaker and enhances the dielectric constant. A plot of log (rate constant) against reciprocal of the dielectric constant shows that differential effects of changes in solvent structure occur between the initial and the transition states and, as in theinvestigations using structure-enhancing cosolvents, the principal effect of change in solvent structure on the cobalt(III) cation occurs on the penta-coordinated ion in the transition state.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180503
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  • 2
    Electronic Resource
    Electronic Resource
    Kinetics of the solvolysis of chloropentacyanocobaltate (III) ions in mixtures of ethane-1,2-diol or ethanonitrile with water (1992)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 24 (1992), S. 1043-1053 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the solvolysis of [Co(CN)5Cl]3- ions have been investigated in mixtures formed by the addition of ethane-1,2-diol or ethanonitrile to water where the physical properties indicate little enhancement of structure in water-rich conditions. The effect on the kinetics of this solvolysis of this lack of structural change in the solvent shows in the linearity of the variation of log (rate constant) with the reciprocal of the dielectric constant for the addition of ethane-1,2-diol to water and the absence of any prominent extrema in the enthalpy or entropy of activation using either co-solvent. However, the effect of changes in solvation on the solvolysis with these two co-solvents appears to operate in a similar manner to the effects found when the hydrophobic co-solvent propan-2-ol is added to water. The application of a free energy cycle to the process of the initial state going to the transition state for this dissociative process suggests that, with both co-solvents, [Co(CN)5]2- in the transition state is more stable than [Co(CN)5Cl]3- in the initial state. © John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550241203
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  • 3
    Electronic Resource
    Electronic Resource
    The products of the reaction of the hydroxyl radical with 2-ethoxyethyl acetate (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 475-480 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase reaction products of the OH radical with 2-ethoxyethyl acetate (EEA, CH3C(O)OCH2CH2OCH2CH3) have been investigated. 1,2-Ethanediol acetate formate (EAF, CH3C(O)OCH2CH2OC(O)H) and ethyl formate (EF, HC(O)OCH2CH3) were identified as the two main products. A third product, ethylene glycol diacetate (EGD, CH3C(O)OCH2CH2OC(O)CH3), was also observed. EAF, EF, and EGD formation yields were determined to be 0.37 ± 0.03 and 0.328 ± 0.018 and 0.040 ± 0.005, respectively. Proposed reaction mechanisms are discussed and compared with these data. © 1996 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.1
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  • 4
    Electronic Resource
    Electronic Resource
    The hydroxyl radical reaction rate constant and products of ethyl 3-ethoxypropionate (1997)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 637-644 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The relative rate technique has been used to measure the hydroxyl radical (OH) reaction rate constant of ethyl 3-ethoxypropionate (EEP, CH3CH2(SINGLE BOND)O(SINGLE BOND)CH2CH2C(O)O(SINGLE BOND)CH2CH3). EEP reacts with OH with a bimolecular rate constant of (22.9±7.4)×10-12 cm3 molecule-1s-1 at 297±3 K and 1 atmosphere total pressure. In order to more clearly define EEP's atmospheric reaction mechanism, an investigation into the OH+EEP reaction products was also conducted. The OH+EEP reaction products and yields observed were: ethyl glyoxate (EG, 25±1% HC((DOUBLE BOND)O)C((DOUBLE BOND)O)(SINGLE BOND)O(SINGLE BOND)CH2CH3), ethyl (2-formyl) acetate (EFA, 4.86±0.2%, HC((DOUBLE BOND)O)(SINGLE BOND)CH2(SINGLE BOND)C((DOUBLE BOND)O)(SINGLE BOND)O(SINGLE BOND)CH2CH3), ethyl (3-formyloxy) propionate (EFP, 30±1%, HC((DOUBLE BOND)O)(SINGLE BOND)O(SINGLE BOND)CH2CH2(SINGLE BOND)C((DOUBLE BOND)O)(SINGLE BOND)O(SINGLE BOND)CH2CH3), ethyl formate (EF, 37±1%, HC((DOUBLE BOND)O)O(SINGLE BOND)CH2CH3), and acetaldehyde (4.9±0.2%, HC((DOUBLE BOND)O)CH3). Neither the EEP's OH rate constant nor the OH/EEP reaction products have been previously reported. The products' formation pathways are discussed in light of current understanding of oxygenated hydrocarbon atmospheric chemistry. © 1997 John Wiley & Sons, Inc.
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  • 5
    Electronic Resource
    Electronic Resource
    The kinetics of the Diels-Alder addition of cyclopentadiene to acetylene and the decomposition of norbornadiene (1975)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 7 (1975), S. 319-329 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title reactions have been investigated in a static system. The addition of acetylene to cyclopentadiene (CPD) results in formation of norbornadiene (BCH), cycloheptatriene (CHT), and toluene (T), while BCH decomposition produces CPD, C2H2, CHT, and T. Kinetic studies, comprising both product-time evolution and initial pressure variation, support a mechanism These reactions are almost certainly homogeneous and molecular in nature. Least mean square analysis of the data yield for temperatures of 525-656°K, log k-1 (1./mole·s)=7.51±0.05- (24.19±0.15 kcal/mole)/RT ln 10, and for temperatures of 584-630°K, \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_1 (s^{ - 1}) = 14.78 \pm 0.10 - (51.37 \pm 0.29\,kcal/mole)/RT\ln 10 $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_1 (s^{ - 1}) = 14.90 \pm 0.11 - (51.36 \pm 0.30\,kcal/mole)/RT\ln 10 $$\end{document}
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550070302
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  • 6
    Electronic Resource
    Electronic Resource
    Kinetics of the solvolysis of [Co(3Rpy)4Cl2]+ ions (R = Me or Et) in water and in water + methanol mixtures (1990)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 891-903 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rates of solvolysis of ions [Co(3Rpy)4Cl2]+ with R = Me and Et have been measured over a range of temperatures for a series of water-rich water + methanol mixtures to investigate the effect of changes in solvent structure on the solvolysis of complexes presenting a largely hydrophobic surface to the solvent. The variation of the enthalpies and entropies of activation with solvent composition has been determined. A free energy cycle relating the free energy of activation in water to that in water + methanol is applied using free energies of transfer of individual ionic species from water into water + methanol. Data for the free energy of transfer of chloride ions ΔGt∘(Cl-) from both the spectrophotometric solvent sorting method and the TATB method for separating ΔGt∘(salt) into ΔGt∘(i) for individual ions are used: irrespective of the source of ΔGt∘(Cl-), in general, -ΔGt∘(Co(Rpy)4Cl2+) 〉 -ΔGt∘(Co(Rpy)4Cl2+), where Rpy = py, 4Mepy, 4Etpy, 3Etpy, and 3Mepy, showing that changes in solvent structure in water-rich water + methanol mixtures generally stabilize the cation in the transition state more than the cation in the initial state for this type of complex ion. A similar result is found when the free energy cycle is applied to the solvolysis of the dichloro (2,2′,2″-triaminotriethylamine)cobalt(III) ion. The introduction of a Me or Et group on the pyridine ring in [Co(Rpy)4Cl2]+ has little influence on the difference {ΔGt∘(Co(Rpy)4Cl2+)-ΔGt∘(Co(Rpy)4Cl2+)} in water + methanol with the mol fraction of methanol 〈 0.20.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550220902
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  • 7
    Electronic Resource
    Electronic Resource
    Kinetics of the solvolysis of [Co(3Rpy)4Cl2]+ (R = Me or Et) in water + propan-2-ol mixtures (1991)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 23 (1991), S. 161-172 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rates of solvolysis of complex ions [Co(3Rpy)4Cl2]+ with R = Me and Et have been determined in mixtures of water with the hydrophobic co-solvent propan-;2-ol for a range of temperatures. The variations of the enthalpies and entropies of activation with the solvent composition have been correlated with the physical properties of the solvent and it has been shown that the linear plot found for ΔH* against ΔS* in water + propan-2-ol is coincident with that found for water + methanol mixtures. A free energy cycle has been applied to the dissociative-type process of initial state (Cn+) going to the transition state (M(n+1)+…‥ Cl-) using values for the free energy of transfer of the chloride ion from water into the mixture, ΔGt∘(Cl-), derived from the solvent sorting technique or from the TATB/TPTB method. Irrespective of the source of ΔGt∘(Cl-), it is found that ΔGt∘(Co(3Rpy)4Cl2+*) ca. ΔGt∘(Co(3Rpy)4Cl2+) (where * indicates a species in the transition state) for mol fractions of propan-2-ol x2 ≳ 0.04-0.05 with ΔGt∘(Co(3Rpy)4Cl2+*) becoming increasingly more negative than ΔGt∘(Co(3Rpy)4Cl2+) as x2 increases above 0.05. These variations are compared with those for the solvolysis of the same ions in water + methanol mixtures and of a range of other ions in water + propan-2-ol mixtures. It is concluded that, using values for ΔGt∘(Cl-) from either source, the stabilizing influence of changes in solvent structure is greater on the cation in the transition state than on the cation in the initial state for the solvolyses of complexes [Co(Rpy)4Cl2+] and [Coen2LCl]n+.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550230207
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  • 8
    Electronic Resource
    Electronic Resource
    Kinetics of the solvolysis of [Co(3Rpy)4Cl2]+ ions (R = Me or Et) in Water + t-butyl alcohol mixtures (1992)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 24 (1992), S. 563-577 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rates of solvolysis of complex ions [Co(3Rpy)4Cl2]+ with R = Me and Et have been determined in mixtures of water with t-butyl alcohol over a range of temperatures. Extrema found in the enthalpy ΔH* and entropy ΔS* of activation are correlated with the physical properties of the solvent mixtures which are influenced by changes in the solvent structure and these extrema are compared with those found for the solvolysis of related complexes in water + alcohol mixtures. Isokinetic plots over wide ranges of ΔH* and ΔS* are compared for the solvolysis of CoIII complexed to a variety of ligands. The application of a free energy cycle shows that the emergent cobalt (III) cation in the transition state becomes increasingly stabilized in water-rich mixtures relative to the cobalt (III) cation in the initial state as the mol fraction of t-butyl alcohol increases.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550240606
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  • 9
    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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  • 10
    Electronic Resource
    Electronic Resource
    Kinetics of solvolysis of trans-dichlorotetra (t-butylpyridine)-cobalt(III) ions in mixtures of water with ethane-1,2-diol and with 2-methoxyethanol. A contrast with the effect of hydrophobic co-solvents (1995)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 27 (1995), S. 17-25 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the solvolysis of the hydrophobic ion, Co(4-t-Bupy)4Cl2+, have been followed in mixtures of water with co-solvents having a hydrophilic tendency, ethane-1,2-diol and 2-methoxyethanol. The variation of In(rate constant) with the reciprocal of the dielectric constant is nonlinear for both co-solvents. The enthalpy and the entropy of activation are rather insensitive to changes in the solvent composition in both mixtures, but low maxima may exist at mol fractions of co-solvent Ca. 0.10-0.20. The application of a Gibbs energy cycle to the process of the initial state going to the transition state suggest that, in water-rich conditions, the increase in the stability of the emergent solvated CoIII ion in the transition state relative to the increase in the stability of Co(4-t-Bupy)4Cl2+ in the initial state as the co-solvent content rises is greater for 2-methoxyethanol than for ethane-1,2-diol. © 1995 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550270104
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